CN100439432C

CN100439432C - Polymer foam containing hydrogenated copolymer

Info

Publication number: CN100439432C
Application number: CNB2004800096598A
Authority: CN
Inventors: 笹川雅弘; 白木利典; 柳徖善; 尹晸植; 崔景满; 严基龙
Original assignee: Asahi Kasei Chemicals Corp
Current assignee: Asahi Kasei Corp
Priority date: 2003-04-10
Filing date: 2004-04-09
Publication date: 2008-12-03
Anticipated expiration: 2024-04-09
Also published as: CN1771284A

Abstract

A polymer foam having a specific gravity of from 0.05 to 0.5 and comprising a plurality of cells defined by cell walls which constitute a polymer matrix, wherein the polymer matrix is comprised of 5 to 100 parts by weight of (A) a hydrogenated copolymer obtained by hydrogenating an unhydrogenated copolymer which contains at least one copolymer block S comprised of vinyl aromatic monomer units and conjugated diene monomer units, and 95 to 0 part by weight of (B) at least one polymer selected from the group consisting of an olefin polymer and a rubbery polymer, and wherein at least one peak of loss tangent (tandelta) is observed at -40 DEG C. to lower than -10 DEG C. in a dynamic viscoelastic spectrum obtained with respect to the hydrogenated copolymer (A).

Description

The foam of polymers that contains hydrogenated copolymer

Background of invention

Invention field

The present invention relates to a kind of foam of polymers that contains hydrogenated copolymer.More specifically, the present invention relates to a kind of proportion and be 0.05-0.5 and comprise the foam of polymers of many bubbles that define by the walls that constitutes polymeric matrix, wherein said polymeric matrix is made up of 5-100 weight part (A) and 95-0 weight part (B): (A) hydrogenated copolymer for making by the not hydrogenated copolymer hydrogenation that will comprise vinyl aromatic monomer units and conjugated diene monomeric unit, described not hydrogenated copolymer contains at least one copolymer block S that is made up of vinyl aromatic monomer units and conjugated diene monomeric unit, (B) be at least a polymkeric substance that is selected from olefin polymer and rubbery polymer, the vinyl aromatic monomer units content of wherein said hydrogenated copolymer (A) is greater than 40 weight % to 60 weight %, and observes at least one loss tangent (tan δ) peak in-40 ℃ in-10 ℃ of scopes to being lower than in the dynamic viscoelasticity spectrum figure of the hydrogenated copolymer that obtains (A).Foam of polymers of the present invention (for example has excellent flexibility, cold property, snappiness under the low temperature), impact absorbency (low bounce impact elasticity), incompressible tension set etc., so this foam of polymers can be advantageously used for absorbing body (especially footgear material) etc.

Prior art

For the segmented copolymer that comprises vinyl aromatic monomer units and conjugated diene monomeric unit, when its vinyl aromatic monomer units content is low, even do not cure, this segmented copolymer or synthetic rubber natural with traditional sulfuration compared not only has elasticity excellent under the room temperature, and compares the workability that also has excellence high temperature under with traditional thermoplastic resin.Therefore, the segmented copolymer that this vinyl aromatic monomer units content is lower extensively is used in the multiple field, for example footgear field, plastic modifier, asphalt modifier and tackiness agent.

On the other hand, when the segmented copolymer that comprises vinyl aromatic monomer units and conjugated diene monomeric unit had higher vinyl aromatic monomer units content, this segmented copolymer was the thermoplastic resin with excellent transparency and shock-resistance.Therefore, the higher segmented copolymer of this vinyl aromatic monomer units content can be advantageously utilised in the multiple field, and for example food is with in packaging vessel, daily necessities wrapping material, household electrical appliance wrapping material, industrial part wrapping material and the toy.

In addition, the hydrogenation goods of above-mentioned segmented copolymer have excellent weathering resistance and excellent thermotolerance, so these hydrogenation goods not only can be advantageously utilised in above-mentioned each field, also can be used in the fields such as trolley part, medical facilities.

But above-mentioned segmented copolymer is disadvantageous in the following areas.When this segmented copolymer has lower vinyl aromatic monomer units content, though described segmented copolymer has excellent flexibility, but this segmented copolymer has bad impact absorbency, the therefore feasible use range that is difficult to enlarge this segmented copolymer.On the other hand, when this segmented copolymer had higher vinyl aromatic monomer units content, this segmented copolymer had bad snappiness under room temperature and low temperature, therefore was not suitable for as flexible materials.

At the multipolymer that comprises vinyl aromatic monomer units and conjugated diene monomeric unit, attempted to work out and improved described multipolymer so that it shows the technology of excellent flexibility.For example, publication number is to put down into the not careful Japanese patent application of 2-158643 (corresponding to U.S. Patent No. 5,109,069) a kind of composition that comprises hydrogenated copolymer and acrylic resin is disclosed, wherein hydrogenated copolymer makes by inciting somebody to action not hydrogenated copolymer hydrogenation, and this not hydrogenated copolymer comprise vinyl aromatic monomer units and conjugated diene monomeric unit, and its vinyl aromatic monomer units content is 3-50 weight %, molecular weight distribution is 10 or littler (wherein molecular weight distribution is defined as the ratio (Mw/Mn) of weight-average molecular weight (Mw) and number-average molecular weight (Mn), and the ethylenic linkage content that records with regard to conjugated diene monomeric unit in the described not hydrogenated copolymer is 10-90%.Yet although the snappiness of said composition and cold property are improved to a certain extent, the shock absorption character of said composition still can not be satisfactory.

Publication number is a kind of composition that comprises hydrogenated copolymer and acrylic resin of not examined Japanese Patent Application Publication of putting down into 6-287365, wherein hydrogenated copolymer makes by inciting somebody to action not hydrogenated copolymer hydrogenation, this not hydrogenated copolymer comprise vinyl aromatic monomer units and conjugated diene monomeric unit, and its vinyl aromatic monomer units content is 5-60 weight %, record with regard to conjugated diene monomeric unit in the described not hydrogenated copolymer ethylenic linkage content be 60% or more.But the snappiness of said composition and shock absorption character can not be satisfactory.

In recent years, attempt to improve above-mentioned vinyl aromatic monomer units and conjugated diene monomeric unit and the higher segmented copolymer of vinyl aromatic monomer units content of comprising, so that it shows excellent flexibility always.For example, publication number is to put down into a kind of homopolymer block that comprises vinyl aromatic monomer units of not examined Japanese Patent Application Publication of 2-300250 and the segmented copolymer of the polymer blocks be made up of conjugated diene monomeric unit, wherein the conjugated diolefin polymer block only comprises the mixture of isoprene monomer unit or isoprene monomer unit and butadiene monomer unit, and they are 3 years old, 4-ethylenic linkage and 1, the total content of 2-ethylenic linkage is 40% or more, and in the dynamic viscoelasticity spectrum figure that this segmented copolymer is obtained, under 0 ℃ or higher temperature, observe at least one loss tangent (tan δ) peak.Yet although this segmented copolymer has excellent impact absorbency, the snappiness of this segmented copolymer and cold property still can not be satisfactory.

Disclose a kind of moulding material of mainly being made up of hydrogenated block copolymer among the WO98/12240, wherein this hydrogenated block copolymer is to obtain by the segmented copolymer hydrogenation that will comprise following compositions: mainly by styrene monomer unit polymer blocks of forming and the copolymer block of mainly being made up of butadiene monomer unit and styrene monomer unit.But the hydrogenated block copolymer of describing in this patent documentation has unsafty snappiness and cold property.

Therefore, respectively for the multipolymer that comprises vinyl aromatic monomer units and conjugated diene monomeric unit, by this multipolymer hydrogenation is obtained hydrogenated copolymer, comprise described hydrogenated copolymer and be different from the composition of the polymkeric substance of described hydrogenated copolymer, by the shaped object that above-mentioned multipolymer, hydrogenated copolymer or composition make, make it all show excellence aspect snappiness, cold property, the impact absorbency thereby can not improve described multipolymer, composition or shaped object.

Summary of the invention

In this case, the present inventor has carried out extensive research, contains the shaped object of hydrogenated copolymer with exploitation, and wherein this shaped object is all showing excellence aspect snappiness, cold property (for example snappiness under the low temperature) and the impact absorbency.The result unexpectedly finds, foam of polymers with following properties can be realized this shaped object: the proportion of this foam of polymers is 0.05-0.5 and the foam of polymers that comprises many bubbles that defined by the walls that constitutes polymeric matrix, wherein said polymeric matrix is made up of 5-100 weight part (A) and 95-0 weight part (B): (A) hydrogenated copolymer for making by the not hydrogenated copolymer hydrogenation that will comprise vinyl aromatic monomer units and conjugated diene monomeric unit, described not hydrogenated copolymer contains at least one copolymer block S that is made up of vinyl aromatic monomer units and conjugated diene monomeric unit, (B) be at least a polymkeric substance that is selected from olefin polymer and rubbery polymer, the vinyl aromatic monomer units content of wherein said hydrogenated copolymer (A) is greater than 40 weight % to 60 weight %, and observes at least one loss tangent (tan δ) peak in-40 ℃ in-10 ℃ of scopes to being lower than in the dynamic viscoelasticity spectrum figure of the hydrogenated copolymer that obtains (A).The present inventor finds that also this foam of polymers also has excellent incompressible tension set etc.Finished the present invention based on this discovery.

Therefore, an object of the present invention is to provide a kind of foam of polymers, it all shows excellence at aspects such as snappiness, cold property (for example, the snappiness under the low temperature), shock absorption character (low bounce impact elasticity), incompressible tension sets.

May be obvious that above-mentioned purpose of the present invention and other purpose, characteristic and superiority from following detailed description and appending claims.

Detailed Description Of The Invention

According to the present invention, it provides a kind of foam of polymers that comprises many bubbles that defined by the walls that constitutes polymeric matrix,

Described polymeric matrix is made up of following substances:

With respect to the component of 100 weight parts (A) altogether and (B), the hydrogenated copolymer that (A) of 5～100 weight parts makes by the not hydrogenated copolymer hydrogenation that will comprise vinyl aromatic monomer units and conjugated diene monomeric unit, described not hydrogenated copolymer contain at least one copolymer block S that forms by vinyl aromatic monomer units and conjugated diene monomeric unit and

With respect to the component of 100 weight parts (A) altogether and (B), at least a polymkeric substance that is selected from the olefin polymer that is different from described hydrogenated copolymer (A) and is different from the rubbery polymer of described hydrogenated copolymer (A) of (B) of 95～0 weight parts,

Described hydrogenated copolymer (A) has following feature (1) and (2):

(1) in the weight of described hydrogenated copolymer (A), the vinyl aromatic monomer units content of described hydrogenated copolymer (A) be greater than 40 weight % to 60 weight % and

(2) in the dynamic viscoelasticity spectrum figure of the described hydrogenated copolymer (A) that obtains, observe at least one loss tangent (tan δ) peak in-10 ℃ of scopes to being lower than in-40 ℃,

The proportion of described foam of polymers is 0.05-0.5.

In order to be more readily understood the present invention, essential characteristic of the present invention and multiple preferred embodiment have been enumerated below.

1. foam of polymers that comprises many bubbles that define by the walls that constitutes polymeric matrix,

Described polymeric matrix is made up of following substances:

Described hydrogenated copolymer (A) has following feature (1) and (2):

The proportion of described foam of polymers is 0.05-0.5.

2. according to above-mentioned the 1st foam of polymers, wherein with respect to the component of 100 weight parts (A) altogether and (B), the amount of hydrogenated copolymer (A) and polymkeric substance (B) is respectively 5-95 weight part and 95-5 weight part.

3. according to above-mentioned the 1st or the 2nd 's foam of polymers, wherein in differential scanning calorimetric (DSC) figure of the hydrogenated copolymer that obtains (A), do not observe the peak crystallization that is produced by at least one hydrogenated copolymer block that described at least one copolymer block S hydrogenation is obtained basically in-50 to 100 ℃ of scopes.

4. according to each foam of polymers in the above-mentioned 1-3 item, wherein in described not hydrogenated copolymer, at least one among described at least one copolymer block S has the structure that wherein said vinyl aromatic monomer units distributes with the gradient form.

5. according to each foam of polymers in the above-mentioned 1-4 item, wherein said not hydrogenated copolymer also contains the homopolymer block H of vinyl aromatic monomer units, in the weight of described not hydrogenated copolymer, the amount of the described homopolymer block H in the described not hydrogenated copolymer is 1～40 weight %.

6. according to each foam of polymers in the above-mentioned 1-3 item, wherein said not hydrogenated copolymer is at least a polymkeric substance that is selected from respectively by the multipolymer of following formula representative:

(1)S，

(2)S-H，

(3)S-H-S，

(4)(S-H) _m-X，

(5)(S-H) _n-X-(H) _p，

(6)H-S-H，

(7)S-E，

(8)H-S-E，

(9)E-S-H-S，

(10) (E-S-H) _m-X and

(11)(E-S-E) _m-X，

Wherein each S independently represents the copolymer block of being made up of vinyl aromatic monomer units and conjugated diene monomeric unit, each H independently represents the homopolymer block of vinyl aromatic monomer units, each E independently represents the homopolymer block of conjugated diene monomeric unit, each X independently represents the coupling agent residue, each m independently represents 2 or bigger integer, and each n and p independently represent 1 or bigger integer.

7. according to each foam of polymers in the above-mentioned 1-6 item, be connected with properties-correcting agent on the wherein said hydrogenated copolymer (A) with functional group.

8. according to above-mentioned the 7th foam of polymers, wherein said properties-correcting agent is one-level properties-correcting agent, and it has at least one functional group that is selected from hydroxyl, epoxy group(ing), amino, silanol group and alkoxysilane group.

