Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUSRE27145 E
Publication typeGrant
Publication dateJun 22, 1971
Filing dateMay 20, 1969
Priority dateMay 20, 1969
Publication numberUS RE27145 E, US RE27145E, US-E-RE27145, USRE27145 E, USRE27145E
InventorsRobert C. Jones
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Side-chain
US RE27145 E
Images(1)
Previous page
Next page
Description  (OCR text may contain errors)

June 22, 1971 TEIPERATURE, C

TEISILE, PSI N LII c O o 3 8 8 I I I R- C. JONES I Re. 27,145

APPAREIIT GLASS POINT, C

l l l 1.0.Sl0E-0HMN FIG. I

TEIISILE STRENGTH AT 75C I I l as c, suns-cam FIG. 3

BALL REBOUND, 7.

TEISILE, PSI

REBOUND,

7o C SIDE-CIIAIN FIG. 2

TENSILE STREIIGIH AT I00C I l I so 5o 10 1. 0, sum -cmuu FIG. 4

INVENTOR:

ROBERT C. JONES BY I @QM HIS AGENT States Patent Re. 27,145 Re issued June 22, 1971 27 145 HYDROGENATED BL( )CK COPOLYMERS F BUTADIENE AND A MONOVINYL ARYL HYDROCARBON Robert C. Jones, San Francisco, Calif., assignor to Shell Oil Company, New York, NY.

Original No. 3,431,323, dated Mar. 4, 1969, Ser. No. 338,795, Jan. 20, 1964. Application for reissue May 20, 1969, Ser. No. 848,755

Int. Cl. C08f /04 US. Cl. 260-880 10 Claims Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.

ABSTRACT OF THE DISCLOSURE Hydrogenated block copolymers having a superior combination of physical properties are prepared by block polymerizing a vinyl arene with butadiene in the presence of a polar compound tocause a limited amount of branching in the polybutadiene block and thereafter hydrogenating the polymer.

This invention is concerned with novel block copolymers, their compositions and processes for their preparation. More particular, the invention is directed to certain hydrogenated block copolymers having optimum physical properties based upon a critical microstructure of the elastomeric polymeric blocks contained therein.

Rubbers and elastomers of either natural or synthetic origin normally require vulcanization in order to obtain useful elastomeric properties. Before vulcanization, rubbers possess tacky properties and low strength which makes them of little utility except as rubber cements. Another of their prime shortcomings is that of stability relative to either heat or oxidation.

Optimum elastomeric properties are not usually attained until the rubber has been subjected to a vulcanization treatment such as by means of heating with sulfur, sulfur compounds, peroxides or other means. Vulcanization usually results in insolubilization of the rubber in most common solvents. While this may be of advantage in certain situations, for many purposes such as the application of paints, etc., and in the formation of molded objects, insolubilization is in fact a substantial disadvantage. It has been necessary in many cases to apply vulcanized rubbers in the form of latices or to vulcanize the rubber after it has been formed in a molding operation or the like. vulcanization under such circumstances often results in substantial losses of product, since the flashings from moldings etc., cannot be readily reworked but must be incorporated in other compositions acting merely as a filler or reinforcing agent.

It would be desirable to have a rubber which behaves like a vulcanized rubber without the necessity for vulcanization, as well as having the property of being soluble in a selected class of relatively inexpensive solvents such as certain hydrocarbons. Recently, a critically limited class of block copolymers has been investigated to determine the optimum structure for obtaining these combinations of properties. The block copolymers under consideration comprise primarily those having a general structure ABA wherein the two terminal polymer blocks A comprise thermoplastic polymer blocks of vinylarenes such as polystyrene, while block B is a polymer block of a conjugated diene. The proportion of the thermoplastic terminal blocks to the center elastomeric polymer block and the relative molecular weights of each of these blocks is balanced to obtain a rubber having an optimum combination of properties such that it behaves as a vulcanized rubber without requiring the actual step of vulcanization. Moreover, these block copolymers can be designed not only with this important advantage but also so as to be handled in thermoplastic forming equipment and are soluble in a variety of relatively low cost solvents.

While these block copolymers have a number of outstanding technical advantages, one of their principal limitations lies in their sensitivity to oxidation. This is due to their unsaturated character which can be minimized by hydrogenating the copolymer, especially in the center section comprising the polymeric diene block. Hydrogenation may be effected over the entire molecule, converting the terminal blocks such as polystyrene to polyvinylcyclohexaue blocks, while the diene polymer block is converted to a straight chain hydrocarbon having a relatively high degree of saturation, this portion of the block copolymer having properties similar to polymers of alpha olefins.

The elastomeric properties of certain alpha olefin polymers appear to be due in part to their degree of branching. While the alpha olefin polymers have a basic straight carbon chain backbone, those with elastomeric properties always have dependent alkyl radicals. For example, EPR (ethylene-propylene rubber) has a structure of dependent methyl radicals which appears to provide elasticity and other elastomeric properties. When an essentially unbranched straight chain polymer is formed, such as some polyethylenes, the resulting polymer is essentially nonelastomeric or in the other words relatively rigid, and behaves like a typical thermoplastic without possessing resilience, elongation, tensile strength without yield, low set or other properties characteristic of desirable elastomers.

The problem therefore exists of forming a block copolymer having the self-curing property discussed hereinbefore, solubility in relatively low cost solvents, stability toward oxidation and retention of the elastomeric properties over a wide temperature range in spite of hydrogenation of the polymer to obtain the desired degree of stability.

