CA2082372A1 - Method for producing thermoplastic elastomer composition - Google Patents

Method for producing thermoplastic elastomer composition

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Publication number
CA2082372A1
CA2082372A1 CA002082372A CA2082372A CA2082372A1 CA 2082372 A1 CA2082372 A1 CA 2082372A1 CA 002082372 A CA002082372 A CA 002082372A CA 2082372 A CA2082372 A CA 2082372A CA 2082372 A1 CA2082372 A1 CA 2082372A1
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Canada
Prior art keywords
copolymer rubber
olefinic
weight
particulate
olefinic copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA002082372A
Other languages
French (fr)
Inventor
Tatsuo Hamanaka
Noboru Komine
Tadashi Hikasa
Yuji Gotoh
Keitaro Kojima
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Publication of CA2082372A1 publication Critical patent/CA2082372A1/en
Abandoned legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/14Peroxides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/20Carboxylic acid amides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00Crosslinking

Abstract

ABSTRACT

METHOD FOR PRODUCING THERMOPLASTIC ELASTOMER COMPOSITION

Provided is a method for producing a thermoplastic elastomer composition excellent in flexibility, mechanical properties and extrusion moldability which comprises directly feeding a particulate olefinic copolymer rubber (A) having a particle shape index .alpha. defined below of 0.1-0.9 and an olefinic plastic (B) to a continuous kneading extruder to carry out melt kneading and then, feeding an organic peroxide to downstream side of said extruder to carry out dynamic crosslinking:

.alpha.=DA/DB

wherein DA denotes bulk density of the particulate olefinic copolymer rubber (A) and DB denotes bulk density of the olefinic plastic (B).

Description

, i METHOD FOR PRODUCING THERMOPLASl'IC ELASTOMER COMPOSITION

The present invention relates to a method for producing thermoplastic elastomer compositions. More particularly, it relates to a method Eor producing olefinic ~r thermoplastic elastomer compositions excellent in mechanical properties and substitutable for vulcanized rubbers.

Various uses oE thermoplastic elastomers (herein-after reEerred to as "TPE") have been developed in thefields of automobile parts, appliance parts and haber-dasheries utilizing their Eeatures that vulcanizing step is not required and they can be processed by molding machines for ordinary thermoplastic resins. Among them, olefinic TPE compositions are known, Eor example, in Japanese Patent Kokai No. 58-26838. However, these compo-sitions have limit in their use in the fièld of substitutes for ~ulcanized rubbers because they are inferior to vulcanized rubbers in flexibility, tensile strength at break, eloncJation at break and compression set.

Various attempts have been made for improving these properties, for ex~ttple, impartation of flexibility by adding mineral oil type softeners or peroxide-uncross-linking type hydrocarbvn rubbery materials or improvementof compression set by increasing crosslinking degree using crosslinkin~ aids, as reported in Japanese Patent Kokoku Mo. 56-15740 and Japanese Patent Rokai Nos. 58--25340, 58-152023 and 59-580~3.
f~owever, even it compression set o f these compo-sitions is improved by increasing crosslinking degree, there occurs reduction in flexibility, decrease in breaking strength and breaking extension in tensile strength tests cr bleedin~ of the soEtener to the surface of the '~ compositions and thus, it is difEicult to obtain oleEinic : :, .: 20s2372 TPE compositions well balanced in properties.

Accordingly, th~ object oE the present invention is to provide a method for producing o]efinic TPE composi-tions which are s~bstitutable for vulcanized rubbers in respect of fle~ibility and mechanical properties, especially, tensile strength at break, elongation at break and compression set and are excellent in blow moldability, extrusion moldability and injection rnoldability.
As a result of intensive research conducted by the inventors, it has been found that compositions prepared by ~yn~nic crosslinking of particulate ole~inic copolymer rllbbers having a specific parti~le shap~ index and olefinic plastics by a specific method are excellent in flexibility and mechanical properties. Thus, th~
present invention has been accomplishcd.

That i.s, the present invention relates to a method for producing a thermoplastic ela~tomer composition, characterized by directly feeding (A) a particulate olefinic copolymer rubber having a particle shape index a shown by th~ following formula o~ 0.1-0.9 and (B) an oleEinic ~Iastic to a continuous kneading extruder to carry Z5 out melt kneading and then, feeding an organic pero~ide at downstream side of the extruder to carry out dynamic crosslinking.