9. according to above-mentioned the 7th foam of polymers, wherein said properties-correcting agent comprises one-level properties-correcting agent and the secondary properties-correcting agent that is connected thereon,

Wherein said one-level properties-correcting agent have at least one functional group that is selected from hydroxyl, epoxy group(ing), amino, silanol group and alkoxysilane group and

Wherein said secondary properties-correcting agent has the functional group that at least one is selected from hydroxyl, carboxyl, anhydride group, isocyanate groups, epoxy group(ing) and alkoxysilane group.

10. according to each foam of polymers in the above-mentioned 1-9 item, wherein the described olefin polymer as component (B) is at least a following ethene polymers that is selected from: polyethylene, ethylene/propene copolymer, ethylene/propene/butylene copolymer, ethylene/butylene copolymers, ethylene/hexene multipolymer, ethylene/octene, ethylene/vinyl acetate copolymer, ethene/acrylic ester multipolymer and ethylene/methacrylic acid ester copolymer.

11. according to each foam of polymers in the above-mentioned 1-9 item, wherein the described rubbery polymer as component (B) is at least a following material that is selected from: 1, the 2-polyhutadiene; The hydrogenated products of conjugated diene homopolymers; Multipolymer and the hydrogenated products thereof formed by vinyl aromatic monomer units and conjugated diene monomeric unit; By the homopolymer block of vinyl aromatic monomer units with at least aly be selected from segmented copolymer and the hydrogenated products thereof that following polymer blocks is formed: the homopolymer block of conjugated diene monomeric unit and the copolymer block of forming by vinyl aromatic monomer units and conjugated diene monomeric unit; Acrylonitrile/butadiene rubber and hydrogenated products thereof; Ethylene/propylene/diene rubber (EPDM); Isoprene-isobutylene rubber and natural rubber.

12. according to above-mentioned the 11st foam of polymers, wherein the described rubbery polymer as component (B) is at least a following material that is selected from: the hydrogenated products of the multipolymer of being made up of vinyl aromatic monomer units and conjugated diene monomeric unit, in the weight of described hydrogenated products, the vinyl aromatic monomer units content of described hydrogenated products is greater than 60 weight % to 90 weight %; With by the homopolymer block of vinyl aromatic monomer units with at least aly be selected from segmented copolymer and the hydrogenated products thereof that following polymer blocks is formed: the homopolymer block of conjugated diene monomeric unit and the copolymer block of forming by vinyl aromatic monomer units and conjugated diene monomeric unit.

13. according to each foam of polymers in the above-mentioned 1-12 item, it demonstrates 40% or littler bounce impact elasticity.

14. according to each foam of polymers in the above-mentioned 1-13 item, its proportion is 0.1-0.3.

15. according to each foam of polymers in the above-mentioned 1-14 item, it is an absorbing body.

Hereinafter will describe the present invention.

In the present invention, the monomeric unit of described polymkeric substance is named according to following nomenclature: the initial monomers title that wherein derives described monomeric unit is used to enclose term " monomeric unit ".For example, term " vinyl aromatic monomer units " is meant the monomeric unit that forms in the polymkeric substance by vi-ny l aromatic monomers polymerization gained.This vinyl aromatic monomer units has following molecular structure: wherein derive by the vinyl that replaces and two carbon atoms of the substituted ethylene group that comes respectively with adjacent vinyl aromatic monomer units Cheng Jian.Similarly, term " conjugated diene monomeric unit " is meant the monomeric unit that forms in the polymkeric substance by conjugate diene monomer polymerization gained.This conjugated diene monomeric unit has following molecular structure: wherein corresponding to two carbon atoms of the alkene of conjugate diene monomer respectively with adjacent conjugated diene monomeric unit Cheng Jian.

Foam of polymers of the present invention comprises many bubbles that defined by the walls that constitutes polymeric matrix.Have no particular limits for bubble structure.For example, all bubbles all can be perforates.As selection, all bubbles can be closed pore.In addition, described foam of polymers can also contain perforate and closed pore in combination.That is to say, foam of polymers of the present invention can have perforate honeycomb structure (opencell cellular structure), perhaps can have closed pore honeycomb structure (closed cell cellularstructure), perhaps can not only have the perforate honeycomb structure but also have the closed pore honeycomb structure.

Polymeric matrix is made up of following substances: with respect to the component of 100 weight parts (A) altogether and (B), and (A) hydrogenated copolymer of 5-100 weight part; With with respect to the component of 100 weight parts (A) altogether and (B), at least a polymkeric substance that is selected from the olefin polymer that is different from hydrogenated copolymer (A) and is different from the rubbery polymer of hydrogenated copolymer (A) of (B) of 95-0 weight part.

Hydrogenated copolymer (A) is to make by the not hydrogenated copolymer hydrogenation that will comprise vinyl aromatic monomer units and conjugated diene monomeric unit.Described not hydrogenated copolymer contains at least one copolymer block S that is made up of vinyl aromatic monomer units and conjugated diene monomeric unit.(hereinafter, described not hydrogenated copolymer so-called " basis is hydrogenated copolymer not ".)

Hydrogenated copolymer (A) has following properties (1) and (2):

(2) in the dynamic viscoelasticity spectrum figure of the described hydrogenated copolymer (A) that obtains, observe at least one loss tangent (tan δ) peak in-10 ℃ of scopes to being lower than in-40 ℃.

Provide following explanation at above-mentioned characteristic (1).In the weight of described hydrogenated copolymer (A), the content of vinyl aromatic monomer units is greater than 40 weight % to 60 weight % in hydrogenated copolymer (A).From snappiness and impact absorbency, the content of vinyl aromatic monomer units is preferably 43-57 weight %, more preferably 45-55 weight % in hydrogenated copolymer (A).

The content of vinyl aromatic monomer units in described hydrogenated copolymer (A) approximate vinyl aromatic monomer units on described basis the content in the hydrogenated copolymer not.Therefore, use vinyl aromatic monomer units on described basis not the content in the hydrogenated copolymer as the content of vinyl aromatic monomer units in described hydrogenated copolymer (A).Vinyl aromatic monomer units on described basis not the content in the hydrogenated copolymer measure by ultraviolet spectrophotometer.

Provide following explanation at above-mentioned characteristic (2).In the dynamic viscoelasticity spectrum figure of the hydrogenated copolymer that obtains (A), at-40 ℃ to being lower than-10 ℃, preferred-35 ℃ to-12 ℃, more preferably-30 ℃ extremely observing at least one loss tangent (tan δ) peak in-14 ℃ of scopes.In dynamic viscoelasticity spectrum figure, be considered to belong to the hydrogenated copolymer block that copolymer block by will being made up of vinyl aromatic monomer units and conjugated diene monomeric unit (on described basis not in the hydrogenated copolymer) hydrogenation obtains to being lower than observed loss tangent peak in-10 ℃ of scopes at-40 ℃.To have at least one loss tangent peak in-10 ℃ the scope be vital for obtain the well balanced of snappiness, cold property and impact absorbency (low bounce impact elasticity) in described foam of polymers to being lower than at-40 ℃.

Loss tangent in the dynamic viscoelastic collection of illustrative plates (tan δ) peak records under the 10Hz frequency with dynamic viscoelastic atlas analysis instrument.

As mentioned above, described basis not hydrogenated copolymer contain the copolymer block S that at least one is made up of vinyl aromatic monomer units and conjugated diene monomeric unit.Not special restriction the weight ratio of conjugated diene monomeric unit/vinyl aromatic monomer units in copolymer block S.But, when considering the above-mentioned fact---must there be at least one loss tangent peak at-40 ℃ to being lower than in-10 ℃ of scopes, then the weight ratio of conjugated diene monomeric unit/vinyl aromatic monomer units is preferably 50/50-90/10 among the copolymer block S, 53/47-80/20 more preferably, even 56/44-75/25 more preferably.

In the present invention, preferably in differential scanning calorimetric (DSC) figure of the hydrogenated copolymer that obtains (A), do not observe the peak crystallization that belongs in-50 to 100 ℃ of scopes by at least one hydrogenated copolymer block that at least one copolymer block S hydrogenation is obtained basically.In the present invention, statement " not observing the peak crystallization that belongs in-50 to 100 ℃ of scopes by at least one hydrogenated copolymer block that at least one copolymer block S hydrogenation is obtained in differential scanning calorimetric (DSC) figure of the hydrogenated copolymer that obtains (A) basically " is meant that not observing expression in the said temperature scope crystalline peak occurs (promptly, peak crystallization), perhaps be meant in the said temperature scope and observe peak crystallization, but the heat at peak crystallization place is less than 3J/g, preferably less than 2J/g, be more preferably less than 1J/g, even more preferably 0.

Distribution in copolymer block S is not particularly limited for described vinyl aromatic monomer units.For example, but described vinyl aromatic monomer units uniform distribution or can distribute with the gradient form.In addition, copolymer block S can have many segments that wherein are uniform-distribution with vinyl aromatic monomer units, and/or can have many wherein with the distributing segment of vinyl aromatic monomer units of gradient form.In addition, copolymer block S can have the different segment of many vinyl aromatic monomer units content.In the present invention, statement " vinyl aromatic monomer units distributes with the gradient form " is meant chain length direction increase or the minimizing of the content of vinyl aromatic monomer units along copolymer block S.

The homopolymer block H of vinyl aromatic monomer units is contained on preferably described basis not hydrogenated copolymer.From snappiness and impact absorbency, in the basis weight of hydrogenated copolymer not, described basis not in the hydrogenated copolymer amount of homopolymer block H be preferably 40 weight % or littler.In the described basis weight of hydrogenated copolymer not, described basis is the amount of homopolymer block H 1-40 weight % more preferably in the hydrogenated copolymer not, even 5-35 weight % more preferably, even 10-30 weight % more preferably, even 13-25 weight % more preferably.

Described basis not in the hydrogenated copolymer content of vinyl aromatic monomer units homopolymer block (hereinafter, this homopolymer block so-called " vinyl aromatic polymer blocks ") can measure according to following method.Record the weight of vinyl aromatic polymer blocks component by following method: use in the presence of as the perosmic anhydride of catalyzer tert-butyl hydroperoxide to described basis not hydrogenated copolymer carry out oxidative degradation (promptly, in 1,429 page of (1946) middle method of describing of people's such as I.M.KOLTHOFF J.Polym.Sci. volume) (hereinafter so-called " perosmic anhydride edman degradation Edman ").Use the weight of the vinyl aromatic polymer blocks component of gained, calculate on described basis the not content of vinyl aromatic polymer blocks in the hydrogenated copolymer by following formula, condition is in the polymer chain (being formed by described oxidative degradation) corresponding to vinyl aromatic polymer blocks, does not consider that in measuring vinyl aromatic polymer blocks content the polymerization degree is about 30 or littler polymer chain.

The content of vinyl aromatic polymer blocks (weight %)

={ (described basis is the weight of vinyl aromatic polymer blocks part in the hydrogenated copolymer not)/(described basis is the weight of hydrogenated copolymer not) } * 100.

In addition, the content of described vinyl aromatic polymer blocks can obtain by following method: use nucleus magnetic resonance (NMR) device directly to hydrogenated copolymer (A) analyze (referring to people such as Y.Tanaka " RUBBER CHEMISTRY and TECHNOLOGY; roll up 54,685 pages (1981)) (hereinafter this method so-called " NMR method ").

The content value of the vinyl aromatic polymer blocks that is obtained by the perosmic anhydride edman degradation Edman (hereinafter, this value is called " Os value ") with the content value (hereinafter, this value so-called " Ns value ") of the vinyl aromatic polymer blocks that obtains by the NMR method between have cognation.More particularly, the inventor studies the multiple multipolymer with differing ethylene base aromatic(based)polymer block content, found that above-mentioned cognation can be expressed from the next:

Os value=-0.012 (Ns value) 2+1.8 (Ns value)-13.0

In the present invention, when obtaining the Ns value, use the formula of relation between above-mentioned representative Os value and the Ns value that gained Ns value is converted into the Os value by the NMR method.

To described basis not the structure of hydrogenated copolymer have no particular limits, as long as described basis not hydrogenated copolymer comprises vinyl aromatic monomer units and conjugated diene monomeric unit and contains the copolymer block S that at least one is made up of vinyl aromatic monomer units and conjugated diene monomeric unit, and as long as by with the basis not the hydrogenated copolymer (A) of hydrogenated copolymer hydrogenation acquisition have above-mentioned characteristic (1) and (2).The described basis not example of hydrogenated copolymer comprises the multipolymer of the block structure with following formula representative:

S，

(H-S) _n，

H-(S-H) _n，

S-(H-S) _n

[(S-H) _n] _m-X，

[(H-S) _n] _m-X，

[(S-H) _n-S] _m-X，

[(H-S) _n-H] _m-X，

(S-H) _n-X-(H) _p，

(E-S) _n，

E-(S-E) _n，

S-(E-S) _n，

[(E-S) _n] _m-X，

[(S-E) _n-S] _m-X，

[(E-S) _n-E] _m-X，

E-(S-H) _n，

E-(H-S) _n，

E-(H-S-H) _n，

E-(S-H-S) _n，

H-E-(S-H) _n，

H-E-(H-S) _n，

H-E-(S-H) _n-S，

[(H-S-E) _n] _m-X，

[H-(S-E) _n] _m-X，

[(H-S) _n-E] _m-X，

[(H-S-H) _n-E] _m-X，

[(S-H-S) _n-E] _m-X，

[(E-S-H) _n] _m-X，

[E-(S-H) _n] _m-X，

[E-(H-S-H) _n] _m-X and

[E-(S-H-S) _n] _m-X，

Wherein S distinguishes the copolymer block that independent expression is made up of vinyl aromatic monomer units and conjugated diene monomeric unit, the homopolymer block of the independent respectively expression vinyl aromatic monomer units of H, each E independently represents the homopolymer block of conjugated diene monomeric unit, independent respectively expression coupling agent residue of X or multifunctional polymerization initiator residue, independent respectively expression 2 of m or bigger integer, be preferably the integer of 2-10, n and p difference be expression 1 or bigger integer independently, is preferably the integer of 1-10.