Now, in accordance with the present invention, a particular type of block copolymer has been prepared meeting in large measure the above requirements and combining within its structure, a configuration enabling the combination of a maximum number of physical properties especially desirable for such products. These polymers are hydrogenated block copolymers having a configuration, prior to hydrogenation, of ABA wherein each of the As is an alkenyl-substituted aromatic hydrocarbon polymer block and B is a butadiene polymer block wherein 3555 mol percent of the condensed butadiene units in the butadiene polymer block have 1,2 configuration. of the carbon atoms present in the butadiene polymer block are in the form of dependent vinyl side chains] Still in accordance with this invention, a means has been devised for the preparation of such branched block copolymers which comprises the steps of utilizing an alkyl lithium catalyst in a relatively inert hydrocarbon solvent for the block copolymer at each stage of its formation modified with a critically defined proportion of a polar compound of the group consisting of ethers, thio-ethers and tertiary amines; forming a first polymer block of an alkenyl aromatic hydrocarbon in said medium to form a living polymer block; adding butadiene thereto and continuing polymerization until the desired weight has been obtained; thereafter introducing an alkenyl arene and continuing block copolymerization to finally obtain the ABA block copolymer wherein the center polybutadiene block has the recited degree of branched configura- 3 :ion. Following the preparation of this unsaturated block :opolymer, the latter is subjected to hydrogenation of auch a degree that the unsaturation of the polybutadiene )lOCk is reduced to less than 10% of its original value.

The block copolymer having the diene center block it least 90% hydrogenated but less than 10% of the )olystyrene units hydrogenated exhibits the dual advanages of improved stability while maintaining good procssability. Block copolymers wherein at least about 25% )f the polystyrene blocks are hydrogenated have the tdvantages both improved stability and increased softenng points. Such compositions may be mixtures of block :opolymers wherein at least part of the molecules are saturated over their entire length, the remaining molecules reing those in which only the butadiene polymer block is it least 90% saturated. Alternatively, the hydrogenated olymers may be those in which at least 90% of the )olybutadiene linkages are hydrogenated and in which he polystyrene blocks are those containing both saturated 1nd unsaturated styrene units.

The figures forming a part of the specification indicate l number of physical properties of block copolymers of his variety containing a Wide range of C side chains howing that a critical range between about 35 and 55 nol percent 1,2 structure, of the carbon atoms in side :hains is required] in order to obtain the optimum comination of the most desired properties, while at the tame time retaining the benefits of self-curing and the )ossibility of processing the polymer in thermoforming :quipment such as extrusion or other thermoplastic moldng devices.

In order to have the most desirable properties, it is referred to form terminal blocks A having average molecilar weights of 4,000-115,000 and polybutadiene blocks 1aving average molecular weights of 20,000450,000. Still more preferably, the terminal blocks have average molec- Jlar weights of 8,00060,000 while the polybutadiene polymer block has an average molecular weight between about 50,000 and 300,000. Likewise, in order to promote the optimum combination of physical properties, it is desirable that the terminal plastic blocks comprise 530% by Weight of the total block copolymer.

The proportion of polar modifying compounds to be used in forming the branched polybutadiene blocks in the above types of block copolymers will depend upon a iumber of factors such as the identity of the polar compound, the precise degree of branching desired, the hydro- :arbon medium utilized and the amount of lithium catalyst present. For the purpose of the present invention, the imount of polar compound will be expressed as a molar ratio of polar compound to lithium alkyl. In order to achieve 3555 mol percent 1,2 structure, of carbon atoms in dependent side chains,] the molar ratio of polar :ompound to lithium should be between about 7 and 70, preferably between about 10 and 40.

The degree of branching of the polybutadiene block is essentially linear with the molar ratio of polar compounds :0 lithium. Consequently, if the ratio is too low, then the desired degree of branching is correspondingly decreased and the resulting block copolymer, when hydrogenated, Is essentially a plastic having substantially non-elastomeric properties e.g. poor rubber properties. On the other hand, if the molar proportion is increased beyond the maximum :imit recited, the degree of branching is excessive and, as I will be seen by reference to the figures, the elastomeric properties of the resulting products following hydrogenazion are drastically damaged. Consequently, the major abjective of the process is to utilize the correct proportion )f polar compound to lithium initiator such that the aranching of the polybutadiene block is within the desired 'ecited range of 35-55 mol percent. or in other terms, 35-55% of the carbon atoms in the polybutadiene block are in the form of dependent C side chains] While the center elastomeric block is preferably a polymerized butaliene polymer having a recited degree of branching, this 4 may be modified, with about 25% by weight of elastomeric block-producing monomers of other conjugated dienes such as isoprene and the like.

The non-elastomeric end polymer blocks comprise homopolymers or copolymers preferably prepared from alkenyl aromatic hydrocarbons and particularly from vinyl aromatic hydrocarbons wherein the aromatic may be either monocyclic or polycyclic (followed by hydrogenation). Typical monomers include styrene, alpha methyl styrene, vinyl xylene, ethyl vinyl xylene, vinyl naphthalene and the like. Mixtures of such monomers may be utilized as well. The two end blocks may be the same or different as long as they meet the generic description of these end blocks insofar as their thermoplastic character is concerned as differentiated from the elastomeric major of the center block. Where, in the specification, general reference is made to polystyrene blocks, it will be understood that other types of poly(-vinyl arenes) may be used in place thereof. The center block may be an elastomer in accordance with the definition contained in ASTM Special Technical Bulletin, No. 184 as follows:

A substance that can be stretched at room temperature to at least twice its original length and, after having been stretched and the stress removed, returned with force to approximately its original length in a short time.