(I -DA/V~
DA: Bulk density of particulate olefinic copolymer rubber (A) DH: Bulk density of olefinic plastic (B) ~ 3 ~ 2~2372 r~ Fig. 1 is an electron microscope which shows particle structure of the composition obtained in Example.

Fig. 2 is an electron microscope which shows particle structure of the composition obtained in Comparative ~xample.
, The particulate olefinic copolymer rubber (A) is preferably a particulate oil extended olefinic copolymer rubber containing 20-150 parts by weight of a mineral oil softener per 100 parts by weight of the olefinic copolymer rubber.

Furthermore, the dynamic crosslinking is preferably carried out at a maximum shear rate of 500/sec or higher.

The olefinic copolymer rubbers which constitute the particulate olefinic copolymer rubbers (A) used in the present invention are amorphous and random elastomeric copolymers mainly composed of olefins such as ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene rubber, ethylene-butene-1-non-conjugated diene rubber and propylene-butene-1 copolymer rubber.
Among them, ethylene-propylene-non-conjugated diene rubber (hereinafter referred to as "EPDM~) is especially preferred.
The non-conjugated dienes include, for example, dicyclo-pentadiene, 1,4-hexadiene, cyclooctadiene, methylene-norbornene and ethylidenenorbornene. Ethylidenenorbornene is especially preferred.

More specific preferable examples are ethylene-propylene-ethylidenenorbornene copolymer rubbers containing 10-55% by weight, preferably 20-40~ by weight of propylene and 1-30% by weight, preferably 3-20% by weight of ethylidenenorbornene.

- 4 _ 2~82372 If propylene content is ~ess than 10% by weight, flexibility is lost and if it is more than 55% by weight, mechanical properties deteriorate. If ethylidenenorbornene content is less than 1~ by weight, mechanical properties deteriorate and if it is more than 30% by weight, injection moldability is inferior.

Mooney viscosity MLl+4 100C of the olefinic copolymer rubbers is preferably 30-350. If it i5 lower than 30, mechanical properties are lost and if it is higher than 350, appearance of molded products is damaged.

If necessary, mineral oil softeners can be used in the present invention. They can be fed from optional portions of the extruder or can be used as oil extended olefinic copolymer rubbers by previously incorporating into the olefinic copolymer rubbers.

When MLl~4 ~00C is 30-150, preferably the former method is employed and when it is 80-350, preferably the latter method is employed.

From the point of properties of olefinic TPE
compositions obtained by the present invention, olefinic copolymer rubbers having an MLl t4 100C of 80-350 are preferred. Mechanical properties such as tensile strength at break and elongation at break are markedly improved and compression set is also improved due to increase of cross-linking degree by using the olefinic copolymer rubbers having an ML1 t4 100C of B0-350. From the point of properties, MLl t4 lnC is more preferably 120-350, e.~pecially prefer.~bly ]40-300.

When oil extended oleEinic copolymer rubbers are used, they contain mineral oil softeners in an amount of 20-150 parts by weight, preferably 30-120 parts by weight per lOa parts by weight of the olefinic copolymer rubbers.
If the content is less than 20 parts by weight, Elowability of olefinic TPE compositions decreases and e~pecially extrusion processability and injection moldability are damaged. If it is more than 150 parts by weight, plasticity much increases and processability deteriorates and besides, performances of the products deteriorate.

Mooney viscosity ML1~4 100C of the oil extellded olefinic copolymer rubhers is preferably 3n-150, more preferably 40-100. If it is lower than 30, mechanical properties are lost and if it is higher than 150, process-ability is inferior.

The mineral oil softerlers used in the oil extended olefinic copolymer rubbers are petroleum fractions of high boiling point added or improvement of processahility and mechanical properties ana include, for example, paraffinic, naphthenic and aromatic oils and paraffinic oils are preferred. When aromatic components increase, contamina-tion increases and there are limits in use for making transparent products or light color products.

Next, properties and production of oil extended olefinlc copolymer rul)bers (oil extended EPDM) will be explained taking the case oE ~E'DM.
~0 When the mineral oil softeners are added in a large amount to EPDM having an MLl~4 100C of 80-350, vlefinic TPE: compo~it;ons capable of simultaneously attclining the improvement of processability resulting ~5 fram ensuriny of flexibility and increase of flowability - 6 - 208237~

and the impro~ement of mechanical properties can be obtained.

Mineral oil softeners are generally used as flowability improvers in olefinic TPE compositions, but according to the research conducted by the inventors, when oil extended EPDM is not used, addition of more than 40 parts by weight of mineral oil softeners to 100 parts by weight of EPDM causes bleeding of the softeners to the surface of TPE compositions to bring about staining and tackiness of products.