The example of coupling agent residue comprises following coupling agent residue.The example of multifunctional polymerization initiator residue comprises the residue of the reaction product of di isopropenylbenzene and s-butyl lithium, and by Vinylstyrene, s-butyl lithium and a small amount of 1,3-butadiene being reacted the residue of the reaction product that obtains.

In above-mentioned not hydrogenated copolymer, preferably at least one is selected from the not hydrogenated copolymer by the multipolymer of following formula representative:

(1)S，

(2)S-H，

(3)S-H-S，

(4)(S-H) _m-X，

(5)(S-H) _n-X-(H) _p，

(6)H-S-H，

(7)S-E，

(8)H-S-E，

(9)E-S-H-S，

(10) (E-S-H) _m-X and

(11)(E-S-E) _m-X，

Wherein, S, H, E, X, m, n and p define as mentioned.

Weight-average molecular weight for hydrogenated copolymer (A) has no particular limits.But from the physical strength (for example tensile strength) and the incompressible tension set of described foam of polymers, the weight-average molecular weight of hydrogenated copolymer (A) is preferably 60,000 or bigger.In addition, from the workability of described foam of polymers, the weight-average molecular weight of hydrogenated copolymer (A) is preferably 1,000, and 000 or littler.The weight-average molecular weight of hydrogenated copolymer (A) is more preferably greater than 100,000 to 800,000, even more preferably 130,000-500,000.With regard to the molecular weight distribution of described hydrogenated copolymer (A), molecular weight distribution is preferably 1.05-6.From the workability of described foam of polymers, the molecular weight distribution of hydrogenated copolymer (A) is 1.1-6 more preferably, even 1.2-5 more preferably, even 1.4-4.5 more preferably.

The weight-average molecular weight of described hydrogenated copolymer approximates the not weight-average molecular weight of hydrogenated copolymer of described basis.Therefore, use described basis not the weight-average molecular weight of hydrogenated copolymer as the weight-average molecular weight of described hydrogenated copolymer.Use the not weight-average molecular weight of hydrogenated copolymer of the described basis of calibrating curve determining that obtains by commercially available standard monodisperse polystyrene by gel permeation chromatography (GPC) with predetermined molecular weight.The number-average molecular weight of described hydrogenated copolymer can obtain according to the mode identical with the weight-average molecular weight of described hydrogenated copolymer.The molecular weight distribution of described hydrogenated copolymer can be by calculating, and it is the ratio (Mw/Mn) of weight-average molecular weight (Mw) with the number-average molecular weight (Mn) of described hydrogenated copolymer of described hydrogenated copolymer.

For the hydrogenation ratio of the hydrogenated copolymer that records according to conjugated diene monomeric unit (A), have no particular limits.But, from the physical strength and the compression set resistant of described foam of polymers, the hydrogenation ratio of the hydrogenated copolymer (A) that records according to conjugated diene monomeric unit is generally 70% or bigger, is preferably 80% or bigger, more preferably 85% or bigger, even more preferably 90% or bigger.Above-mentioned hydrogenation is than measuring by nucleus magnetic resonance (NMR) device.

Use following polar compound etc. can suitably control the not microtexture (that is the content of cis key, trans key and ethylenic linkage) of conjugated diene monomeric unit in the hydrogenated copolymer of described basis.

Ethylenic linkage content to the conjugated diene monomeric unit of the copolymer block be not made up of vinyl aromatic monomer units and conjugated diene monomeric unit in the hydrogenated copolymer on described basis has no particular limits; But preferably ethylenic linkage content is 5% to (ethylenic linkage content hereinafter is meant 1,2-ethylenic linkage and 3 less than 40%, the total content of 4-ethylenic linkage, condition are when only 1,3-butadiene being used as conjugate diene monomer, ethylenic linkage content is meant 1, the content of 2-ethylenic linkage).From the low bounce impact elasticity and the handling property (adhesion inhibiting properties) of described foam of polymers, ethylenic linkage content is 5-35% more preferably, even 8-30% more preferably, even 10-25% more preferably.Herein, " adhesion inhibiting properties " refers to the characteristic of anti-adhesive phenomenon (its so-called " adhesion "), wherein for example when piling up resin forming object or roll extrusion resin molding (it has the resin surface that contacts with each other) long storage, can occur strong adhesive attraction unfriendly between resin surface, therefore described resin surface becomes and is difficult to be separated from each other.Ethylenic linkage content is measured by infrared spectrophotometer.

In the present invention, conjugate diene monomer is the diolefine with paired conjugated double bond.Be used for described basis not the example of the conjugate diene monomer of hydrogenated copolymer comprise 1,3-butadiene, 2-methyl isophthalic acid, the 3-divinyl is (promptly, isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl isophthalic acid, 3-pentadiene and 1,3-hexadiene.In these conjugate diene monomers, preferably 1,3-butadiene and isoprene.These conjugate diene monomers can individually or be united use.

Be used for described basis not the example of the vi-ny l aromatic monomers of hydrogenated copolymer comprise vinylbenzene, alpha-methyl styrene, p-methylstyrene, Vinylstyrene, 1,1-diphenylethlene, N, the N-dimethyl-to amino-ethyl vinylbenzene and N, the N-diethyl-to amino-ethyl vinylbenzene.In these vi-ny l aromatic monomers, vinylbenzene is preferred.These vi-ny l aromatic monomers can individually or be united use.

To prepare described basis not the method for hydrogenated copolymer provide following explanation.To prepare described basis not the method for hydrogenated copolymer have no particular limits, can use any ordinary method.For example, can prepare not hydrogenated copolymer of described basis by the active anionic polymerization that in hydrocarbon solvent, in the presence of polymerization starter (for example organic alkali metal compound), carries out.

The example of hydrocarbon solvent comprises aliphatic hydrocrbon, for example normal butane, Trimethylmethane, Skellysolve A, normal hexane, normal heptane and octane; Clicyclic hydrocarbon, for example pentamethylene, hexanaphthene, suberane and methyl suberane; And aromatic hydrocarbon, for example benzene,toluene,xylene and ethylbenzene.

The example of polymerization starter comprises aliphatic hydrocrbon-alkali metal compound, aromatic hydrocarbon-alkali metal compound and organic amino-alkali metal compound, and above-mentioned substance has the active anionic polymerization activity to conjugate diene monomer and vi-ny l aromatic monomers.The specific examples of polymerization starter comprises the reaction product of n-propyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, di isopropenylbenzene and s-butyl lithium, and by reaction product with Vinylstyrene, s-butyl lithium and a small amount of 1,3-butadiene reaction gained.Other example of polymerization starter comprises U.S. Pat 5,708,092, the organic alkali metal compound described in English Patent GB 2,241,239 and the U.S. Pat 5,527,753.

In the present invention, when in the presence of organic alkali metal compound, carrying out the copolyreaction of conjugate diene monomer and vi-ny l aromatic monomers as polymerization starter, can use tertiary amine or ether compound to form reagent as ethylenic linkage, its amount that is used to improve the ethylenic linkage that is formed by conjugate diene monomer (promptly, 1,2-ethylenic linkage and 3, the 4-ethylenic linkage).

The example of tertiary amine comprises the compound of following formula representative: R ¹R ²R ³N, wherein R ¹, R ²And R ³The independent respectively C that represents ₁-C ₂₀Alkyl or the C that is replaced by uncle's amino ₁-C ₂₀Alkyl.The specific examples of tertiary amine comprises Trimethylamine 99, triethylamine, tributylamine, N, accelerine, N-ethylpiperidine, N-crassitude, N, N, N ', N '-Tetramethyl Ethylene Diamine, N, N, N ', N '-tetraethylethylenediamine, 1,2-two piperidino-(1-position only) ethane, trimethylammonium aminoethylpiperazine, N, N, N '; N ", N "-pentamethyl-second triamine and N, N '-dioctyl-Ursol D.

The example of ether compound comprises linear ether compound and cyclic ether compound.The linear ether examples for compounds comprises dme; Diethyl ether; Phenyl ether; Ethylene glycol bisthioglycolate alkyl oxide, for example glycol dimethyl ether, ethylene glycol diethyl ether and ethylene glycol dibutyl ether; With the glycol ether dialkyl ether, for example diglyme, diethyl carbitol and diethylene glycol dibutyl ether.The cyclic ether examples for compounds comprises tetrahydrofuran (THF), diox, 2,5-dimethyl tetrahydrofuran, 2,2,5,5-tetramethyl-tetrahydrofuran, 2, the alkyl oxide of two (2-tetrahydrofuran base) propane of 2-and furfuryl alcohol.

In the present invention, in the presence of organic alkali metal compound, be used to prepare as polymerization starter described basis not the copolyreaction of hydrogenated copolymer can carry out off and on or continuously.In addition, this copolyreaction can use the mode of periodical operation and operate continuously to carry out wherein to unite.The temperature of reaction of described copolyreaction is generally 0-180 ℃, is preferably 30-150 ℃.The reaction times of described copolyreaction can change according to other condition, but usually in 48 hours, is preferably 0.1-10 hour.The atmosphere of preferred described copolymerization system is rare gas element, for example nitrogen.Pressure to described copolyreaction has no particular limits, as long as this pressure is enough to make described monomer and solvent to keep liquid in above-mentioned range of reaction temperature.In addition, must be noted that to prevent from impurity (for example, water, oxygen and carbonic acid gas) is introduced in the described copolymerization system that these impurity can reduce the activity of described catalyzer and reactive polymer.

After described copolyreaction is finished, the coupling agent with two or more functionality can be added in the described copolymerization system to carry out linked reaction.Coupling agent with two or more functionality is had no particular limits, can use any conventional coupling agent.The example of difunctionality coupling agent comprises dihalide, for example dimethyldichlorosilane(DMCS) and dimethyl two bromo-silicanes; And acid ester, for example methyl benzoate, ethyl benzoate, phenylformic acid phenyl ester and phthalic ester.Example with coupling agent of three or more functionality comprises the polyvalent alcohol with three or more hydroxyls; The multivalence epoxy compounds, for example epoxidised soybean oil and diglycidyl dihydroxyphenyl propane; Multi-halogenated compounds, for example, the halo silicon compound of formula R4-nSiXn representative, the wherein independent respectively C that represents of R ₁-C ₂₀Alkyl, it is 3 or 4 that X independently represents halogen atom, n respectively; Formula R _4-nS _nX _nThe halo tin compound of representative, the wherein independent respectively C that represents of R ₁-C ₂₀Alkyl, it is 3 or 4 that X independently represents halogen atom, n respectively.The specific examples of halo silicon compound comprises methyl-silicane base trichloride, tertiary butyl silyl trichloride, silicon tetrachloride and brominated product thereof.The specific examples of halo tin compound comprises methyl tin trichloride, tertiary butyl tin trichloride and tin tetrachloride.In addition, methylcarbonate, diethyl carbonate etc. also can be used as multifunctional coupling agent.

By the not hydrogenated copolymer hydrogenation that in the presence of hydrogenation catalyst, will make thus, can make hydrogenated copolymer (A).Have no particular limits for hydrogenation catalyst, can use any conventional hydrogenation catalyst.The example of hydrogenation catalyst comprises:

(1) the heterogeneous hydrogenation catalyst that supports, this catalyzer comprise the carrier (for example, carbon, silicon-dioxide, aluminum oxide or diatomite) that has supported metal (for example Ni, Pt, Pd or Ru) on it;

(2) so-called Ziegler-type hydrogenation catalyst, it unites use transition metal salt (for example, the organic acid salt of metal or acetylacetonate, this metal for example are Ni, Co, Fe or Cr) and reductive agent (for example organo-aluminium compound); With

(3) homogeneous hydrogenation catalyst, for example so-called organometallic complex, as contain for example organometallic compound of Ti, Ru, Rh or Zr metal.

The specific examples of hydrogenation catalyst comprises that publication number is clear and 63-4841, equals into 1-53851 peace and become that 2-9041's examine those that describe in the Japanese patent application.As the preferred embodiment of hydrogenation catalyst, what can mention is the mixture of two cyclopentadiene titanium compounds and two cyclopentadiene titanium compounds and reduction organometallic compound.

The example of two cyclopentadiene titanium compounds comprise publication number be put down into 8-109219 examine those that describe in the Japanese patent application.Specific examples as two cyclopentadiene titanium compounds, can mention and have at least one compound that has the part of (replacement) cyclopentadienyi skeleton, indenyl skeleton or fluorenyl skeleton (as, the molybdenyl dichloride cyclopentadienyl closes titanium and the single pentamethyl-cyclopentadienyl of tri-chlorination closes titanium).The example of reduction organometallic compound comprises organic alkali metal compound, for example organolithium compound; Organo-magnesium compound; Organo-aluminium compound; Organoboron compound; And organic zinc compound.

The hydrogenation that is used to prepare described hydrogenated copolymer carries out under 0-200 ℃ usually, preferably carries out under 30-150 ℃.Hydrogen pressure in the described hydrogenation is generally 0.1-15MPa, is preferably 0.2-10MPa, more preferably 0.3-5MPa.The described hydrogenation time was generally 3 minutes-10 hours, was preferably 10 minutes-5 hours.Described hydrogenation can intermittently or carry out continuously.In addition, described hydrogenation can use the mode of periodical operation and operate continuously to carry out to unite.

By aforesaid method, obtain described hydrogenated copolymer with its solution form in solvent.From gained solution, isolate this hydrogenated copolymer.If necessary, before separating hydrogenated copolymer, can from described solution, isolate catalyst residue.Separate described hydrogenated copolymer and solvent and for example comprise following method with the method that reclaims this hydrogenated copolymer: for example acetone or alcohol join in the described solution that contains hydrogenated copolymer with polar solvent (it is poor solvent for described hydrogenated copolymer), thereby be settled out this hydrogenated copolymer, reclaim the precipitated hydrogenated copolymer that goes out afterwards; Also comprise under agitation and join the described solution that contains hydrogenated copolymer in the hot water, remove described solvent to reclaim the method for described hydrogenated copolymer by the steam extracting afterwards; Also comprise directly the described solution that contains hydrogenated copolymer is heated to steam the method for solvent.