The catalysts employed in the process of the present invention may be defined broadly as lithium based initiators although alkyl lithium initiators are preferred. Other suitable initiators include lithium metal and aryl lithium compounds and in certain instances, dilithium initiators such as dilithium stilbene, lithium l-diphenyl ethylene or lithium naphthalene. Alkyl lithium initiators, the preferred class, may be generally divided into normal alkyl lithiums and branched alkyl lithiums, the latter having a number of functional aspects making them more desirable than the former. Branched alkyl lithium initiators exhibit no disadvantageous induction period in the startup of the polymerization, the rate of polymerization is reasonably rapid but sutficiently steady so that it can be controlled and the products obtained are of a relatively narrow molecular Weight range also adding to the product control and effectiveness thereof for a number of purposes.

Polymerization is normally conducted at temperatures in the order of 20 to about C., preferably about +20 C. and 65 C. The proportion of initiators will depend upon the molecular weight of the products desired, but may be varied, with the latter qualification, between about 1 and about 200 parts per million based on the Weight of the monomers involved.

The basic process when using the lithium-based catalysts comprises forming a solution of the first alkenyl arene monomer in an inert hydrocarbon such as alkanes, alkenes or cycloalkanes modified by the presence of the polar compounds of the group consisting of ethers, thioethers and tertiary amines. Of course, since the presence of the polar compound is not essential in the formation of the first polymer block with many initiators, it is not essential to introduce the polar compounds at this stage since it may be introduced just prior to or together with addition of the butadiene for the formation of middle elastomeric branch block. Among the polar compounds which may be added in accordance with the one aspect of this invention ae dimethyl ether, diethyl ether, ethyl methyl ether, ethyl propyl ether, dioxane, dibenzyl ether, diphenyl ether, dimethyl sulfide, diethyl sulfide, tetramethylene oxide (tetrahydro furane), tripropyl amine, tributyl amine, trimethyl amine, triethyl amine, pyridine and quinoline. Mixtures of these polar compounds may be employed in the practice 'of the present invention. The proportion of polar compounds should be restricted in accordance with the limits set forth hereinbefore in order to obtain the desired critical degree of branching in the center elastomeric block.

When the lithium initiator, polar compound, alkenyl aromatic monomer and inert hydrocarbon are combined,

polymerization proceeds to produce the first terminal polymeric block having an average molecular weight between about 4000 and 100,000, this block being terminated on one end with a lithium radical and being referred to as a living polymer. At this time, without further alteration or removal of this lithium radical, butadiene is injected into the system and block polymerization occurs, the presence of the polar compound now becoming important in producing the desired degree of branching of the polybutadiene block. The temperature, initiator concentration and solvent may be adjusted at this time to optimize the desired degree of polymerization or rate of reaction. The resulting product is then typified by the general structure ABLi, a living polymer block of the two monomers thus far employed. After this, a second addition of an alkenyl aromatic hydrocarbon is made to produce the final terminal block and result in the formation of the three block system ABA which is the result of polymerization followed by termination with a polar terminator such as an alcohol and the like.

Having obtained the basic polymer with the described degree of branching in the center elastomeric butadiene polymer block, the next necessary stage is to hydrogenate -the polymer in order to increase its service temperature and at the same time to improve the oxidation stability of the product. Hydrogenation may be conducted utilizing a variety of hydrogenation catalysts such as nickel on kieselguhr, Raney nickel, copper chromate, molybdenum sulfide, and finely divided platinum or other noble metals on a low surface area carrier.

Hydrogenation may be conducted at any desired temperature or pressure, say, from atmospheric to 3000 p.s.i.g., the usual range being between 100 and 1000 p.s.i.g. at temperatures from about 75 F. to 600 F., for times between about 0.1 and 24 hours, preferably 0.2-8 hours. Preferred catalysts comprise the reduced metal products obtained by reduction of cobalt nickel, tungsten or molybdenum compounds with aluminum alkyls or hydrides. These catalysts are selective, in that the elasomeric block, a set of block copolymers was prepared having similar individual block molecular weights. While the polar compound was varied relative to the amount of lithium alkyl initiator present, the following is a typical example by which this set of block copolymers were prepared: Styrene (60 grams) was dissolved in benzene 1400 grams) containing varying proportions of tetrahydrofurane as the polar compound. This mixture was brought to C. and 0.003 mol of secondary butyl lithium was added. Polymerization was conducted at 40 C. in a reactor until all of the styrene had been converted to a polymer terminated with a lithium radical. Thereafter, butadiene was added to the reaction mixture (450 grams) and polymerization was continued until complete utilization of the butadiene monomer. The styrene-butadiene block polymer so formed was then modified by the addition of styrene (60 grams) and polymerization continued until no monomer remain: The resulting polystyrene-polybutadiene-polystyrene block polymer had average block molecular Weights of 15,000l00,00015,000.

The block copolymers so prepared by variation in tetrahydrofurane ratio relative to secondary butyl lithium were then hydrogenated at 500 p.s.i.g. hydrogen pressure, for 18 hours at 160 C. utilizing 0.3 gram of nickel on kieselguhr support per gram of polymer. The hydrogenated polymers were then tested for physical properties which are shown in the table below.