However, when oil extended EPDM previously containing 20-150 parts by weight of mineral oil softeners per 100 parts by weight of EPDM having an ML1~4 100C of 80-350 is used, TP~ compositions can be obtained which show little bleeding of softener, have no stain and tackiness and are excellent in properties such as tensile strength at break, elongation at break and compression Z0 set. Bleeding of softener is not seen in spite of the high content of the softener. It is considered that this is because upper limit of oil eztension amount of the mineral oil softener increases when EPDM of relatively high Mooney viscosity is used and previously properly added softener is uniformly dispersed in EPDM.

Oil extension of EPDM is carried out by known methods. For example, oil extension can be performed by mechanical kneading of EYDM and mineral oil softener using apparatuses such as roll and ~anbury mixer. Alternatively, a given amount of mineral oil softener is added to EPDM
solution and then the solvent is removed by steam stripping or the like. Prcferred is to use the EPDM solution and u~e o EPI)M solution obtained by polymerization is ~5 preferable for easy operation.

Particulate ole~inic copolymer rubbers (A) can be obtained from (oil extended) oleEinic copoly~er rubbers by the following methods.

1. Grinding of bale form rubbers.
(1) Grin~ing by grinders generally used for rubbers.
(2) Grinding by high-speed mills or jet yrinders at low temperatures.
2. &ranulation by extruders and the like.
I0 3. Sheeting by roll and the like and granulating the sheet by pelletizer 4. Using crumby polymer per se obtained by removal of solvent after polymerization.

The methods 1 and ~ are preferred.

Particles of the particulate rubbers mean amorphous particles and include not only spherical or columnar particles, but alsD rectangular, flaky, crumby and linty particles and further include those which contain voids such as foamed particles. That is, there are no limitations in their form as far as they can be recognized as individual particles.

Moreover, a small amount of powders such as inorganic fillers, olefinic plastics, organic lubricants and inorganic lubricants and liquid materials such as silicone oil can be deposited on the surface of the particulate rubbers or incorporated into the particulate rubbers for inhibition of sticking of the particles to each other.

The olefinic plastics (~) used in the present inventLon are polypropylene or copolymers of propylene with a -olefins of two or more carbon atoms. Examples of the a -olefins of two or more carbon atoms are ethylene, l-butene, 1-pentene, 3-methyl-1-butene, l-hexene, l-decene, 3-methyl-l-pentPne, 4-methyl-1-pentene and l-octene.

Melt 10w rate of the po-yme~s is preferably O.l-lOO ~/10 min, more preferably 0.5-50 g/10 min. If the melt flow rate is less than 0.1 g/10 min or more than 100 g/lO min, there may occur problems in processability.

Weight ratio of the particulate olefinc copolymer rubbers (A) and the olefinic plastics (B) is preferably (A)/(B)=20-95/80-5, more preferably 35-90/65-15, especially preferably 35-85/65-15.

The particle shape inde~1 in the present inven-tion i5 a ratio of bu1k density DA of the particulate olefinic copolymer rubber ~A) and bulk density D B of the olefinic plastic (~) which is represented by the following formula.

(1 =DA/D~3 The (I is an index which greatly influences the step o~ carrying out melt kneading of the components (A) and (B) by directly feeding them to an extruder.
~5 Especially, in thc case of using an olefinic copolymer rubber having a high MLl+4 lOOnC, the has a great in1uence on morpho109y oE the composition o~ said copolymer:rubber and olefinic plastic.
The dispersibiLity of the resulting composition exerts a great inluence on properties and processability of the TPE composition obtained through the subsequent dynamic crosslinking step ,:' ' 208237~
g J The particle shape index a in the present invention is in the range of 0.1-0.9. If it is less than 0.1, transporting efficiency is inferior in solid transporting part o~ the continuous kneading extnlder and sometimes blockage occurs. Further, mixability and kneadability in kneading part of kneader also reduce and , besides, it is dificult to fonn satisEactory morphology in the resulting TPE composition.
,.
The ~ is preferably in the range of 0.3-0.8.

Organic peroxides used for dynamic crosslinking of a mixture comprising particulate olefinic copolymer rubber (A) and olefinic plastic (B) include ~,5-dimethyl-2,5-di-(t-butylpero~y)hexane, 2,5-dimethyl-2,5-di(t-butyl-peroxy)hexyne-3, 1,3-bis(t-butylperoxyisopropyl)benzene, 1,1-di-(t--butylperoxy)-3,5,5-trimethylcyclohexane, 2,5-dimethyl-Z,5-di(peroxybenzoyl)hexyne-3 and dicumyl peroxide. Among them, especi.ally preferred i~s 2,5-dimethyl-2,5-di(t-butylperoxy)hexane Erom the points of smell and scorch.