Can sneak into stablizer in the hydrogenated copolymer (A).The example of stablizer comprises phenolic stabilizer, phosphorus type stablizer, sulphur type stablizer and amine type stablizer.

Can connect properties-correcting agent (hereinafter, this hydrogenated copolymer (A) so-called " modified hydrogenated copolymer (A) ") on the hydrogenated copolymer (A) with functional group.

As the properties-correcting agent with functional group, what can mention is to have the one-level properties-correcting agent that at least one is selected from following functional group: hydroxyl; carboxyl; carbonyl; thiocarbonyl; acid halide; anhydride group; hydroxy-acid group; thiocarboxyl group; aldehyde radical; the sulfo-aldehyde radical; the carboxylate group; amido group; sulfonic acid group; sulfonate ester group; phosphate group; bound phosphate groups; amino; imino-; itrile group; pyridyl; quinolyl; epoxide group; the sulfo-epoxide group; sulfide group (su1fide group); isocyanate groups; the lsothiocyanates group; the silicon halide group; silanol; alkoxysilane groups (it preferably has 1-24 carbon atom); the tin halides group; alkoxyl group tin group and phenyltin group.In above-mentioned functional group, preferably hydroxyl, epoxide group, amino, silanol groups and alkoxysilane groups (it preferably has 1-24 carbon atom).(hereinafter, the hydrogenated copolymer (A) that has connected one-level properties-correcting agent on it is called " hydrogenated copolymer of one-level modification (A) ").

As the example of one-level properties-correcting agent with above-mentioned functional group, can mention be publication number be put down into 4-39495 examine the terminal groups modification agent of describing among Japanese patent application (corresponding to U.S. Pat 5,115,035) and the WO03/8466.The specific examples of this properties-correcting agent comprises four glycidyl group-m-xylene diamine, four glycidyl group-1, the two amino methyl hexanaphthenes of 3-, 6-caprolactone, 4-methoxy benzophenone, γ-epoxy third oxygen ethyl trimethoxy silane, γ-epoxy third oxygen-butyl Trimethoxy silane, γ-epoxypropoxy triple phenoxyl silane, two (γ-epoxypropoxy) methyl-prop TMOS, 1,3-dimethyl-2-imidazolone, 1,3-diethyl-2-imidazolone, N, N '-dimethylpropylene urea and N-Methyl pyrrolidone.

Described properties-correcting agent can comprise one-level properties-correcting agent and the secondary properties-correcting agent that is connected thereon.The functional group that this secondary properties-correcting agent has described one-level properties-correcting agent is reactive functional group.(hereinafter, connected the hydrogenated copolymer (A) that comprises one-level properties-correcting agent and the properties-correcting agent that is connected secondary properties-correcting agent thereon on it and be called " hydrogenated copolymer of secondary modification (A) ").

The example of one-level properties-correcting agent that is used for the hydrogenated copolymer (A) of described secondary modification comprises having the properties-correcting agent that at least one is selected from following functional group: hydroxyl; carboxyl; carbonyl; thiocarbonyl; acid halide; anhydride group; hydroxy-acid group; thiocarboxyl group; aldehyde radical; the sulfo-aldehyde radical; the carboxylate group; amido; sulfonic group; sulfonate ester group; phosphate group; bound phosphate groups; amino; imino-; itrile group; pyridyl; quinolyl; epoxy group(ing); the sulfo-epoxy group(ing); sulfide group; isocyanate groups; the lsothiocyanates group; the silicon halide group; silanol; alkoxysilane groups (it preferably has 1-24 carbon atom); the tin halides group; alkoxyl group tin group and phenyltin group.The preferred embodiment of one-level properties-correcting agent comprises having the properties-correcting agent that at least one is selected from following functional group: hydroxyl, epoxy group(ing), amino, silanol and alkoxysilane group (it preferably has 1-24 carbon atom).Example with one-level properties-correcting agent of above-mentioned functional group comprise above-mentioned publication number be put down into 4-39495 examine the terminal groups modification agent of describing among Japanese patent application (corresponding to U.S. Pat 5,115,035) and the above-mentioned WO03/8466.

The preferred embodiment of secondary properties-correcting agent comprises having the properties-correcting agent that at least one is selected from following functional group: carboxyl, anhydride group, isocyanate groups, epoxide group, silanol and alkoxysilane group (it preferably has 1-24 carbon atom).The functional group that particularly preferably is described secondary properties-correcting agent comprises at least two groups that are selected from above-mentioned functional group, wherein when described at least two groups comprise anhydride group, has only one at least in preferred described two groups and is anhydride group.

Enumerated the specific examples of secondary properties-correcting agent below.The specific examples that contains the secondary properties-correcting agent of carboxyl comprises aliphatic carboxylic acid, for example toxilic acid, oxalic acid, succsinic acid, hexanodioic acid, nonane diacid, sebacic acid, dodecanedicarboxylic acid, carbalic acid, cyclohexane dicarboxylic acid and pentamethylene dicarboxylic acid; And the aromatic carboxylic acid, for example terephthalic acid, m-phthalic acid, phthalic acid, naphthalene dicarboxylic acids, diphenyl dicarboxylic acid, 1,3,5-benzenetricarboxylic acid, trimellitic acid and pyromellitic acid.

Specific examples with secondary properties-correcting agent of anhydride group comprises maleic anhydride, itaconic anhydride, pyromellitic acid acid anhydride, suitable-4-hexanaphthene-1,2-dicarboxylic anhydride, 1,2,4,5-benzene tertacarbonic acid dianhydride, and 5-(2,5-dioxy tetrahydroxy furyl)-and 3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride.

Specific examples with secondary properties-correcting agent of isocyanate groups comprises tolylene diisocyanate, '-diphenylmethane diisocyanate and multifunctional aromatic isocyanate.

Specific examples with secondary properties-correcting agent of epoxide group comprises four glycidyl group-1, the two amino methyl hexanaphthenes of 3-, four glycidyl group-m-xylene diamine, 2-glycidyl aniline, ethylene glycol diglycidylether, propylene glycol diglycidylether, terephthalic acid diglycidyl ester acrylate and the above-mentioned hydrogenated copolymer (A) that is used to obtain the one-level modification that is listed as) the epoxy compounds of one-level properties-correcting agent.

Specific examples with secondary properties-correcting agent of silanol comprises the hydrolysate of the above-mentioned alkoxysilane compound containing trialkylsilyl group in molecular structure of the one-level properties-correcting agent that is listed as the hydrogenated copolymer (A) that is used to obtain the one-level modification.

The specific examples of secondary properties-correcting agent with alkoxysilane groups of 1-24 carbon atom comprises two (3-triethoxysilylpropyltetrasulfide)-four sulfanes, two (3-triethoxysilylpropyltetrasulfide)-disulphanes, oxyethyl group siloxane oligomer and the above-mentioned silane compound that is listed as the one-level properties-correcting agent of the hydrogenated copolymer (A) that is used to obtain the one-level modification.

The particularly preferred example that is used in the secondary properties-correcting agent in the hydrogenated copolymer (A) of secondary modification comprises carboxylic acid and the acid anhydrides thereof with two or more carboxyls; And have the secondary properties-correcting agent that two or more are selected from following groups: anhydride group, isocyanate groups, epoxide group, silanol and have the alkoxysilane groups of 1-24 carbon atom.The specific examples of particularly preferred secondary properties-correcting agent comprises maleic anhydride, pyromellitic acid acid anhydride, 1,2,4,5-benzene tertacarbonic acid dianhydride, tolylene diisocyanate, four glycidyl group-1, the two amino methyl hexanaphthenes of 3-and two (3-triethoxysilylpropyltetrasulfide)-four sulfanes.

As mentioned above, when being used in when comprising one-level properties-correcting agent as the properties-correcting agent in the modified hydrogenated copolymer of component (A), the hydrogenated copolymer of described modification is known as " hydrogenated copolymer of one-level modification (A) "; When being used in when comprising one-level properties-correcting agent with the secondary properties-correcting agent that is connected thereon as the properties-correcting agent in the modified hydrogenated copolymer of component (A), the hydrogenated copolymer of described modification is known as " hydrogenated copolymer of secondary modification (A) ".

Provide following explanation for preparation as the method for the one-level modified hydrogenated copolymer of component (A).Can prepare the hydrogenated copolymer of described one-level modification according to following method: with described basis not hydrogenated copolymer hydrogenation to obtain hydrogenated copolymer, and one-level properties-correcting agent is connected on the hydrogenated copolymer of gained (hereinafter, this method is commonly referred to as " method of carrying out modification after the hydrogenation ").As selection, the hydrogenated copolymer of described one-level modification can be according to the preparation of following method: with one-level properties-correcting agent be connected described basis not on the hydrogenated copolymer to obtain to have connected on it not hydrogenated copolymer of one-level properties-correcting agent, and the not hydrogenated copolymer hydrogenation (hereinafter, this method is commonly referred to as " method of carrying out modification before the hydrogenation ") of one-level properties-correcting agent will have been connected on its of gained.

As the example that carries out the method for modification after the hydrogenation, can mention following method: with described basis not hydrogenated copolymer hydrogenation to obtain hydrogenated copolymer, with gained hydrogenated copolymer and organic alkali metal compound (for example, organolithium compound) reaction (this reaction is called " metallization reaction "), thereby obtain to have connected on it alkali-metal hydrogenated copolymer, make the reaction of this hydrogenated copolymer and one-level properties-correcting agent afterwards.

As the example that carries out the method for modification before the hydrogenation, can mention following method: in the presence of organolithium compound as polymerization starter, obtain having the not hydrogenated copolymer of active end group by aforesaid method, with the not hydrogenated copolymer with active end group of gained and the reaction of one-level properties-correcting agent with the not hydrogenated copolymer that obtains being connected on it one-level properties-correcting agent (this not hydrogenated copolymer be called " the not hydrogenated copolymer of modification "), and with the not hydrogenated copolymer hydrogenation of described modification, thereby obtain the hydrogenated copolymer of one-level modification.In addition, the hydrogenated copolymer of one-level modification also can be according to the preparation of following method: hydrogenated copolymer and organic alkali metal compound be not (for example on the basis that will not have an active end group, organolithium compound) reaction (this reaction is called " metallization reaction "), thereby obtain having connected alkali-metal not hydrogenated copolymer, to connect the reaction of alkali-metal not hydrogenated copolymer and one-level properties-correcting agent to obtain the not hydrogenated copolymer of modification, and with the not hydrogenated copolymer hydrogenation of described modification, thereby obtain the hydrogenated copolymer of one-level modification.

Carry out carrying out in the method for modification before the method for modification or the hydrogenation after hydrogenation, the temperature of described modified-reaction is preferably 0-150 ℃, more preferably 20-120 ℃.The modified-reaction time can change according to other condition, but preferably in 24 hours, more preferably 0.1-10 hour.

When described basis not during the reaction of hydrogenated copolymer and one-level properties-correcting agent,, the hydroxyl that comprises in the one-level properties-correcting agent, amino etc. can be converted into its organic metal salt according to the type of one-level properties-correcting agent.In this case, by making described organic metal salt and active hydrogen-containing compound (for example water or alcohol) reaction organic metal salt can be converted into hydroxyl, amino etc. again.

By with described basis not the hydrogenated copolymer of the one-level modification that obtains of the active end group of hydrogenated copolymer and the reaction of one-level properties-correcting agent, hydrogenation afterwards can contain unmodified multipolymer fraction.In the weight of the hydrogenated copolymer of described one-level modification, the amount of described unmodified multipolymer fraction in the hydrogenated copolymer of one-level modification preferably is no more than 70 weight %, more preferably no more than 60 weight %, even more preferably no more than 50 weight %.

Method for the hydrogenated copolymer for preparing the secondary modification provides following explanation.The hydrogenated copolymer of described secondary modification is to make by hydrogenated copolymer and the reaction of secondary properties-correcting agent with above-mentioned one-level modification.

When the hydrogenated copolymer of one-level modification and the reaction of secondary properties-correcting agent, with respect to the described functional group of 1 equivalent that is connected the one-level properties-correcting agent on the one-level modified hydrogenated copolymer, the amount of secondary properties-correcting agent is generally 0.3-10mol, is preferably 0.4-5mol, more preferably 0.5-4mol.

The method of reacting for one-level modified hydrogenated copolymer and secondary properties-correcting agent has no particular limits, and can use conventional method.The example of ordinary method comprises use fusion-kneading method (following this is described) and wherein is dissolved or dispersed in the method for under the state in the solvent described component being reacted each other jointly in described component.A kind of method in back has no particular limits solvent, as long as this solvent can dissolve or disperse each component.The example of solvent comprises hydrocarbon, for example aliphatic hydrocrbon, clicyclic hydrocarbon and aromatic hydrocarbon; Halogen-containing solvent; Ester solvent; And ether solvents.Described therein component is dissolved or dispersed in the method in the solvent jointly, and the temperature that one-level modified hydrogenated copolymer and secondary properties-correcting agent react is generally-10-150 ℃, be preferably 30-120 ℃.In the method, the reaction times can change according to other condition, but usually in 3 hours, is preferably several seconds to 1 hour.As a kind of particularly preferred method for preparing the secondary modified hydrogenated copolymer, can mention following method: secondary properties-correcting agent is added in the solution of one-level modified hydrogenated copolymer reacting, thereby obtain the hydrogenated copolymer of secondary modification.In the method, before in the solution of described one-level modified hydrogenated copolymer, adding secondary properties-correcting agent, can carry out neutralizing treatment to the solution of one-level modified hydrogenated copolymer.

Can use α, beta-unsaturated carboxylic acid or derivatives thereof (for example, acid anhydrides, ester, acid amides or imide) carries out grafting-modification to the hydrogenated copolymer (its non-modified) as component (A).α, the specific examples of beta-unsaturated carboxylic acid and its derivative comprises maleic anhydride, maleimide, vinylformic acid, acrylate, methacrylic acid, methacrylic ester and interior-suitable-dicyclo (2,2,1)-5-heptene-2,3-dicarboxylic acid and acid anhydrides thereof.