These data were then plotted in part in FIGURES l-4. It will be evident from a study of these figures and the accompanying table of data that block copolymers wherein the 1,2 content [side chain content] is between 35 and mol percent of the elastomeric center block appear to offer the best elastomeric compromise between low temperature resilience and stress-strain properties. At lower side chain levels, lower rebound and higher glass points are experienced. At higher side chain levels, tensile strength decreases along with rebuond, and glass point increases. Furthermore, tensile strength at elevated temperatures sulfers at 1,2 [side chain] contents above 55 mol diene block is hydrogenated rapidly, while the styrene percent. When the block copolymers having little or no PROPERTIES OF HYDROGENATED SBS, PRECURSOR HAVING VARYING 1,2 CONTENT AND 15-100-15Xl0' BLOCK LENGTHS Precursor, Modulus percent 1,2 in I.V., dl./g. Tensile Elongation butadiene (toluen I2 No at. break, 300%, 500%, at break, Set, Shore A block 25 0.) g 12/100 g p.s.i. p.s.i. p.s.i. percent percent hardness blocks are more slowly hydrogenated unless hydrogenation temperatures are increased.

Since the polybutadiene block is that most subject to oxidative attack, it is the primary objective of hydrogenation to reduce the unsaturation of this block, the hydrogenation of the terminal plastic blocks being of less importance. With some selective catalysts, this is readily accomplished whereas with others, the hydrogenation proceeds along the entire chain.

To improve the stability of the block copolymers, the diene unsaturation (measured by iodine number) should be reduced to less than 10% (preferably less than 5%) of its original value. Reduction of styrene unsaturation (measured by ultra violet) may be expressed as an average of 0100%; e.g., no reduction at all, and up to complete reduction. At intermediate reduction levels, it will be understood that the hydrogenation product may be a mixture of products in which some of the polystyrene blocks are hydrogenated more than others.

In order to compare the physical properties of the branched copolymers according to the present invention with those containing either less or more branching in the side chain branching in the center blocks were hydrogenated, the products resulted in a plastic-type polymer of limited solubility presumably due to a degree of crystallinity in the center segment.

I claim as my invention:

1. As a new composition of matter, a hydrogenated block copolymer having the general configuration ABA wherein, prior to hydrogenation.

(1) each A is a polymerized mono alkenyl aromatic hydrocarbon block having an average molecular weight of about 4,000115,000;

(2) B is a polymerized butadiene hydrocarbon block having an average molecular weight of about 20,000- 450,000;

(3) the blocks A constituting 2-33 weight percent of the copolymer;

(4) 35-55 mol percent of the condensed butadiene units in block B having 1,2-configuration; of the butadiene carbon atoms in block B being vinyl side chains;]

() and the unsaturation of block B having been reduced to less than of the original unsaturation.

2. A new composition of matter according to claim 1 wherein prior to hydrogenation the polymeric blocks A are polymer blocks of a vinyl aromatic hydrocarbon.

3. A new composition of matter according to claim 1 wherein the blocks A comprise 5-30% by weight of the copolymer, the unsaturation of block B is reduced to less than 5% of its original value and the average unsaturation of the hydrogenated block copolymer is reduced to less than of the original value.

4. As a new composition of matter, a hydrogenated block copolymer having the general configuration wherein, prior to hydrogenation,

(1) each A is a polymerized styrene block having an average molecular weight of about 8,00060,000;

(2) B is a polymerized butadiene block having an average molecular weight of about 50,000300,000, 40- 50 mol percent of the condensed butadiene units in block B having 1,2-c0nfigurati0n; of the butadiene carbon atoms in the block being vinyl sidechains;]

(3) the blocks A comprising 530% by weight of the copolymer; the unsaturation of block B having been reduced by hydrogenation to less than 10% of its original value.

5. A hydrogenated block copolymer composition acaccording to claim 1 wherein an average of less than about 10% of the mono alkenyl aromatic hydrocarbon units are hydrogenated.

6. A hydrogenated block copolymer composition ac- V cording to claim 1 wherein an average of more than about 25% of the mono alkenyl aromatic hydrocarbon units are hydrogenated. [hydrogeanted] 7. The process for the preparation of a block copolymer comprising the steps:

(a) polymerizing a mono alkenyl arene in the presence of an inert hydrocarbon solvent and alithium alkyl catalyst whereby a polymer block A having an average molecular weight of 4,000115,000 terminated with a lithium ion is formed;

(b) adding butadiene to the lithium-terminated block and block copolymerizing it with said first block in the presence of a polar compound of the group consisting of ethers, thioethers and tertiary amines, the molar ratio of said polar compound to lithium alkyl catalyst being between about 7 and 70, whereby a block copolymer terminated with lithium is formed 3555 mol percent of the condensed butdiene units in block B having 1,2-c0nfigurati0n; of the carbon atom in the butadiene polymer block being vinyl side chains,] the *butadiene polymer block B having an average molecular weight of 20,000450,000;

(0) adding thereto a mono alkenyl arene and block polymerizing it with the block copolymer of step (b), to form a block polymer ABA;

(d) and hydrogenating the block polymer whereby the unsaturation of the diene polymer block B is reduced to less than 10% of its original value.

8. A process according to claim 7 'Wherein the polar compound in step (b) is an ether.

9. A process according to claim 7 wherein the mono alkenyl arene is styrene and the polar compound is tetrahydrofiuran.

10. A process according to claim 9 wherein the lithium alkyl is a lithium secondary alkyl.

References Cited The following references, cited by the Examiner, are of record in the patented file of this patent or the original patent UNITED STATES PATENTS 3,333,024 7/1967 Haefele 260-880 3,140,278 7/ 1964 Kuntz 260879 3,149,182 9/1964 Porter 260879 3,239,478 3/1966 Harlan 260879 3,251,905 5/1966 Zelinski 260-879 3,299,174 1/1967 Kuhre 260879 OTHER REFERENCES Kuntz: Journal Polymer Science, vol. 54, pp. 569-586 1961), pp. 576-577 and 583-584 specifically relied upon.