Amount of the organic peroxide can be selec:ted fr:om theran~e of 0.005-2.0 p~rts by weight, preferably 0.01-0.6 partby weight for totally 100 parts by weight of the oleEinic copolymer rubber and the olefinic plastic.
If it is less than 0.005 part by weight, the eEfect of crosslinkiny reaction is low and if it is more than 2.0 parts hy weight, the reaction can be controlled with ~() difficulty and besides, this is economically not advantageous, As crosslinking aids in dynamic crosslinking with organic peroxides in production of the composition of the present invention, there may be used peroxide crosslinking aids such as N,N'-m-phenylenebismaleimide, '';

. . .
toluylenehismaleimide, p-quinone dioxime, nitrobenzene, diphenylguanidine and tri.methylolpropane and polyfunctional vinyl monomers such as divinylbenzene, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and allyl methacrylate.
Addition o~ these compounds results in occurrence of - uniform and gentle crosslinki.ny reaction and a reaction - ~etween the olefinic copolymer rubber and the olefinic plastic, whereby mechanical properties can be improved.
Amount of the crosslinking aid can be selected from the range of 0.01-4.0 parts by weight, preferably 0.05-2.0 parts by weight for totally 100 parts by weight of the olefinic copo:lymer rubber and the ol.efinic plastic.
lf the amount is less than 0.0~ part by weight, the effect of addition hardl~ appears and if it is more than 4 parts by weight, this is economically no advantaqeous Speci~ic process for production of the TPE
composition by dynamically crosslinking a mixture comprising olefinic copolymer rubber and olefinic plastic will be explained below.

First, particulate olefinic copolymer rubber (A) and olefinic plastic (~) at a specific ratio are directly fed to a continuous kneading extruder and melt kneaded therein.

Then, organic peroxide is ~ed from a feed ~0 open.ing provided at downstream side of the extruder and dynam.ic crosslinkin~l is carried out to obtain the desired T~ compos~tion.

As the contLnuous kneadin~ extruder, there may ~'j be used s.ingle screw continuous kneading extruders, twin screw continuous kneading extruders and three screw or - 1t -,:
more multiple screw continuous kneading extruders fitted with screws or rotors designed to have kneadability improving functions and combination of these extruders connected so that materials ~n the extruders can be moved - 5 in ~olten state.
,, Screws and rotors designed to have kneadability improving functions include Dulmage, pin and multiple flight screws for single screw type and kneading disk and rotor for twin screw type.

In the present invention, twin screw continuous kneading extnlders. Rotating can be either different direction type or same direction type.
As these continuous kneading extruders, the following types can be exemplified among those which are con~ercially available. ~uss Ko-kneader (manufactured by Puss AG.) and Model HM tmanufactured by Mitsubishi Heavy Industries, Ltd.) as single screw continuous kneading extruders and Model ZSK (manuPactured by Werner &
Pfleiderer GmbH~, Model TEX (manufactured by The Japan Steel Works, Ltd.), Model TEM (manufactured by Toshiba Machine Co., Ltd.), Model KTX (manufactured by Kobe Steel, Ltd.) and Mixtron LCM (manufactured by Kobe Steel, Ltd.) as twin screw continllous kneading extruders.

In the present invention, maximum shear rate at dynamic crosslinking is preferably 500/sec or higher and this can be attained only by using the above continuous kneading extruders and cannot be obtained by the conventional batch type mixers such as Panbury mixer and ,, roll.

If the shear rate is less than 500/sec, production efficiency is low and TPE compositions excellent in - 12 - 2~82372 appearance and properties can hardly be obtained, Specific steps in the production methoa will be , explained below.
In the step for melt kneading of particulate olefinic copolymer n1bber (A) and olefinic plastic (B), first, belt type and screw type feeders can be used for feeding of components (A) and (~) to extruders and screw type forcinq apparatuses can also be used.

Weight ratio of components (A)/(B) is preferably Z0-95/80-5 and if t~) is less than this range, properties are apt to deteriorate at the time of dynamic crosslinking and much heat tends to generate by shearing.

~reset temperature oE continuous kneadin~
extruder varies depending on melting point and flowability of the materials, especially olefinic plastics, but is preferably in the range of 100-250C.