With respect to the hydrogenated copolymer of 100 weight parts, described α, the amount of beta-unsaturated carboxylic acid or derivatives thereof is generally the 0.01-20 weight part, is preferably the 0.1-10 weight part.

When described hydrogenated copolymer being carried out grafting-modified-reaction, grafting-modified-reaction preferably 100-300 ℃, more preferably carry out under 120-280 ℃.

But for the details reference example of the method for grafting-modification such as publication number be clear and 62-79211 examine Japanese patent application.

When hydrogenated copolymer (A) is one-level modified hydrogenated copolymer or secondary modified hydrogenated copolymer, for be connected on the hydrogenated copolymer (A) properties-correcting agent (promptly, one-level properties-correcting agent (for the hydrogenated copolymer of one-level modification), or one-level properties-correcting agent and secondary properties-correcting agent (for the hydrogenated copolymer of secondary modification)), its functional group is not only to polymkeric substance (B), mineral filler, it is reactive that the additive of polar functionalities etc. is, also has nitrogen-atoms, Sauerstoffatom or carbonyl, therefore because physics affinity interaction (for example hydrogen bond) therebetween, the functional group of properties-correcting agent and polymkeric substance (B), mineral filler, can interact effectively between the polar group of the additive of polar functionalities etc., thereby can strengthen the excellent properties of foam of polymers of the present invention.When hydrogenated copolymer (A) carries out above-mentioned grafting-modification, also can produce this enhancement to the excellent properties of described foam of polymers.

As mentioned above, with respect to the component of 100 weight parts (A) altogether and (B), be respectively 5-100 weight part and 95-0 weight part as the amount of the hydrogenated copolymer (wherein this hydrogenated copolymer can be the hydrogenated copolymer of one-level modification or the hydrogenated copolymer of secondary modification) of component (A) with as the amount of the polymkeric substance of component (B).Preferably, with respect to the component of 100 weight parts (A) altogether and (B), component (A) and amount (B) are respectively 5-95 weight part and 95-5 weight part.More preferably, with respect to the component of 100 weight parts (A) altogether and (B), component (A) and amount (B) are respectively 20-65 weight part and 80-35 weight part.

When component (A) during for the hydrogenated copolymer of modification (that is, the hydrogenated copolymer of the hydrogenated copolymer of one-level modification or secondary modification), (component (A)) part except that described properties-correcting agent is called " component (A-1) ".With respect to the component of 100 weight parts (A-1) altogether and (B), the amount of properties-correcting agent is generally the 0.01-20 weight part, is preferably the 0.02-10 weight part, more preferably the 0.05-7 weight part.Component (A-1) is preferably 10/90-90/10 with the weight ratio of component (B), more preferably 20/80-65/35.

As mentioned above, polymkeric substance (B) is at least one material that is selected from the olefin polymer that is different from hydrogenated copolymer (A) and is different from the rubbery polymer of hydrogenated copolymer (A).

Have no particular limits for olefin polymer as component (B).The example of olefin polymer (B) comprising: ethene polymers, polyethylene for example, ethene with can with the comonomer of ethylene copolymer (wherein, ethylene monomer unit content is 50 weight % or bigger) multipolymer (as, ethylene/propene copolymer, ethylene/propene/butylene copolymer, ethylene/butylene copolymers, the ethylene/hexene multipolymer, ethylene/octene, ethylene/vinyl acetate copolymer or its hydrolysate, ethene and acrylate (it obtains by vinylformic acid and alcohol with 1-24 carbon atom or glycidic alcohol reaction) (as, methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester or Ethyl acrylate) multipolymer, or ethene and methacrylic ester (it reacts with alcohol with 1-24 carbon atom or glycidic alcohol by methacrylic acid and obtains) (as, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester or N-Hexyl methacrylate) multipolymer, ethylene/acrylic acid ionomer, and chlorinatedpolyethylene; Propene polymer, for example polypropylene, propylene and can with the comonomer of copolymerization of propylene (wherein, propylene monomer units content is 50 weight % or bigger) multipolymer, the multipolymer that forms of propylene/ethylene copolymer, propylene/ethylene/butene multipolymer, propene/but-1-ene copolymer, propylene/hexene copolymer, propylene/octene copolymer, propylene and any aforesaid propylene acid esters for example, the perhaps multipolymer of propylene and any above-mentioned methacrylic ester formation, and Chlorinated Polypropylene III; Cyclic olefin polymer (as, ethene/norbornene polymer); And butene polymers.

In above-mentioned olefin polymer, ethene polymers preferably.Polyvinyl preferred embodiment comprises polyethylene, ethylene/propene copolymer, ethylene/propene/butylene copolymer, ethylene/butylene copolymers, ethylene/hexene multipolymer, ethylene/octene, ethylene/vinyl acetate copolymer, ethene/acrylic ester multipolymer and ethylene/methacrylic acid ester copolymer.

Above-mentioned olefin polymer can individually or be united use.When olefin polymer was multipolymer, olefin polymer can be segmented copolymer or can not be segmented copolymer.

Have no particular limits for the method for preparing olefin polymer (B), can use conventional method.For example, olefin polymer (B) can pass through method preparations such as progressively polymerization, radical polymerization, ionic polymerization.

When requiring foam of polymers of the present invention to have excellent processability, under 230 ℃, 2.16kg load, the melt flow rate (MFR) of the olefin polymer (B) that records according to JIS K6758 is preferably 0.05-200g/10min, more preferably 0.1-150g/10min.Olefin polymer (B) can be used the secondary modifier modification in advance.

Have no particular limits for rubbery polymer as component (B).The example of rubbery polymer (B) comprises that conjugated diolefin polymer (for example, divinyl rubber or synthetic polyisoprene) and hydrogenated products, the multipolymer of being made up of vinyl aromatic monomer units and conjugated diene monomeric unit (for example, styrene/butadiene rubbers) and hydrogenated products, be selected from segmented copolymer and the hydrogenated products thereof that following polymer blocks is formed by the homopolymer block of vinyl aromatic monomer units and at least one: the homopolymer block of conjugated diene monomeric unit and the copolymer block be made up of vinyl aromatic monomer units and conjugated diene monomeric unit are (for example, styrene/butadiene block copolymer or styrene/isoprene segmented copolymer), acrylonitrile/butadiene rubber and hydrogenated products thereof, chloroprene rubber, ethylene/propylene/diene rubber (EPDM), ethylene/butylene/elastoprene, isoprene-isobutylene rubber, acrylic rubber, viton, silicone rubber, chlorinated polyethylene rubber, epichloro hydrin rubber, α, alpha, beta-unsaturated nitriles/acrylate/conjugated diene copolymer rubber, urethanes, thiorubber and natural rubber.These rubbery polymers can individually or be united use.

Above-mentioned each rubbery polymer can be for being connected with the modified rubber of functional group on it.For example, this rubbery polymer is by the modified rubber of secondary modifier modification.

The weight-average molecular weight of described rubbery polymer is generally 30,000-1, and 000,000, be preferably 50,000-800,000, more preferably 70,000-500,000.The weight-average molecular weight of described rubbery polymer is measured by GPC.

In above-mentioned rubbery polymer, preferably 1, the 2-polyhutadiene, the hydrogenated products of conjugated diene homopolymers, multipolymer and the hydrogenated products thereof formed by vinyl aromatic monomer units and conjugated diene monomeric unit, be selected from segmented copolymer and the hydrogenated products thereof that following polymer blocks is formed by vinyl aromatic monomer units homopolymer block and at least one: the homopolymer block of conjugated diene monomeric unit and the copolymer block of forming by vinyl aromatic monomer units and conjugated diene monomeric unit (for example, styrene/butadiene block copolymer or styrene/isoprene segmented copolymer), acrylonitrile/butadiene rubber and hydrogenated products thereof, ethylene/propylene/diene rubber (EPDM), isoprene-isobutylene rubber and natural rubber.

In above-mentioned rubbery polymer, impact absorbency (low bounce impact elasticity) from described foam of polymers, the hydrogenated products of the multipolymer of forming by vinyl aromatic monomer units and conjugated diene monomeric unit more preferably, wherein in the weight of hydrogenated products, the vinyl aromatic monomer units content of this hydrogenated products is greater than 60 weight % to 90 weight %; Be selected from segmented copolymer and the hydrogenated products thereof that following polymer blocks is formed by vinyl aromatic monomer units homopolymer block and at least one: the homopolymer block of conjugated diene monomeric unit and the copolymer block of forming by vinyl aromatic monomer units and conjugated diene monomeric unit.

In the present invention, the material that will comprise 5-100 weight part hydrogenated copolymer (A) and 95-0 parts by weight polymer (B) is used to prepare described foam of polymers (wherein component (A) and amount (B) are represented with weight part, and it is with respect to the component of 100 weight parts (A) altogether with (B)).This material constitutes the polymeric matrix of foam of polymers of the present invention.Hereinafter, this material (it comprises component (A) or component (A) and mixture (B)) is known as " matrix-formation material ".

Described matrix-formation material can also comprise the thermoplastic resin that is different from as the olefin polymer of component (B).When described matrix-when the formation material contains the thermoplastic resin that is different from olefin polymer, from keeping the flexible angle of foam of polymers, with respect to the component of 100 weight parts (A) altogether and (B), the amount of this thermoplastic resin is generally the 1-100 weight part, is preferably the 5-80 weight part.

The example that is different from the thermoplastic resin of olefin polymer comprises the copolymer resin that any vi-ny l aromatic monomers (it is above doing to enumerate in the component (A)) and at least a vinyl monomer (except that described vi-ny l aromatic monomers) form, described vinyl monomer for example be ethene, propylene, butylene, vinylchlorid, vinylidene chloride, vinyl acetate, vinylformic acid, acrylate (as, methacrylic acid), methacrylic acid, methacrylic ester (as, methyl methacrylate), vinyl cyanide or methacrylonitrile; Rubber-modified styrene resin (HIPS); Acrylonitrile/butadiene/styrene copolymer resin (ABS); And methacrylic ester/butadiene/styrene copolymers resin (MBS).

Other example of thermoplastic resin comprises polyvinyl chloride, polyvinylidene dichloride, vinyl chloride resin, vinyl acetate resin and hydrolysate thereof, the polymkeric substance of acrylate copolymer and ester thereof or acid amides, the polymkeric substance of methacrylate polymer and ester thereof or acid amides, acrylate resin, polyacrylonitrile, polymethacrylonitrile, vinyl cyanide/methacrylonitrile copolymers, and nitrile resin, described nitrile resin is vinyl cyanide type monomer and the multipolymer (wherein, described vinyl cyanide type monomeric unit content is 50 weight % or more) that can form with the comonomer of vinyl cyanide type monomer copolymerization.

Other example of thermoplastic resin comprises polyamide resin, for example nylon-46, nylon-6, nylon-66, nylon-610, nylon-11, PA-12 and nylon-6/PA-12 multipolymer; Vibrin; TPU(Thermoplastic polyurethanes); Polycarbonate for example, gathers-4,4 '-dioxydibenze base-2,2 '-propane carbonic ether; Thermoplasticity polysulfones, for example polyethersulfone and polyene propyl group sulfone; Polyformaldehyde resin; Polyphenylene oxide resin, for example poly-(2,6-dimethyl-1,4-phenylene) ether; Polyphenylene sulfide, polyphenylene sulfide and poly--4 for example, 4 '-diphenylene thioether; The poly-allylat resin; Ether ketone homopolymer or multipolymer; The polyketone resin; Fluoro-resin; Polyoxy benzoyl type polymkeric substance; Polyimide resin; With polymerizing butadiene resin, for example trans polybutadiene.

Above-mentioned thermoplastic resin can individually or be united use.

Described thermoplastic resin can be used the secondary modifier modification in advance.

The number-average molecular weight of described thermoplastic resin is generally 1,000 or bigger, is preferably 5,000-5,000,000, more preferably 10,000-1,000,000.The number-average molecular weight of thermoplastic resin is measured by GPC.

In order to improve the processability of matrix-formation material, described matrix-formation material can contain tenderizer.As tenderizer, preferably use mineral oil, or liquid or low-molecular-weight synthetic tenderizer.Usually, the mineral oil origin tenderizer (being called " process oil " or " extending oil ") that is generally used for improving the volume of rubber or is used to improve the processability of rubber is the mixture of aromatic substance, naphthenic hydrocarbon and paraffinic hydrocarbons.For the mineral oil origin tenderizer, the carbonatoms that constitutes the alkane hydrocarbon chain be 50% or the tenderizer of more (based on the sums of the carbon atom that exists in the tenderizer) be called " paraffinic hydrocarbons type tenderizer "; Formation naphthenic carbonatoms is that the tenderizer of 30-45% (based on the total number of carbon atoms that exists in the tenderizer) is called " naphthenic type tenderizer "; Be called " aromatics type tenderizer " with the carbonatoms that constitutes aromatic ring greater than the tenderizer of 30% (based on the total number of carbon atoms that exists in the tenderizer).Preferred mineral oil origin tenderizer is at least a tenderizer that is selected from naphthenic type tenderizer and paraffinic hydrocarbons type tenderizer.

As synthetic tenderizer, can use polybutene, low molecular weight polybutadiene and liquid paraffin.But above-mentioned mineral oil origin tenderizer is preferred.

With respect to the hydrogenated copolymer (A) of 100 weight parts, the amount of tenderizer is generally the 0-200 weight part, is preferably the 0-100 weight part.

If necessary, described matrix-formation material can contain additive.Have no particular limits for additive, as long as it is used in thermoplastic resin or the rubbery polymer usually.

The example of additive comprises mineral filler, for example silicon-dioxide, talcum, mica, Calucium Silicate powder, hydrotalcite, kaolin, diatomite, graphite, lime carbonate, magnesiumcarbonate, magnesium hydroxide, aluminium hydroxide, calcium sulfate and barium sulfate; And organic filler, for example carbon black.