JAMES A. SEIDLECK, Primary Examiner R. A. GAITHER, Assistant Examiner US. Cl. X.R. 260879

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4970254 *Sep 22, 1988Nov 13, 1990Shell Oil CompanyMethod for hydrogenating functionalized polymer and products thereof
US4970265 *Mar 27, 1989Nov 13, 1990Shell Oil CompanyFunctionalized polymers and process for modifying unsaturated polymers
US4983673 *Dec 22, 1988Jan 8, 1991Shell Oil CompanyBlend of polyamide with block polymer of hydrogenated alkyenyl arene and conjugated diene
US4988765 *Dec 22, 1988Jan 29, 1991Shell Oil CompanyHigh impact resistant blends of thermoplastic polyamides and modified diblock copolymers
US5051457 *Jul 16, 1990Sep 24, 1991Shell Oil CompanyAsphalt-block copolymer roofing composition
US5106917 *Feb 28, 1990Apr 21, 1992Shell Oil CompanyPeelable lidstock based on polybutylene block copolymer blends
US5149895 *Jan 16, 1990Sep 22, 1992Mobil Oil CorporationVulcanizable liquid compositions
US5166277 *Oct 31, 1991Nov 24, 1992Shell Oil CompanyNickel hydrogenation catalysts for lithium diene polymers
US5175212 *Nov 4, 1991Dec 29, 1992Shell Oil CompanyImpact strength
US5177155 *May 13, 1991Jan 5, 1993Shell Oil CompanySelective hydrogenation of conjugation diolefin polymers with rare earth catalysts
US5187236 *Jan 16, 1990Feb 16, 1993Mobil Oil CorporationHigh elongation, good aging properties
US5189110 *Sep 16, 1991Feb 23, 1993Asahi Kasei Kogyo Kabushiki KaishaBlock polymer of a vinyl aromatic compound and/or a hydrogenated product thereof, butadiene and/or a hydrogenated product thereof
US5209862 *Jan 30, 1991May 11, 1993Shell Oil CompanyCarboxylated Hydrogenated Vinylaromatic-Conjugated Polyene Block Polymer
US5218033 *Nov 25, 1991Jun 8, 1993Shell Oil CompanyHigher tensile strength; improved processibility
US5266635 *Feb 26, 1993Nov 30, 1993Shell Oil CompanyLow temperature impact strength
US5308676 *Sep 20, 1991May 3, 1994Shell Oil CompanyComprising a reinforcing mat saturated with a bituminous composition containing both a hydrogenated and unhydrogenated aromatic vinylaryl/conjugated diene copolymer; heat resistance; high strength; materials handling
US5336726 *Mar 11, 1993Aug 9, 1994Shell Oil CompanyButadiene polymers having terminal silyl groups
US5342885 *Dec 8, 1989Aug 30, 1994Shell Oil CompanyDiglycidyl compounds reacted with rubber particles having carboxy groups to form stable dispersions which cure to polyepoxides; low viscosity
US5349015 *Dec 8, 1989Sep 20, 1994Shell Oil CompanyMelt blending acid or anhydride-crafted block copolymer pellets with epoxy resin
US5369167 *Mar 28, 1994Nov 29, 1994Shell Oil CompanyMelt blending acid or anhydride-grafted block copolymer pellets with epoxy resin
US5376745 *Dec 1, 1993Dec 27, 1994Shell Oil CompanyLow viscosity terminally functionalized isoprene polymers
US5378761 *Jun 24, 1993Jan 3, 1995Shell Oil CompanyPolymer coating with epoxy resins
US5389711 *Feb 14, 1990Feb 14, 1995Shell Oil CompanyPlasticisers for salt functionalized polyvinyl aromatics
US5391637 *Nov 23, 1993Feb 21, 1995Shell Oil CompanyPolymers having terminal primary hydroxyl groups
US5393843 *Aug 31, 1992Feb 28, 1995Shell Oil CompanyButadiene polymers having terminal functional groups
US5405911 *Sep 15, 1994Apr 11, 1995Shell Oil CompanyButadiene polymers having terminal functional groups
US5405914 *Jul 29, 1993Apr 11, 1995Shell Oil CompanyAcid extraction and water washing
US5418296 *Oct 6, 1994May 23, 1995Shell Oil CompanyCapping of anionic polymers with oxetanes
US5458791 *Jul 1, 1994Oct 17, 1995Shell Oil CompanyOil additives
US5460739 *Sep 9, 1994Oct 24, 1995Shell Oil CompanyStar polymer viscosity index improver for oil compositions
US5554691 *Aug 31, 1994Sep 10, 1996Shell Oil CompanyReacting monohydroxylated conjugated diene polymer with diisocyanate or multifunctional isocyanate, reacting the product with an epoxy resin or acrylic resin having hydroxyl groups
US5594072 *Aug 1, 1995Jan 14, 1997Shell Oil CompanyLiquid star polymers having terminal hydroxyl groups
US5602206 *Mar 4, 1992Feb 11, 1997Basf CorporationBlock copolymer process
US5616542 *Apr 3, 1996Apr 1, 1997Shell Oil CompanyOil with asymmetric radial polymer having block copolymer arm
US5658526 *Nov 1, 1995Aug 19, 1997Shell Oil CompanyMelting in an extruder; passing through die having a source of gas pressure inside outlet; cooling gas stream
US5663250 *May 16, 1996Sep 2, 1997Shell Oil CompanyDeprotection with molten salt
US5681895 *Aug 29, 1996Oct 28, 1997Shell Oil CompanyAnionic polymerization using a trialkylsiloxyhydrocarbyl lithium compound and coupling with a trialkoxysilane; acidolysis to produce very reactive hydroxy end groups; coatings, seals and adhesives
US5777031 *Jul 25, 1997Jul 7, 1998Shell Oil CompanyHigh 1,2 content thermoplastic elastomer/oil/polyolefin composition