In order to form good morphology of compositions comprifiing components (A) and (B), the kneading part preferably has screws or rotors designed to have a function to improve kneadability.

In the subsequent step o~ dynamic crosslinking, the organic peroxide can be used after diluted with liquid or powdery materials.
3~
Feeding of the peroxide from the ~eed opening provided halfway the extruder is carr-ied out by dropping it to the feed opening or injecting it into cylinder by a met~.ri,ncJ pump in the case oE liquid and by feeding it to tSle feed openincg by a weighing Eeeder in the case of pvwder, 208~372 As the diluents, there may be used oils, organic solvents and inorganic fillers such as silca and talc.

Preset temperature of dynamic crosslinking part o~ the extruder is prefer~bly 150C or higher though it depends on decomposition temperature of the organic peroxide used. It is preferably l50-3nO~C since it is important that the organic peroxide has been nearly completely consumed at the outlet of the extruder.

It is preferred that the dynamic crosslinking part has devices having the function to improve knead-ability, such as rotors and kneading discs in the case of twin screw kneaders.

Maximum shear rate of the dynamic crosslinking part is preferably 500/sec or higher. However, if it is too high, decomposition, deterioration and coloration are apt to be brought about due to heat generation.

In the present invention, addi1:ional olefillic plastic may be intro~uced at any positions of upstream-downstream of the extruder. It may be introduced after the dynamic cro6slinking step.

When crosslinking aid is used in the present invention, it is preferred to feed it before or simulta-- neously with feeding of the organic peroxide.
Furthermore, if necessary, inorganic fillers, antLoxidants, weathering agents, antistatic agents, lubricants and coloring picJments may also be used. These may be Introduced at any portions of the extruder.
Further, the mineral oil softener may be fed at - l4 -any portions of the e:~tn:lder. ~Iowever, when it is used in a larye antount, i.t is preferably fed in portions from many feed openlngs. When the mineral oil softener is needed, it is further preferred to use it as particulate 5 oil extended olefinic copolymer rubbers.

Uses of the olefinic TPE compositions of the present invention as substitutes for vulcanized rubbers include automobile parts such as weatherstrips, ceililIg 10 materials, interior sheets, bumper molding, side moldi.ng, air spoiler, air duct hoses and various backings, civil engineering materials and construct ion materials such as waterstops, joint fillers and window frantes for buildings, sporting goods such as gol f clubs and grips oE tennis 15 rackets, industrial parts such as hose tubes and gaskets, and appl iance parts xuch as hoses and backings .

The preseIlt invention will be illustrated by the fol lowing example!3 .
Methods for measurement of properti.es in the examples and comparative exa~ttples are as follows.

( 1 ) Mooney viscosity (ML1+4 100C) (hereinafter referred to as "viscosity" ): This was measured in accordance w i th ASTM D-927-57T .
Viscosity (ML1 ~ of EPDM was calculated hy the following formula.
log(ML1/ML2)=0.0066( ~, PHR) Ml.l: Viscosity of EPDM
ML2: Viscosity of oil extended EPDM
/'~ Y~{R: Oil extension antount per 10() parts by we ight of EPDM

- 15 ~

(2) Particle shape index ( a ):
Bulk density D A of particulate olefinic copolymer rubber was measured by measurin~ the weight of thereof per 1 L (kg/L).

(Graduated measuring cylinder of 500 ml was used.~

Similarly, bulk density D~ of olefinic plastic was measured.
Particle shape index a was calculated by the following formula.

a -DA/

(3) i~ardness: This was measured in accordance with ASTM D-2240. (Type A, instantaneous value).

~ 4) Tensile strength at break: This was measured in accordance with JIS K-6301 (JIS No. 3 dumbbell, pullin~
,, ra,te Z00 mmJmin).

(5) Elongation at break: Same as for tensile strength at break.
(6) Compression set: ~rhis was measured in accordance with JIS K-6301. ('70C, 22 hours, compressibility 25~).
(7) Melt fLow rate (MFR): This was measured in accordarlce with JIS K-7210 (230C).

~ xt:rusion moldabillty: This was evaluated by surfacc texture of extruded sheet of 0.2 mm thick made by USV 25mm~ extruder manufactured by Union Plastic Co. usin~y full flight type screw and T die. This was graded by the - 16 - 20~2372 following criteria O : Excellent x : Rou~hened surface (9) Injection moldability: Injection moldecl article was made by FS-15N injection molding machine manu~actured - by Nissei Plastic Industrial Co., Ltd., at a molding temperature of 220C and a mold temperature of 50C for an injection time of l0 seconds and a coolin~ time of 30 seconds under an injection pressure o~ 2.5 kg/c~2 which is a minimum filling pressure required for completely filling the composition in the mold with a mold haviny the shape of 150 mm x 90 mm x 2 mm with using a normal gate. The moldability was evaluated by the surface te~ture of the molded article and graded by the following criteria.