Other example of additive comprises lubricant, for example stearic acid, mountain Yu acid, Zinic stearas, calcium stearate, Magnesium Stearate and ethylenebisstearamide; Releasing agent; Softening agent, for example organopolysiloxane and mineral oil; Antioxidant, for example fortified phenol type antioxidant, phosphorus type thermo-stabilizer, sulphur type thermo-stabilizer and amine type thermo-stabilizer; Hindered amine type light stabilizer; The benzotriazole type UV light absorber; Fire retardant; Static inhibitor; Toughener, for example organic fibre, glass fibre, carbon fiber and scrap metal; Tinting material, for example titanium oxide, ferric oxide and carbon black; The additive of describing in " Gomu Purasuchikku HaigouYakuhin (Additives for Rubber and Plastic) " (Rubber Digest Co., Ltd., Japan) (being different from above-mentioned additive).

The proportion of foam of polymers of the present invention is 0.05-0.5, is preferably 0.1-0.3.Because the proportion of foam of polymers of the present invention is 0.05-0.5, so this foam of polymers has excellent mechanical property (for example, excellent tensile strength and excellent tearing toughness), in light weight, and very economical.The proportion of this foam of polymers records by automatic specific weight measurer.

Type by suitably selecting following linking agent and crosslinking accelerator and consumption and crosslinked condition (for example, crosslinking temperature and crosslinking time) can be regulated the proportion of described foam of polymers.

For foamy bounce impact elasticity of the present invention, preferred bounce impact elasticity is 40% or littler, more advantageously 35% or littler, even more advantageously 30% or littler.In the present invention, define the bounce impact elasticity of foam of polymers in the following manner.With thickness is that the foam of polymers sample of 15-17mm is placed on the plate with flat surface.Under 22 ℃, be that the steel ball of 16.3g falls from the descent altitude that is higher than sample with weight, so that this ball and sample bump.Bounce impact elasticity by following formula definition foam of polymers:

Bounce impact elasticity (%)=(HR/HO) * 100,

Wherein, HO represents the height of drop of ball, the rebound height of HR representative ball behind the ball impact sample.

The bounce impact elasticity of described foam of polymers is more little, and the impact absorbency of this foam of polymers is good more.

Foam of polymers of the present invention has excellent following character: snappiness, cold property are (for example, snappiness under the low temperature), impact absorbency (low bounce impact elasticity), incompressible tension set etc., so this foam of polymers can be advantageously used for absorbing body (especially footgear material) etc.

Have no particular limits for the method for preparing foam of polymers of the present invention.Basically, this foam of polymers can prepare by following mode: add whipping agent and make matrix-formation material foam in matrix-formation material, thereby obtain the alveolate foam of polymers that distributes in polymeric matrix.The example of whipping agent comprises chemical foaming agent and pneumatogen.

When matrix-formation material is foamed, can prepare foam of polymers by the method that comprises following three steps:

(1) provide matrix-formation material,

(2) in described matrix-formation material, add chemical foaming agent, but and mediate the gained mixture with obtain foam material and

(3) with step (2) but in the foam material foaming that obtains, thereby obtain foam of polymers.

Matrix-formation material is provided in step (1).Have no particular limits for the method that matrix-formation material is provided.For example, can provide matrix-formation material by following manner: the component that will be used for matrix-formation material infeeds the mixture of kneader and fusion-kneading gained, thereby obtains matrix-formation material.The example of kneader comprises conventional mixing machine, for example roll kneader (the open type rolling mill that has two rollers), Banbury mixing machine, kneader, compound mixing roll, single screw extrusion machine, twin screw extruder and multiple screw extruder.In the present invention, from the angle of productivity and kneading property, the preferred fusion-kneading method of utilizing forcing machine of using.Mediate temperature and be generally 80-250 ℃, be preferably 100-230 ℃.The kneading time is generally 4-80 minute, is preferably 8-40 minute.

Also can adopt following method that matrix-formation material is provided: will be used for the components dissolved of matrix-formation material or be dispersed in solvent, and add the heat extraction solvent afterwards.

In step (2), in described matrix-formation material, add whipping agent, and add linking agent if desired (and crosslinking accelerator), thereby but obtain foam material.As the kneader that is used for step (2), can use top at the cited any kneader of step (1).Mediate temperature and be generally 60-200 ℃, be preferably 80-150 ℃.The kneading time is generally 3-60 minute, is preferably 6-30 minute.When using linking agent, must under the kneading temperature that crosslinking reaction can excessively not carried out, mediate.The temperature range that crosslinking reaction can excessively not carried out changes according to the type of used linking agent.For example, when using dicumyl peroxide, must under 80-130 ℃, mediate as linking agent.

This kneader (used in the step (1)) can be used for the kneading of step (2) equally once more.

As the chemical foaming agent that is used for step (2), what can mention is inorganic foaming agent and organic blowing agent.

The example of inorganic foaming agent comprises sodium bicarbonate, volatile salt, bicarbonate of ammonia, ammonium nitrite, triazo-compound, sodium borohydride and metal-powder.

The example of organic blowing agent comprises azodicarbonamide, Cellmic C 121, Diisopropyl azodicarboxylate, barium azodicarboxylate, diazoamino pyridine, N; N '-dinitrosopentamethylene tetramine, N; N '-dinitroso-N; N '-dimethyl terephthalamide, benzenesulfonyl hydrazine, p-toluenesulfonyl hydrazine, p, p '-oxo two (benzenesulfonyl hydrazine) and p-toluenesulfonyl Urea,amino-.

Above-mentioned chemical foaming agent can individually or be united use.

With respect to the component of 100 weight parts (A) altogether with (B), the amount of chemical modifier is generally the 1.0-10 weight part, is preferably the 0.3-8 weight part, 0.5-6 weight part more preferably, even 1-5 weight part more preferably.

In step (2), can use linking agent (vulcanizing agent) if necessary.When using linking agent in step (2), the foaming effect in crosslinked (sulfuration) effect and the subsequent step (3) carries out simultaneously.

The example that is used for the linking agent of step (2) comprises free-radical generating agent (for example, organo-peroxide or azo-compound), oxime, nitroso compound, polyamine, sulphur and sulfocompound.The example of sulfocompound comprises sulfur monochloride, sulfur dichloride, disulphide and high molecular polysulfide.With respect to the component of 100 weight parts (A) altogether and (B), the amount of linking agent is generally the 0.01-20 weight part, is preferably the 0.1-15 weight part, more preferably the 0.5-10 weight part.When hope with foam of polymers as absorbing body, with respect to the component of 100 weight parts (A) altogether and (B), the amount of linking agent is preferably the 0.8-10 weight part, more preferably the 1-8 weight part.

The example of organo-peroxide comprises that dicumyl peroxide, ditertiary butyl peroxide, benzoyl peroxide, chloro benzoyl peroxide, peroxidation 2,4 dichloro benzene formyl, tert-butyl peroxide cumyl, the tertiary butyl cross sec.-propyl carbonic ether, diacetyl peroxide, lauroyl peroxide, cyclohexanone peroxide, tert-butyl hydroperoxide, methylethyl ketone peroxide, t-butyl per(oxy)benzoate, phthalic acid di-t-butyl diperoxy ester, lauric acid t-butyl peroxy ester and acetic acid t-butyl peroxy ester.

Other example of organo-peroxide comprises 4; two (tert-butyl hydroperoxide) n-butyl pentanoates of 4-; toxilic acid t-butyl peroxy ester; 2; two (t-butyl peroxy) butane of 2-; 1; 1-two (tert-butyl hydroperoxide) hexanaphthene; 2; 5-dimethyl-2; 5-two (t-butyl peroxy) hexane; 2,5-dimethyl-2,5-two (t-butyl peroxy)-hexin-3; 2; 5-dimethyl-2; 5-two (benzoyl peroxide) hexane; 2,5-dimethyl-2,5-two (benzoyl peroxide)-hexin-3; 2; two (tert-butyl hydroperoxide sec.-propyl) benzene of 2-; 1; two (t-butyl peroxy sec.-propyl) benzene of 3-; 1, two (t-butyl peroxy)-3,3 of 1-; 5-trimethyl-cyclohexane and 1; two (t-butyl peroxy)-3,5 of 1-, the 5-trimethyl-cyclohexane.

For above-mentioned organo-peroxide, from the little and scorching of smell stability angle, dicumyl peroxide, 2 preferably, 5-dimethyl-2,5-two (t-butyl peroxy) hexane, 2,5-dimethyl-2,5-two (t-butyl peroxy)-hexin-3,1, two (t-butyl peroxy sec.-propyl) benzene, 1 of 3-, two (t-butyl peroxy)-3 of 1-, 3,5-trimethyl-cyclohexane, 4, two (t-butyl peroxy) n-butyl pentanoates of 4-and ditertiary butyl peroxide.

In addition, when using above-mentioned organo-peroxide, auxiliary crosslinking agent (crosslinking accelerator) and organo-peroxide can be united use.The example of auxiliary crosslinking agent (crosslinking accelerator) comprises sulphur; p-quinone dioxime; right; right '-dibenzoyl quinone dioxime; N-methyl-N-4-dinitrosoaniline; nitrosobenzene; vulkacit D; TriMethylolPropane(TMP)-N; a N '-phenylenedimaleimide; Vinylstyrene; the triallylcyanurate cyanacrylate; the polyfunctional acrylic ester monomer (for example; the vinylformic acid butanediol ester; diacrylate glycol ether ester and acrylate metal salt); multifunctional methacrylate monomer (for example; the methacrylic acid butanediol ester; Ethylene glycol dimethacrylate; dimethacrylate glycol ether ester; polyethylene glycol dimethacrylate; trimethylolpropane trimethacrylate; allyl methacrylate(AMA) and methacrylic acid metal salt); with polyfunctional vinyl monomer (for example, vinyl butyrate and stearic acid vinyl ester).

With respect to the component of 100 weight parts (A) altogether and (B), the amount of auxiliary crosslinking agent (crosslinking accelerator) is generally the 0.01-20 weight part, is preferably the 0.05-15 weight part, more preferably the 0.1-10 weight part.Particularly, when foam of polymers of the present invention was used as absorbing body, the amount of auxiliary crosslinking agent (crosslinking accelerator) was preferably the 0.1-5 weight part.

In addition, when sulphur was used as linking agent, any following auxiliary crosslinking agent can be united use with sulphur: sulphenamide type auxiliary crosslinking agent, guanidine type auxiliary crosslinking agent, thiuram type auxiliary crosslinking agent, aldehyde-amine type auxiliary crosslinking agent, aldehyde-ammonia type auxiliary crosslinking agent, thiazole type auxiliary crosslinking agent, thiocarbamide type auxiliary crosslinking agent and dithiocarbamate type auxiliary crosslinking agent.In addition, zinc white or stearic acid also can be used as auxiliary crosslinking agent and sulphur is united use.

In step (3), make step (2) but in the foam material foaming that obtains to obtain foam of polymers.But have no particular limits for the method that is used for the foam material foaming.For example, can obtain foam of polymers in the following manner: but described foam material is infeeded in compacting shape machine, roller mill, stack, forcing machine or the injection moulding machine, but make the foam material foaming to obtain foam of polymers afterwards.

The method of using compacting shape machine is provided following explanation.With step (2) but in the foam material that obtains infeed in the compacting shape machine, and at 100-220 ℃ (preferred 120-200 ℃), 50-250kgf/cm ²(preferred 100-200kgf/cm ²) lower compression moulding 4-80 minute (preferred 8-40 minute), thereby but the foam material that obtains compressing.Compressed moulding finishes back 5-60 minute, when keeping the compacting shape machine internal pressure temperature of compacting shape machine is reduced to room temperature.Then, but discharge the interior pressure of compacting shape machine, thereby obtain foam of polymers so that the foam material of compression foams.

The foam of polymers that obtains can obtain with difform object, for example flap.When in step (2) linking agent and whipping agent being united when using, the foaming in crosslinked and the step (3) is carried out simultaneously, thereby the foam of polymers that obtains is the cross-linked polymer form of foam.When foam of polymers was the cross-linked polymer foam, the intensity of described foam of polymers was improved.

When using pneumatogen, for example can adopt the method that comprises following three steps to obtain foam of polymers as whipping agent:

(1) provide matrix-formation material,

(2) in described matrix-formation material, add pneumatogen, but and under pressure, mediate the gained mixture with obtain foam material and

(3) with step (2) but in the foam material that obtains remain under the barometric point, thereby obtain foam of polymers.

In step (1), provide matrix-formation material in the essentially identical mode of step (1) with the method for above-mentioned use chemical foaming agent.

Step (2) and (3) are provided following explanation, wherein are example with the extrusion and foaming process.

In step (2), matrix-formation material is infeeded in the forcing machine with whipping agent, and at 100-200 ℃, 10-100kgf/cm ²Following fusion-kneading gained mixture, thus whipping agent is dispersed or dissolved in matrix-formation material, but obtain foam material thus.

In step (3), but in air, extrude the whipping agent material via the mould of forcing machine end, thereby but make the foam material foaming, obtain foam of polymers thus.

In extrusion and foaming process, but owing to the bulging force of pneumatogen makes the foam material foaming.

The example of pneumatogen comprises hydrocarbon, for example pentane, butane and hexane; Halohydrocarbon, for example methyl chloride and methylene dichloride; Gas, for example nitrogen and air; And hydrofluoric ether, for example trichlorofluoromethane, Refrigerant 12, Refrigerant R 113, chlorine C2H4F2 C2H4F2 and fluorocarbon.

With respect to the component of 100 weight parts (A) altogether and (B), the amount of pneumatogen is generally the 0.1-8 weight part, is preferably the 0.2-6 weight part, more preferably the 0.3-4 weight part.

In step (2), can use linking agent (vulcanizing agent) if necessary.When using linking agent in step (2), the foaming in crosslinked and the subsequent step (3) is carried out simultaneously.For the type and the consumption of this linking agent, the same interpretation given with the method for using chemical foaming agent can be suitable for.