US5863646 *Mar 25, 1996Jan 26, 1999Ppg Industries, Inc.Coating composition for plastic substrates and coated plastic articles
US6203913Dec 16, 1998Mar 20, 2001Ppg Industries Ohio, Inc.Coating composition for plastic substrates
US6225415Sep 20, 1999May 1, 2001University Of North Carolina At CharlotteProcess to selectively place functional groups within polymer chain
US6300414Aug 28, 1998Oct 9, 2001Basf CorporationCurable coating for thermoplastic olefins
US6420490Nov 24, 1999Jul 16, 2002Kraton Polymers U.S. LlcTelechelic polymers are produced by ozonation degradation of diene polymers
US6423778Jun 30, 1999Jul 23, 2002Basf CorporationProcess for coating olefinic substrates
US6451865Oct 30, 1998Sep 17, 2002Kraton Polymers U.S. LlcFoam composition comprising oil, thermoplastic elastomer and expandable particles
US6451913Aug 21, 2000Sep 17, 2002Kraton Polymers U.S. LlcRadial hydrogenated block copolymers showing one phase melt behavior
US6593423May 3, 2000Jul 15, 2003Ppg Industries Ohio, Inc.Adhesion promoting agent and coating compositions for polymeric substrates
US6630532 *Sep 7, 2000Oct 7, 2003Kraton Polymer U.S. LlcHaving at least two polystyrene endblocks and a midblock of hydrogenated polymerized butadiene blended with polystyrene, and oils
US6699941Nov 7, 2002Mar 2, 2004Kraton Polymers U.S. LlcSelectively hydrogenated; comonomers could comprise 1,3-butadiene, isoprene, 1,3-cyclohexadiene and/or styrene; creep resistance; diapers
US6759454Feb 6, 2003Jul 6, 2004Kraton Polymers U.S. LlcPolymer modified bitumen compositions
US6777026Oct 7, 2002Aug 17, 2004Lord CorporationFilm forming elastomer, a room temperature curing agent, and thermally conductive metal particles; protective
US6844412Jul 25, 2002Jan 18, 2005Lord CorporationAmbient cured coatings and coated rubber products therefrom
US6939916 *Apr 21, 2003Sep 6, 2005Basf CorporationAdhesion promoter, coating compositions for adhesion to olefinic substrates and methods therefor
US6979714Apr 1, 2003Dec 27, 2005Ppg Industries Ohio, Inc.Adhesion promoting agent and coating compositions for polymeric substrates
US6987142Feb 6, 2003Jan 17, 2006Kraton Polymers U.S. LlcAdhesives and sealants from controlled distribution block copolymers
US7001950Mar 24, 2003Feb 21, 2006Kraton Polymers U.S. LlcInjection molding, extrusion; butadiene-styrene copolymer
US7001956Jun 4, 2003Feb 21, 2006Kraton Polymers U.S. LlcArticles prepared from hydrogenated block copolymers
US7012118Oct 8, 2003Mar 14, 2006Kraton Polymers U.S. LlcStability; ozone resistance; radiation transparent; blend of hydrogenated and unhydrogenated resins
US7018962Jun 12, 2003Mar 28, 2006Infineum International Limitedlubricating oil improver of ethylene-alfa-olefin copolymers; diluent oil is Group II, Group III or Group IV or blend; improving low temperature viscosity in crankcase engine oils; cold cranking simulator at -35 C. of less than 3700 cPs
US7067589Feb 10, 2005Jun 27, 2006Kraton Polymers U.S. LlcBlock copolymers and method for making same
US7108873Jul 20, 2002Sep 19, 2006Applied Elastomerics, Inc.Gelatinous food elastomer compositions and articles
US7134236Jul 20, 2002Nov 14, 2006Applied Elastomerics, Inc.Formed from one or a mixture of two or more of a poly(styrene-ethylene-butylene-styrene) block copolymer(s) and one or more plasticizers in sufficient amounts to achieve gel rigidity of 20-800 gram Bloom
US7138456Feb 10, 2005Nov 21, 2006Bening Robert CBlock copolymers and method for making same
US7141621Feb 6, 2003Nov 28, 2006Kraton Polymers U.S. LlcGels from controlled distribution block copolymers
US7166672Jun 4, 2003Jan 23, 2007Kraton Polymers U.S. LlcA hydrogenated butadiene-styrene copolymer is branched with an alkoxy silane coupling agent, with variable molecular weight; use in a blends with polyethylene, extending oil; melt processability, injection molding, extrusion
US7169848Feb 6, 2003Jan 30, 2007Kraton Polymers U.S. LlcLiving copolymer containing a controlled distribution copolymer block of a conjugated diene and a monoalkenyl arene and has terminal regions that are rich in conjugated diene units and center region is rich in monoalkenyl arene
US7169850Feb 10, 2005Jan 30, 2007Kraton Polymers U.S. LlcConjugated diene-arene copolymer for block polymers with organolithium initiators
US7186779Jan 13, 2003Mar 6, 2007Kraton Polymers U.S. LlcButadiene-styrene copolymers; may contain flexible ethylene-propylene copolymer; for food wrapping films
US7208184Jul 20, 2002Apr 24, 2007Applied Elastomerics, Inc.Formed from thermoplastic elastomer block copolymers and one or more plasticizers and a food or components of food, plasticizers being in sufficient amounts to achieve a gel rigidity of 20-1,800 gram Bloom
US7220798Feb 28, 2005May 22, 2007Kraton Polymers Us LlcProcess for preparing block copolymer and resulting composition