O : Excellent x : Roughened surface (l0) Observation by electron microscope:
The molded test piece was treated with vapor of l~, aqueous Ru04 svlution at 60C for l hour to dye the rubber portion and then this test piece was cut by a microtome cooled to -80C to make an ultrathin slice of Z5 about 0.l 1l thick. Morphology of this ultrathi~ slice was observed by a transmission electron microscope (~-8000 manufactu~e by l~itachi Limited). Ma~nification was x 6000.

3(l Production conditions by twin screw kneader were as shown below.

Twin scr~w kneader used: TEX44~lCT manufactured by The Japan Steel Works Ltd. (I./D=38.5, the number oE
cylinder blocks=ll) Construction of cylinder is as shown in the following (1) for Examples 1-4 and is as shown in the - following (2~ for Comparative Examples 1-2. ~oth have 11 cylinder blocks of Cl-Cll and the first feed opening was provided at Cl and venting port was provided at C10. In the construction of (1), the second feed opening for feeding organic peroxide was provided at C5. D indicates a die outlet part. In the construction (1), the direction of C1 ~ C11 is downstream side of the extruder.
(1) The first The second Venting feed opening feed opening port 15 ¦C1 ¦ C2 ¦ C3 ¦ C4 ¦ C5 ¦ C6 ¦ C7 ¦ C8 ¦ C9 ¦ C10 ¦ Cll ¦ D ¦

., , .

(2) The first Venting feed opening port ~Cl ¦ C2 ¦ C3 ¦ C4 ¦ C5 ¦ C6 ¦ C7 ¦ C8 ¦ C9 ¦ C10 ¦ Cll ¦ D ¦

Example 1 To 4 wt% solution of ~PDM (ethylene-propylene-ethylldene norbornene copolymer rubber, viscosity=143, propylene=30~ by weight, iodine value=10) in hexane was added 40 parts by weight of a mineral oil softener (Diana Process Oil PW380 manufactured by Idemitsu Kosan Co.) per - 18 - 20~2372 100 parts by weight of ~'PDM, followed by st-eam stripping to remove the solvent. This oil e~tended EPDM ~viscosity--78) was ground by a yrinder to obtain a particulate oilextended rubber (oil extended EPDM-l) having a bulk ~ensity of 0.39 kg/L.

Then, 100 parts by weight o the resulting particulate oil extended n~bher, 43 parts by weight of crystalline polypropylene having a MFR (230C, 2.16 kg load) of 2 and a bulk density oE 0.55 kg/L (PP-l) and 0.57 part by weight of N,N-m phenylenebis~aleimide (~M) were mi~ed Eor 30 seconds by a super mixer (manufactured by Kawada Seisakusho Co.).

This mixture ((I =0.71) was fed from the first feed opening (Cl) of the twin screw kneader (T~X44HCT
manufactured by The Japan Steel Works, Ltd., h/~=38.5) having the above cylinder construction (1) at 30 kg/hr to carry out melt kneading. Then, 2,5-dimethyl-2,5-di-(tert~
butylperoxy)hexane (hereinafter referred to as 70rganic peroxide") diluted to 10% by weight with a mineral oil (paraffinic oil Diana Process Oil PW90 manufactured by Idemitsu Rosan Co.) (PO-1) was fed from the second Eeed opening (C5 of the cylinder construction (1)) at 240 g/hr to carry out dynamic crosslinking and the product was pelletized. The resulting pellets were evaluated on properties and extrusion moldability. The maximum shear rate in the dynamic crosslinking part was about 1600/sec.

Measurement of hardness, tensiIe strength and compression set were carried out on a sheet of 1 mm thick obtained by the extrllsion molding.

~eslllt:s of the evaluations are shown in Table 1.