Preferred forms of the present invention

Hereinafter will be described in more detail the present invention, but it should not be considered to limitation of the scope of the invention with reference to the following example and comparative example.

Adopt following method to measure multipolymer and foamy character.

A. multipolymer character

(1) styrene monomer unit content

Adopt ultraviolet spectrophotometer (trade(brand)name: UV-2450; Japan Shimadzu Corporation produce and market) determines the not styrene monomer unit content in the hydrogenated copolymer of described basis.The described basis not styrene monomer unit content in the hydrogenated copolymer is used as styrene monomer unit content in the described hydrogenated copolymer.

(2) styrene polymer block content

Adopt the perosmic anhydride edman degradation Edman of people such as I.M.Kolthoff description in J.Polym.Sci. the 1st volume 429 pages (1946) to determine the not styrene polymer block content in the hydrogenated copolymer of described basis.Not for the degraded of hydrogenated copolymer, use the solution that the 0.1g osmic acid is dissolved in gained in the 125ml trimethyl carbinol for described basis.

(3) ethylenic linkage content

Based on ruddiness spectrophotometer (trade(brand)name: FT/IR-230; Japan Japan SpectroscopicCo., Ltd produce and market) test result adopts the Hampton method to calculate the not ethylenic linkage content in the hydrogenated copolymer of described basis.

(4) hydrogenation ratio

Adopt nucleus magnetic resonance (NMR) device (trade(brand)name: DPX-400; Germany BRUKER produce and market) measures the hydrogenation ratio.

(5) weight-average molecular weight and molecular weight distribution

Use GPC device (U.S. Waters Corporation produce and market), adopt gel permeation chromatography (GPC) to measure the basis not weight-average molecular weight and the number-average molecular weight of hydrogenated copolymer, measuring condition: use tetrahydrofuran (THF) as solvent, measuring temperature is 35 ℃.Not in the measurement of the weight-average molecular weight of hydrogenated copolymer and number-average molecular weight, use the working curve that obtains according to commercially available standard monodisperse polystyrene sample on described basis with predetermined molecular weight.Molecular weight distribution is the ratio (Mw/Mn) of weight-average molecular weight (Mw) and number-average molecular weight (Mn).

(6) degree of modification

Modified copolymer is adsorbed on silicagel column rather than the polystyrene gel post.Based on this peculiar property of described modified copolymer, determine the degree of modification of modified copolymer by following method.Preparation contains the cinnamic sample solution of mark in modified copolymer sample and the lower molecular weight, makes the sample solution that makes through using the GPC (trade(brand)name: Shodex of standard type polystyrene gel post; Japan Showa DenkoCo., Ltd. produce and market), its with top (5) used identical, thereby obtain color atlas.On the other hand, use silicagel column (trade(brand)name: Zorbax; U.S. DuPont deNemours﹠amp; Company Inc. produce and market) replace standard type polystyrene gel post, other condition according to top essentially identical mode, make same sample solution obtain another color atlas by GPC.Determine to be adsorbed on the amount of the multipolymer fraction (being included in the modified copolymer) on the silicagel column from using difference between polystyrene gel post color atlas that obtains and the color atlas that uses the silicagel column acquisition.Obtain the degree of modification of modified copolymer according to the amount of the multipolymer fraction of determining.

(7) observe the temperature at loss tangent (tan δ) peak

Adopt dynamic viscoelasticity spectrum map analysis instrument (model: DVE-V4; Japan Rheology Co., the Ltd. produce and market) obtain dynamic viscoelasticity spectrum figure, wherein analyze under the frequency of 10Hz and carry out.Obtain to observe the temperature at loss tangent (tan δ) peak according to dynamic viscoelasticity spectrum figure.

(8) heat at peak crystallization and peak crystallization place

Use differential scanning calorimeter (DSC) (trade(brand)name: DSC3200S; Japan MAC ScienceCo., the Ltd. produce and market), measure the peak crystallization of described hydrogenated copolymer and the heat at peak crystallization place according to following method.Hydrogenated copolymer is infeeded in the differential scanning calorimeter.With the speed of 30 ℃/min the internal temperature of differential scanning calorimeter is increased to 150 ℃ from room temperature, is reduced to-100 ℃ with the speed of 10 ℃/min from 150 ℃ then, thereby obtains the DSC figure (that is crystallization curve) of hydrogenated copolymer.DSC figure according to gained confirms whether to exist peak crystallization.When observing peak crystallization on DSC figure, the temperature of observing peak crystallization is defined as crystallization peak temperature, and measures the heat at peak crystallization place.

B. foam property

(1) foamy proportion

Use automatic specific weight measurer (trade(brand)name: Automatic Sp.Gr.CalibratorDMA3; Japan Ueshima Seisakusho Co., the Ltd. produce and market) mensuration foamy proportion.

(2) hardness

According to ASTM-D2240, (Japanese KOUBUNSHIKEIKI CO. LTD.) measures foamy hardness down at 22 ℃ and-10 ℃ to adopt Asker C type hardness tester meter.Foam hardness under 22 ℃ is more little, and the foamy snappiness is good more.On the other hand, the foam hardness under-10 ℃ is more little, and the foamy cold property is good more.

(3) tensile strength, elongation and tearing toughness

Use No. 2 the dumbbell shaped cutting unit, make the thick sample of 3mm by foam.According to ASTM-D412 sample is measured.

(4) compression set

According to ASTM-D3754, adopt following method to measure foamy compression set.Foam specimen is placed on the compressor, and this foam is the cylindricality of height (thickness) 10mm, diameter 30mm.Compress this sample, make the sample thickness of thickness phase time before compression of gained compression sample reduce 50% (wherein, used thickness is half conductor spacer of the preceding sample thickness of compression).Sample is continued compression 6 hours down in 50 ℃ in compressor.From compressor, take out sample then and place it under the room temperature.Define foamy compression set by following formula:

Cs(％)＝{(TO-TF)/(TO-TS)}×100

Wherein, the sample thickness before the TO representative compression, TF represents the sample thickness after sample is at room temperature placed, and TS represents the thickness of conductor spacer.

Foamy Cs value (compression set) is more little, and the incompressible tension set of foamy is good more.

(5) bounce impact elasticity

Measure the bounce impact elasticity of foam of polymers according to following method.With thickness is that the foam of polymers sample of 15-17mm is placed on the plate with flat surface.Under 22 ℃, be that the steel ball of 16.3g falls from the descent altitude that is higher than sample with weight, so that producing bump, this ball and sample bump.Measure the descent altitude of ball and the rebound height behind the ball impact sample.Bounce impact elasticity by following formula definition foam of polymers:

Bounce impact elasticity (%)=(HR/HO) * 100,

Wherein, HO represents the height of drop of ball, and HR represents the rebound height of ball behind the ball impact sample.

The bounce impact elasticity of foam of polymers is more little, and the impact absorbency of foam of polymers is good more.

C. the preparation of hydrogenation catalyst

Prepare hydrogenation catalyst I and the II that uses in the hydrogenation according to following method.

(1) hydrogenation catalyst I

Use the nitrogen purging reaction vessel.In reaction vessel, infeed 1 liter of exsiccant purity ring hexane, add 100mmol molybdenyl dichloride (η 5-cyclopentadienyl) afterwards and close titanium.When fully stirring in this reaction vessel the gained mixture, the hexane solution that will contain the 200mmol trimethyl aluminium infeeds in the reaction vessel, and at room temperature reacts about 3 days, thereby obtains hydrogenation catalyst I (it contains titanium).

(2) hydrogenation catalyst II

Use the nitrogen purging reaction vessel.In reaction vessel, infeed 2 liters of exsiccant purity ring hexanes, add afterwards that 40mmol two (p-methylphenyl) two (η 5-cyclopentadienyls) closes titanium and the 150g molecular weight is about 1,000 and 1,2-ethylenic linkage content be about 85% 1, the 2-polyhutadiene.In gained solution, add and contain the cyclohexane solution of 60mmol n-Butyl Lithium, and at room temperature reacted 5 minutes.In the gained reaction mixture, add the 40mmol propyl carbinol immediately, stir afterwards, thereby obtain hydrogenation catalyst II.

D. the preparation of hydrogenated copolymer etc.

＜polymkeric substance 1 〉

Use internal volume to be 10 liters and to be equipped with agitator and the reaction vessel of chuck, carry out copolyreaction according to following method.

10 weight part hexanaphthenes are infeeded in the described reaction vessel, and with the temperature regulation to 70 in this reaction vessel ℃.Then, with n-Butyl Lithium and N, N, N ', N '-Tetramethyl Ethylene Diamine (hereinafter being called " TMEDA ") infeeds in the reaction vessel, wherein based on monomeric gross weight (that is, infeed in the reaction vessel divinyl and cinnamic gross weight), the amount of n-Butyl Lithium is 0.08 weight %, and the amount of TMEDA is counted 0.4mol with the mol n-Butyl Lithium.

Contained the cyclohexane solution (concentration of styrene of solution: 22 weight %) infeed in the described reaction vessel of 8 parts by weight of styrene at 3 minutes, when the internal temperature that keeps this reaction vessel is about 70 ℃, polyreaction (first polyreaction) was carried out 30 minutes.

Then, cyclohexane solution (divinyl and the cinnamic total concn in the solution: 22 weight %) infeed continuously in the described reaction vessel, thereby carry out polyreaction (second polyreaction) that in 60 minutes, will contain 48 weight parts of butadiene and 36 parts by weight of styrene with constant speed.In this polymerization process, the internal temperature of reaction vessel is maintained at about under 70 ℃.

Afterwards, cyclohexane solution (the concentration of styrene of solution: 22 weight %) infeed in the described reaction vessel that in 3 minutes, will contain 8 parts by weight of styrene, when the internal temperature that keeps this reaction vessel is about 70 ℃, polyreaction (trimerization reaction) was carried out 30 minutes, thereby obtain not hydrogenated copolymer.

The gained not styrene monomer unit content of hydrogenated copolymer is 52 weight %, and styrene polymer block content is 16 weight %, and the ethylenic linkage content that records at butadiene monomer unit in the described not hydrogenated copolymer is 20 weight %.In addition, the weight-average molecular weight of described not hydrogenated copolymer is 150,000, and molecular weight distribution is 1.1.

Adding above-mentioned hydrogenation catalyst II in described not hydrogenated copolymer, based on the weight of hydrogenated copolymer not, is 100ppm weight in its amount of titanium amount, is that 0.7MPa, temperature of reaction are to carry out hydrogenation under 65 ℃ the condition at hydrogen pressure.After hydrogenation finishes, in reaction vessel, add methyl alcohol, its amount is 0.1 weight % based on hydrogenated copolymer not, add 3-(3 afterwards as stablizer, the 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl, its amount is 0.3 weight % based on hydrogenated copolymer not, thereby obtains hydrogenated copolymer (hereinafter, this multipolymer is known as " polymkeric substance 1 ").

The hydrogenation ratio of polymkeric substance 1 is 99%.In addition, in the dynamic viscoelasticity spectrum figure of the polymkeric substance 1 that obtains, locate to observe tan δ peak at-15 ℃.And, in the DSC figure of the polymkeric substance 1 that obtains, do not observe the peak crystallization that belongs to the styrene/butadiene copolymers block under-50 to 100 ℃ basically.

＜polymkeric substance 2 〉

According to making not hydrogenated copolymer with preparation polymkeric substance 1 essentially identical mode, different is changes the n-Butyl Lithium that infeeds in the reaction vessel and the amount of monomer (that is, divinyl and vinylbenzene) in the following manner: the amount that infeeds the n-Butyl Lithium in the reaction vessel is 0.07 weight %; Infeeding the cinnamic amount that is used for first polyreaction in the reaction vessel is 6 weight parts; Infeed the divinyl and the cinnamic amount that are used for second polyreaction in the reaction vessel and be respectively 54 weight parts and 34 weight parts; Infeeding the cinnamic amount that is used for the trimerization reaction in the reaction vessel is 6 weight parts.

The gained not styrene monomer unit content in the hydrogenated copolymer is 46 weight %, and styrene polymer block content is 12 weight %, at butadiene monomer unit in the hydrogenated copolymer not and the ethylenic linkage content that records is 22 weight %.In addition, the weight-average molecular weight of described not hydrogenated copolymer is 165,000, and molecular weight distribution is 1.1.

According to carrying out hydrogenation, thereby obtain hydrogenated copolymer (hereinafter, this multipolymer is called " polymkeric substance 2 ") with preparation polymkeric substance 1 essentially identical mode.

The hydrogenation ratio of polymkeric substance 2 is 98%.In addition, in the dynamic viscoelasticity spectrum figure of the polymkeric substance 2 that obtains, under-25 ℃, observe tan δ peak.And, in the DSC figure of the polymkeric substance 2 that obtains, do not observe the peak crystallization that belongs to the styrene/butadiene copolymers block under-50 to 100 ℃ basically.

＜polymkeric substance 3 〉

According to obtaining the reactive polymer of solution form with polymkeric substance 1 essentially identical mode.Add 1 in the solution of described reactive polymer, 3-dimethyl-2-imidazolone is as properties-correcting agent, and its molar weight equals to prepare the molar weight of the used n-Butyl Lithium of reactive polymer, thereby obtains the not hydrogenated copolymer of modification.This modification not degree of modification of hydrogenated copolymer is 70%.

Then, modification to the solution form does not add hydrogenation catalyst II in the hydrogenated copolymer, based on the modification weight of hydrogenated copolymer not, be 100ppm weight in its amount of titanium amount, be that 0.7MPa, temperature of reaction are to carry out hydrogenation under 70 ℃ the condition at hydrogen pressure.After hydrogenation finishes, in reactor, add 3-(3 as stablizer, the 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl, with respect to the modification of 100 weight parts hydrogenated copolymer not, its amount is 0.3 weight part, remove afterwards and desolvate, thereby obtain the hydrogenated copolymer (hereinafter, this multipolymer is known as " polymkeric substance 3 ") of modification.