US7223816Feb 7, 2003May 29, 2007Handlin Jr Dale LSolvent-free, hot melt adhesive composition comprising a controlled distribution block copolymer
US7226484Aug 4, 2004Jun 5, 2007Applied Elastomerics, Inc.Tear resistant gels and articles for every uses
US7232864Oct 14, 2004Jun 19, 2007Bening Robert CPolyhedral oligosilsesquioxane coupled to arms of monovinyl arenes and conjugated dienes; a well defined number of arms, coupled to a well-defined molecular structure; reactive functional groups at the coupling site; coupling anionic living polymers to yield polymers having 2 to 10 arms
US7234560Sep 30, 2003Jun 26, 2007Applied Elastomerics, Inc.Inflatable restraint cushions and other uses
US7241540Apr 27, 2004Jul 10, 2007Kraton Polymers U.S. LlcPhotocurable compositions and flexographic printing plates comprising the same
US7244785Feb 10, 2005Jul 17, 2007Bening Robert CBlock copolymers and method for making same
US7262248May 11, 2004Aug 28, 2007Kraton Polymers U.S. LlcArticles prepared from high molecular weight tetrablock copolymers
US7267855Feb 6, 2003Sep 11, 2007Kraton Polymers U.S. LlcArticles prepared from hydrogenated controlled distribution block copolymers
US7268184Jan 13, 2003Sep 11, 2007Kraton Polymers U.S. LlcButadiene-styrene copolymers; may contain flexible ethylene-propylene copolymer; for food wrapping films, fibers, filaments, melt blown or spun bond non-wovens or cast or blown films
US7271207Mar 24, 2003Sep 18, 2007Kraton Polymers U.S. LlcBituminous composition
US7282536Feb 10, 2005Oct 16, 2007Kraton Polymers LlcSulfonation of hydrogenated conjugated diene-arene block polymers via acetyl sulfate, then salt formation with a metal such as zinc acetate; lower melt and solution viscosity
US7290367Dec 25, 2003Nov 6, 2007Applied Elastomerics, Inc.Tear resistant gel articles for various uses
US7332542Feb 10, 2005Feb 19, 2008Kraton Polymers U.S. LlcConjugated diene-arene copolymer for block polymers with organolithium initiators; lower melt and solution viscosity; increase the stretching stiffness of a styrene/diene block copolymer without increasing the plasticity
US7439301Mar 1, 2005Oct 21, 2008Kraton Polymers U.S. LlcBlock copolymers having high flow and high elasticity
US7449518Mar 20, 2007Nov 11, 2008Kraton Polymers U.S. LlcHigh temperature block copolymers and process for making same
US7517932 *Apr 5, 2006Apr 14, 2009Kraton Polymers U.S. LlcPolymer has a coupling efficiency of 50-80%, a styrene block molecular weight of 9,000-9,600 g/mol, a melt flow rate of equal to or greater than 10 g/10 min (200 degrees C., 5 kg), and a butadiene block vinyl content of 20-40%; also contains a tackifier resin, a plasticizer and an antioxidant
US7569281Apr 21, 2006Aug 4, 2009Kraton Polymers U.S. LlcFlexible packaging laminate films including a block copolymer layer
US7576148Nov 9, 2005Aug 18, 2009Kraton Polymers U.S. LlcSelectively hydrogenated block copolymer-modified bituminous compositions; butadiene-styrene copolymers; roofing shingles
US7582702Mar 24, 2006Sep 1, 2009Kraton Polymers U.S. LlcButadiene-isoprene-styrene copolymers; molecular weight control
US7585916Mar 14, 2007Sep 8, 2009Kraton Polymers Us LlcBlock copolymer compositions
US7589152Dec 13, 2004Sep 15, 2009Kraton Polymers U.S. LlcAdhesive formulations for novel radial (S-I/B)x polymers
US7592390Mar 24, 2006Sep 22, 2009Kraton Polymers U.S. Llcanionic hydrogenated block copolymers of mono alkenyl arenes and conjugated dienes, and tailored softening modifiers having a particular polydispersity index that results in a surprising improvement in properties ( living polymer)
US7625851Mar 7, 2007Dec 1, 2009Kraton Polymers Us LlcViscosity index improver for lubricating oils
US7625979Jun 4, 2003Dec 1, 2009Kraton Polymers U.S. LlcProcess for preparing block copolymer and resulting composition
US7645507Oct 24, 2005Jan 12, 2010Kraton Polymers U.S. LlcProtective films and pressure sensitive adhesives
US7714069Sep 22, 2006May 11, 2010E. I. Du Pont De Nemours And CompanyMethod of producing adherent coatings on resinous substrates
US7737224Jul 20, 2006Jun 15, 2010Kraton Polymers U.S. LlcEnd blocks formed from polymerized non-sulfonated p-substituted styrene monomer; one interior block with units of other styrene monomers which have been sulfonated; non-dispersible and solid in water; has a tensile strength greater than 100 psi in the presence of water;
US7763679Sep 22, 2006Jul 27, 2010E.I. Du Pont De Nemours And CompanyBlend of a crosslinkable copolymer from an unsaturated alcohol, especially hydroxyethyl methacrylate, a saturated polymer such as telechelic polybutadiene, and a cycloaliphatic polyisocyanate crosslinking agent e.g., isophorone diisocyanate; coatings for autobody parts
US7847022Feb 6, 2003Dec 7, 2010Kraton Polymers U.S. LlcArticles prepared from controlled distribution block copolymers