Example 2 The procedure of Example 1 was repeated except that a mixture of 100 parts by weight of ail extended EPDM, 43 parts by weight of PP-~ and 0.2g part by weight of N,N-m-phenylenebismaleimide (BM) was fed from the first feed opening and the organic peroxide diluted to 13.3% by weight with sili,ca and talc ~PO-2) was Eed from the second feed opening at 180 g/hr. Results of the evaluations are shown in Table 1. Observation of this , 10 sample by transmission electron microscope revealed that ', superior dispersion was ~ttained as shown in Fig~ 1. That is, it is seen in Fig. 1 that EPDM domain (grey) was finely dispersed in less than about 3~ in polypropylene matrix (white). It is considered that this contributed to the development of the good propertles shown in Table 1.

Example 3 The procedure of Example 2 was repeated e~cept that PO-2 was fed at 90 g/hr. Results of the evaluation are shown in Table l.

Comparative Example ]
A composition was ohtained in the same manner as in Example 1 except that a twin screw extruder having the cylinder construction 12) was used and a mixture comprising 100 parts by weight of oil extended EP~M-1, 43 parts by weiqht of PP-l, 0.57 part by weight of N,N-m-phenylene-bismaleimide and 0.15 part by weight of the organic peroxide diluted to 40~ by weight with silica (PO-3) was fed from the first feed opening (Cl in the cylinder ~. construction (2)).
:;
As shown in Table 1, the su~face of the extruded sheet was very roughened. Further, observation by a transml6sion electron microscope reveals that only very unhomogeneous dispersion was obtained. (See Fig, 2). That - 20 - 20~23~2 is, it is seen in Fig. 2 that EPDM domain (grey) was roughly dispersed in about 4--6 ~ m in po].ypropylene matrix (white)~ This is considered to cause the inerior properties, especially tensile strength and extrusion moldability shown in Table 1.

Example 4 To 4 wt% solution of EPDM (ethylene-propylene-ethylidenenorbornene copolymer rubber, viscosity=242, propylene=2~% by weiqht, iodine value=12) in hexane was added 1()0 parts by weight of a mineral oil sof`tener (Diana Process Oil PW380 manufactured by Idemitsu Kosan Co~) per 100 part~ hy weight of EPDM, followed by steam stripping tu remove the solvent. This oil extended F.PDM (viscosity--53) was gro1lnd by a grinder to obtain a particulate oi.lextended rubber (oil extended EPDM-2) having a bulk density of 0.29 kg/r~

Then, 100 parts by weight of the resulting particulate oil extended rubber, 15 parts by weight of crystalline polypropyl.ene having an MFR (230UC, 2.16 k~
load) of 10 and a bulk ~ensity of U.60 kgJL (PP-2) and 1.27 part by weight oE N,N-m-phenylenebismaleimide (BM) were mixed for 30 seconds by a super mixer (manufactured by Kawada Seisakusho Co.).

This mixture (a --0.48) was fed from the Eirs-t feed opening (Cl of the cylinder construction (1)) at 30 kg/hr as i.n Ex~mple 1. Then, the organic peroxide diluted to 50~ by weiyht with a mineral oil (Di.ana Process Oil PW90 manufactured by Idemitsu Kosan Co.) (PO-4) was fed from the second Eeed opening (C5 of the cylinder construction (I)) at 480 g/hr to carry out dynamlc cro~sl.inkiny and the product was pelleti~ed. The resulting pellets were eva].uated on properties and extrusion moldabillty.

,...

Measurements oE hardness, tensile strength and compression set were carried out on a sheet of Z mm thick obtained by the extrusion molding.

Results of the evaluations are shown in Table 2.
,. .
Comparative E~ample 2 A composition was obtained in the same manner as in Example 4 except that a twin screw ex-truder having the cylinder construction (2) was used and a mixture comprising 100 parts by weight of oil extended EPDM-Z, 15 parts by weight of PP-2, 1.27 part by weight of ~,N-m-phenylenebismaleimide (~M) and 0.92 part by weight of the organic peroxide diluted to 40~ by weight with silica ~PO-3) was fed from the first feed opening (Cl in the cylinder construction (2)).

Results of the evaluation are shown in Table 2.

Note-l and Note-2 in Tables 1-2 are as follows:

, Note-l: Amount (part by weight) of the organic peroxide fed per 100 parts by weight of EPDM-l Note-2: Amount (part by weight) of the organic peroxide fed per 100 parts by weight of EPDM-2 ., ;, - ' .