The hydrogenation ratio of polymkeric substance 3 is 99%.In addition, in the dynamic viscoelasticity spectrum figure of the polymkeric substance 3 that obtains, under-15 ℃, observe tan δ peak.And, in the DSC figure of the polymkeric substance 3 that obtains, do not observe the peak crystallization that belongs to the styrene/butadiene copolymers block under-50 to 100 ℃ basically.

＜polymkeric substance 4 〉

Add maleic anhydride in polymkeric substance 3, be connected in functional group on the polymkeric substance 3 with respect to 1 equivalent, its amount is 2.1mol.Use the twin screw extruder of 30mm Φ, fusion-kneading gained mixture is about 2 minutes under 210 ℃, the condition of screw rod speed of rotation 100rpm, thereby obtains the hydrogenated copolymer (hereinafter, this multipolymer is called " polymkeric substance 4 ") of secondary modification.

In the dynamic viscoelasticity spectrum figure of the polymkeric substance 4 that obtains, under-15 ℃, observe tan δ peak.In addition, in the DSC figure of the polymkeric substance 4 that obtains, do not observe the peak crystallization that belongs to the styrene/butadiene copolymers block in-50 to 100 ℃ of scopes basically.

＜rubbery polymer 1 〉

Make not hydrogenated copolymer according to following method by carrying out the successive polymerization reaction: wherein use two reaction vessels (promptly, first reaction vessel and second reaction vessel), each reaction vessel has 10 liters of internal volumes respectively, and is equipped with agitator and chuck.

The cyclohexane solution (butadiene concentration of solution: 24 weight %) with divinyl, cinnamic cyclohexane solution (concentration of styrene of solution: 24 weight %) and the cyclohexane solution of n-Butyl Lithium (with respect to the divinyl and the vinylbenzene of 100 weight parts altogether, it contains the n-Butyl Lithium of 0.077 weight part) infeed the bottom of first reaction vessel, feeding rate is respectively 4.51 liters/hour, 5.97 rise/hour and 2.0 liters/hour, cyclohexane solution with TMEDA infeeds in first reaction vessel simultaneously, used feeding rate makes the amount of TMEDA count 0.44mol with every mol n-Butyl Lithium, thereby under 90 ℃, carry out the successive polyreaction, obtain polymerization reaction mixture.In described successive polymerization reaction, come the conditioned reaction temperature by the control jacket temperature.Temperature around first reaction container bottom is about 88 ℃, and the temperature around the first reaction vessel top is about 90 ℃.The mean residence time of polymerization reaction mixture in first reaction vessel is 45 about minutes.Divinyl and cinnamic transformation efficiency are respectively about 100% and 99%.

From first reaction vessel, take out polymers soln, and infeed the bottom of second reaction vessel.When infeeding described polymers soln, (concentration of styrene of solution is: the bottom that 24 weight %) infeeds second reaction vessel with cinnamic cyclohexane solution with 2.38 liters/hour feeding rates, thereby under 90 ℃, carry out the successive polymerization reaction, to obtain not hydrogenated copolymer.The styrene conversion rate that records in the outlet of second reaction vessel is 98%.

Analyze the not hydrogenated copolymer of gained according to the method described above.Found that the styrene monomer unit content of hydrogenated copolymer is not 67 weight %, the content of styrene polymer block is 20 weight %, at butadiene monomer unit in the hydrogenated copolymer not and the ethylenic linkage content that records is 14 weight %.Find that also the weight-average molecular weight of hydrogenated copolymer is not 200,000, molecular weight distribution is 1.9.

Then, adding above-mentioned hydrogenation catalyst I in hydrogenated copolymer, based on the weight of hydrogenated copolymer not, is 100ppm weight in this its amount of titanium amount, and is that 0.7MPa, temperature of reaction are to carry out hydrogenation under 65 ℃ the condition at hydrogen pressure.After hydrogenation finishes, in second reaction vessel, add methyl alcohol, add 3-(3 afterwards as stablizer, the 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl, not hydrogenated copolymer with respect to 100 weight parts, its amount is 0.3 weight part, thereby obtains hydrogenated copolymer (hereinafter, this multipolymer is known as " rubbery polymer 1 ").

The hydrogenation ratio of rubbery polymer 1 is 99%.In addition, in the dynamic viscoelasticity spectrum figure of the rubbery polymer 1 that obtains, under 10 ℃, observe tan δ peak.And, in the DSC figure of the rubbery polymer 1 that obtains, do not observe the peak crystallization that belongs to the styrene/butadiene copolymers block in-50 to 100 ℃ of scopes basically.

Embodiment 1

70 weight parts are infeeded in kneader (fusion-kneader) (trade(brand)name: DJ K-1 as the additive shown in " the first step " of the rubbery polymer 1 of rubbery polymer and table 1 with its consumption as polymkeric substance 1,30 weight parts of hydrogenated copolymer; Korea S Dae-Jung Precision MachineryCo. produce and market).About 120 ℃ of following fusions-kneading gained mixture 15 minutes, thus the mixture that obtains mediating (hereinafter, the mixture of this kneading is called " first mediates mixture ").Then, the additive shown in " second step " of the first kneading mixture and table 1 is infeeded (fusion-kneader) (trade(brand)name: DJ M in two roller open type roller mills with its consumption; Korea S Dae-JungPrecision Machinery Co. produce and market), and about 100 ℃ of following fusions-kneading gained mixture 10 minutes, thereby the mixture that obtains mediating (hereinafter, the mixture of this kneading is called " second mediates mixture ").

Use compacting shape machine (trade(brand)name: DJ PT; Korea S Dae-Jung Precision MachineryCo. produce and market), at 160 ℃, 150kgf/cm ²Under this second was mediated mixture compression forming 20 minutes.Compressed moulding finishes back 20 minutes, and the gained compressing mixt is cooled to room temperature, and keeping the pressure in the compacting shape machine simultaneously is 150kgf/cm ²Afterwards, the pressure that discharges in the compacting shape machine makes the compressing mixt foaming, thereby obtains foam of polymers.

Resulting polymers foamy character is as shown in table 1.As seen, this polymeric foam has excellent following character from table 1: snappiness, cold property, incompressible tension set and impact absorbency (low bounce impact elasticity).

Embodiment 2

Except that using the polymkeric substance shown in the table 1 and additive and consumption thereof, all the other obtain foam of polymers according to mode substantially the same manner as Example 1.

Resulting polymers foamy character is as shown in table 1.As seen, this foam of polymers has excellent following character from table 1: snappiness, cold property, incompressible tension set and impact absorbency (low bounce impact elasticity).

Embodiment 3

Embodiment 4

Embodiment 5

Embodiment 6

Except carrying out following variation: the polymkeric substance 1 that uses 35 weight parts is as hydrogenated copolymer; Use the ethylene/vinyl acetate copolymer (trade(brand)name: EVA460 of 30 weight parts; DuPont deNemours﹠amp; Company Inc. (U.S.) produce and market; Vinyl Acetate Monomer unit content: 18 weight %) as olefin polymer; Use hydrogenated products (trade(brand)name: the Hybrar 7125 of the styrene/isoprene segmented copolymer of 35 weight parts; KURARAY CO., LTD. (Japan) produce and market) as rubbery polymer, all the other obtain foam of polymers according to mode substantially the same manner as Example 1.

Resulting polymers foamy proportion is 0.18.In addition, this foam of polymers have with embodiment 1 in the suitable excellent properties of foam of polymers that obtains.

Embodiment 7

Except that using polymkeric substance 3 to replace polymkeric substance 1 as the hydrogenated copolymer, all the other make foam of polymers according to mode substantially the same manner as Example 1.

Resulting polymers foamy proportion is 0.22.In addition, this foam of polymers have with embodiment 1 in the suitable excellent properties of foam of polymers that obtains.

Embodiment 8

Except that using polymkeric substance 4 to replace polymkeric substance 1 as the hydrogenated copolymer, all the other make foam of polymers according to mode substantially the same manner as Example 1.

Resulting polymers foamy proportion is 0.23.In addition, this foam of polymers have with embodiment 1 in the suitable excellent properties of foam of polymers that obtains.

Comparative example 1

Resulting polymers foamy character is as shown in table 1.As seen, the cold property of this foam of polymers (snappinesies under-10 ℃ of low temperature) is bad from table 1.

Industrial applicibility

Foam of polymers of the present invention has excellent following character: pliability, low-temperature characteristics are (for example, Pliability under the low temperature), impact absorbency (low bounce impact elasticity), incompressible permanent deformation etc., So this foam of polymers can be advantageously used for absorbing body, and (especially the footgear material for example is used for The material of the end and midsole in the footwear), the material that is used for domestic electric appliance (is used for rotary machine Absorbing body or padded coaming etc.), be used for material (beam material, the vibration resistance of automobile component Damping material, acoustic material etc.), be used for the padded coaming of connection with wrapping of piece etc.

Claims

Described polymeric matrix is made up of following substances:

Described hydrogenated copolymer (A) has following feature (1) and (2):

(2) in the dynamic viscoelasticity spectrum figure of the described hydrogenated copolymer (A) that obtains, observe at least one losstangenttan peak to being lower than in-10 ℃ of scopes in-40 ℃,

It is characterized in that the proportion of described foam of polymers is 0.05～0.5.

2. according to the foam of polymers of claim 1, it is characterized in that wherein with respect to the component of 100 weight parts (A) altogether and (B), the amount of described hydrogenated copolymer (A) and polymkeric substance (B) is respectively 5～95 weight parts and 95～5 weight parts.

3. according to the foam of polymers of claim 1, it is characterized in that wherein with respect to the component of 100 weight parts (A) altogether and (B), the amount of described hydrogenated copolymer (A) and polymkeric substance (B) is respectively 20～65 weight parts and 80～35 weight parts.

4. according to the foam of polymers of claim 1 or 2, it is characterized in that, wherein in the differential scanning calorimetric DSC of the described hydrogenated copolymer (A) that obtains figure, do not observe the peak crystallization that is produced by at least one hydrogenated copolymer block that described at least one copolymer block S hydrogenation is obtained in-50 to 100 ℃ of scopes, perhaps in described differential scanning calorimetric DSC figure, observe the peak crystallization that described at least one hydrogenated copolymer block is produced in-50 to 100 ℃ of scopes, but the heat at this peak crystallization place is less than 3J/g.

5. according to the foam of polymers of claim 1 or 2, it is characterized in that wherein in described not hydrogenated copolymer, at least one among described at least one copolymer block S has the structure that wherein said vinyl aromatic monomer units distributes with the gradient form.

6. according to the foam of polymers of claim 1 or 2, its special type is, wherein said not hydrogenated copolymer also contains the homopolymer block H of vinyl aromatic monomer units, in the weight of described not hydrogenated copolymer, the amount of the described homopolymer block H in the described not hydrogenated copolymer is 1～40 weight %.

7. according to the foam of polymers of claim 1 or 2, it is characterized in that wherein said not hydrogenated copolymer is at least a polymkeric substance that is selected from respectively by the multipolymer of following formula representative:

(1)S，

(2)S-H，

(3)S-H-S，

(4)(S-H) _m-X，

(5)(S-H) _n-X-(H) _p，

(6)H-S-H，

(7)S-E，

(8)H-S-E，

(9)E-S-H-S，

(10) (E-S-H) _m-X and

(11)(E-S-E) _m-X，

8. according to the foam of polymers of claim 1 or 2, it is characterized in that, be connected with properties-correcting agent on the wherein said hydrogenated copolymer (A) with functional group.

9. foam of polymers according to Claim 8 is characterized in that, wherein said properties-correcting agent is one-level properties-correcting agent, and it has at least one functional group that is selected from hydroxyl, epoxy group(ing), amino, silanol group and alkoxysilane group.

10. foam of polymers according to Claim 8 is characterized in that, wherein said properties-correcting agent comprises one-level properties-correcting agent and the secondary properties-correcting agent that is connected thereon,

11. foam of polymers according to claim 1 or 2, it is characterized in that wherein the described olefin polymer as component (B) is at least a following ethene polymers that is selected from: polyethylene, ethylene/propene copolymer, ethylene/propene/butylene copolymer, ethylene/butylene copolymers, ethylene/hexene multipolymer, ethylene/octene, ethylene/vinyl acetate copolymer, ethene/acrylic ester multipolymer and ethylene/methacrylic acid ester copolymer.

12. the foam of polymers according to claim 1 or 2 is characterized in that, wherein the described rubbery polymer as component (B) is at least a following material that is selected from: 1, and the 2-polyhutadiene; The hydrogenated products of conjugated diene homopolymers; Multipolymer and the hydrogenated products thereof formed by vinyl aromatic monomer units and conjugated diene monomeric unit; Acrylonitrile/butadiene rubber and hydrogenated products thereof; Ethylene/propylene/diene rubber EPDM; Isoprene-isobutylene rubber and natural rubber.

13. foam of polymers according to claim 12, it is characterized in that, it wherein is the hydrogenated products of the multipolymer formed by vinyl aromatic monomer units and conjugated diene monomeric unit as the described rubbery polymer of component (B), in the weight of described hydrogenated products, the vinyl aromatic monomer units content of described hydrogenated products is greater than 60 weight % to 90 weight %.

14. foam of polymers according to claim 1 or 2, it is characterized in that wherein the described rubbery polymer as component (B) is at least a following material that is selected from: by the homopolymer block of vinyl aromatic monomer units with at least aly be selected from segmented copolymer and the hydrogenated products thereof that following polymer blocks is formed: the homopolymer block of conjugated diene monomeric unit and the copolymer block of forming by vinyl aromatic monomer units and conjugated diene monomeric unit.

15. the foam of polymers according to claim 1 or 2 is characterized in that, it demonstrates 40% or littler bounce impact elasticity.

16. the foam of polymers according to claim 1 or 2 is characterized in that, its proportion is 0.1～0.3.

17. according to the foam of polymers of claim 1 or 2 purposes as absorbing body.