Table 1 . Exarnple Exarnple Exar~le Cornparative 1 2 3 Example 1 l __ The first Oil-extented 100 100 100 100 feed EPDM-l Mix- opening PP-l 43 43 43 43 ing (30kg/hr) BM 0.57 0.29 0.29 0.57PO-3(Note 1) _ _ _ (0.06) __ _ _ The second PO-l(Note 1) 240 g/hr _ _ feed (0.12) opening PO-2(Note 2) _ 180 g/hr 90 g/hr _ (0.12) (0.06) _ Dy- Preset temperature of namic dynamic crosslinking 180-200 180-200 180-200 180-200 cros part C
link-ing Resin ternperature at con- die outlet C 255 256 254 258 di-tlons MFR 230C 10 kg load 6.8 10 9.7 13 (g/10 min.) l~ardness (Shore-A) 85 83 86 79 Tensile strength at break (kg/cm2) Mechanical direction165 135 150 110 Prop- Tensile strength at er- break (kg/cm2) ties Traverse direction 161 144 145 102 Elongation at break (~) Mectlanical direction800 790 790 700 Elongation at break (~) Traverse direction 810 820 810 720 Corrpressi.on set (%)61 60 69 69 , xtrus;.on rrlo:l.dability _ O O
~_ ._ ,_~

, ', ! . , - 23 - 2~82372 Table 2 ExampleCornparative 4 Example 2 The first Oil-extented 100 100 feed EPDM~l Mix- opening PP-1 15 15 ing (30kg/hr) BM 1.27 1.27 PO-3(Note 1) _ 0.92 (0-37) The second feed PC-4(Note 2) 384 g/hr _ opening (0.64) _ Dy- Preset temperature of 180-200 180-200 narnic dynamic crosslinking Clrink~ part C
ing Pesin temperature at 258 255 oin- die outlet C
tions MF'R 230C 10 kg load 24 53 (g/10 rnin.) llardness (Shore-~) 65 62 Prop- Tensile strength at 50 47 etriefi break (kg/cm2) Elongation at break (~) 430 420 Corr~ressiorl set (~) 33 32 _ Injectioll moldability O

. ' ' ' . ' .

- 2~ - 2082~72 'rhe present invention provides a method for ; producing olefinic TPE compositions substitutable for vulcanized n~bbers which are improved in mechanical properties such as tensile strength, breaking extension and compression set in low har(lness region of olefinic TPE and are further improved in processability and inhibited from bleeding of oil to the surface of molded articles , ,

Claims (11)

1. A method for producing a thermoplastic elastomer composition which comprises directly feeding a particulate olefinic copolymer rubber (A) having a particle shape index .alpha. defined below of 0.1-0.9 and an olefinic plastic (B) to a continuous kneading extruder to carry out melt kneading and then, feeding an organic peroxide at downstream side of said extruder to carry out dynamic cross- linking:

.alpha.=DA/DB

wherein DA denotes bulk density of the particulate olefinic copolymer rubber (A) and DB denotes bulk density of the olefinic plastic (B).
2. A method according to claim 1, wherein the olefinic copolymer rubber which constitutes the particulate olefinic copolymer rubber has a Mooney viscosity ML1+4 100°C of 30-350.
3. A method according to claim 1, wherein the particulate olefinic copolymer rubber (A) is a particulate oil extended olefinic copolymer rubber containing 20-150 parts by weight of a mineral oil softener for 100 parts by weight of the olefinic copolymer rubber.
4. A method according to claim 3, wherein the olefinic copolymer rubber has a Mooney viscosity ML1+4 10°C
of 80-350.
5. A method according to claim 3, wherein the particulate oil extended olefinic copolymer rubber has a Mooney viscosity ML1+4 100°C of 30-150.
6. A method according to claim 3, wherein the mineral oil softener is a paraffinic softener.
7. A method according to claim 1, wherein weight ratio (A)/(B) of the particulate olefinic copolymer rubber (A) and the olefinic plastic (B) is 20-95/80-5.
8. A method according to claim 1, wherein the olefinic copolymer rubber which constitutes the particulate olefinic copolymer rubber (A) is an ethylene-propylene-non-conjugated diene copolymer rubber.
9. A method according to claim 8, wherein the ethylene-propylene-non-conjugated diene copolymer rubber is an ethylene-propylene-ethylidenenorbornene copolymer rubber containing 10-55% by weight of propylene and 1-30%
by weight of ethylidenenorbornene.
10. A method according to claim 1, wherein the olefinic plastic (B) is at least one member selected from the group consisting of polypropylene and propylene-.alpha. -olefin copolymer resin.
11. A method according to claim 1, wherein the dynamic crosslinking is carried out at a maximum shear rate of 500/sec or higher.
CA002082372A 1991-12-19 1992-11-06 Method for producing thermoplastic elastomer composition Abandoned CA2082372A1 (en)

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