US7858693Mar 24, 2006Dec 28, 2010Kratonpolymers U.S. LlcUnhydrogenated block copolymer compositions
US7893159Dec 22, 2006Feb 22, 2011Dow Global Technologies Inc.Blends of styrenic block copolymers and propylene-alpha olefin copolymers
US7994256Jan 14, 2009Aug 9, 2011Kraton Polymers U.S. LlcGel compositions
US8008398Sep 3, 2004Aug 30, 2011Kraton Polymers U.S. LlcFoamable polymeric compositions and articles containing foamed compositions
US8012539May 9, 2008Sep 6, 2011Kraton Polymers U.S. LlcMethod for making sulfonated block copolymers, method for making membranes from such block copolymers and membrane structures
US8188192Dec 19, 2008May 29, 2012Kraton Polymers U.S. LlcSoft elastomeric films
US8222346Sep 22, 2004Jul 17, 2012Dais-Analytic Corp.Block copolymers and method for making same
US8263713Oct 13, 2009Sep 11, 2012Kraton Polymers U.S. LlcAmine neutralized sulfonated block copolymers and method for making same
US8299177Jan 19, 2011Oct 30, 2012Kranton Polymers U.S. LLCCompositions containing styrene-isobutylene-styrene and controlled distribution block copolymers
US8349950Mar 11, 2009Jan 8, 2013Kraton Polymers Us LlcMiktopolymer compositions
US8377514May 31, 2011Feb 19, 2013Kraton Polymers Us LlcSulfonated block copolymer fluid composition for preparing membranes and membrane structures
US8377515Jul 19, 2011Feb 19, 2013Kraton Polymers U.S. LlcProcess for preparing membranes and membrane structures from a sulfonated block copolymer fluid composition
US8440304Sep 16, 2008May 14, 2013Henkel CorporationAcrylic pressure sensitive adhesive formulation and articles comprising same
US8445087Dec 14, 2009May 21, 2013Kraton Polymers U.S. LlcHydrogenated styrenic block copolymers blends with polypropylene
US8445631Oct 13, 2009May 21, 2013Kraton Polymers U.S. LlcMetal-neutralized sulfonated block copolymers, process for making them and their use
US8552114Nov 30, 2012Oct 8, 2013Kraton Polymers U.S. LlcMiktopolymer compositions
US8580884Nov 11, 2010Nov 12, 2013Kraton Polymers U.S. LlcThermoplastic polyurethane block copolymer compositions
US8703860Sep 19, 2012Apr 22, 2014Kraton Polymers U.S. LlcParamethylstyrene block copolymers and their use
USH1405 *Apr 9, 1992Jan 3, 1995Shell Oil CompanyEmulsifying and blending with block copolymer of hydrogenated conjugated diene and carboxylated monoalkenyl aromatic hydrocarbon
USH1438 *Dec 18, 1992May 2, 1995Shell Oil CompanyModified block copolymers functionalized in the monoalkenyl aromatic or vinylarene block
USH1949Feb 1, 1996Mar 6, 2001Shell Oil CompanyHydrogenated elastomer primed polyolefin film
USH1956Jun 8, 1998Apr 3, 2001Shell Oil CompanyReducing the viscosity of the polymer cement by polymerizing the block copolymer under conditions such that the vinyl content of the polymer produced in the polymerization step is in the range from 45 to 80 percent by weight
USH2100Jul 9, 1997Apr 6, 2004Kraton Polymers LlcElastomeric block copolymers made using large aromatic endblocks formulated with high levels of midblock compatible resin and oil give an adhesive exhibiting superior stress relaxation and set characteristics
USRE39559 *Sep 5, 2003Apr 10, 2007Kraton Polymer Us L.L.C.Useful in making coatings, sealants, binders, and block copolymers with polyesters, polyamides, and polycarbonates
USRE39617Sep 5, 2003May 8, 2007Kraton Polymers Us LlcButadiene polymers having terminal functional groups
EP0254346A2 *Jul 7, 1987Jan 27, 1988Shell Internationale Research Maatschappij B.V.Thermoplastic compositions and process for the preparation thereof
EP0684267A1May 22, 1995Nov 29, 1995Shell Internationale Research Maatschappij B.V.A method for producing asymmetric radial polymers
EP0690082A2Jun 30, 1995Jan 3, 1996Shell Internationale Research Maatschappij B.V.Star polymer viscosity index improver for oil lubricating compositions
EP0697247A2Jul 14, 1995Feb 21, 1996Shell Internationale Research Maatschappij B.V.Process for the conversion of hydrocarbonaceous feedstock
EP0698626A1Aug 10, 1995Feb 28, 1996Shell Internationale Research Maatschappij B.V.Asymmetric triblock copolymer, viscosity index improver for oil compositions
EP0698638A1Jul 14, 1995Feb 28, 1996Shell Internationale Research Maatschappij B.V.Crosslinkable waterborne dispersions of hydroxy functional polydiene polymers and amino resins
EP0700942A2Sep 4, 1995Mar 13, 1996Shell Internationale Research Maatschappij B.V.Star polymer viscosity index improver for lubricating oil compositions
EP0709416A2Sep 26, 1995May 1, 1996Shell Internationale Research Maatschappij B.V.Polyurethane sealants and adhesives containing saturated hydrocarbon polyols
EP0711795A1Nov 6, 1995May 15, 1996Shell Internationale Research Maatschappij B.V.Low viscosity adhesive compositions containing asymmetric radial polymers
EP0712892A1Nov 14, 1995May 22, 1996Shell Internationale Research Maatschappij B.V.Blends of block copolymers and metallocene polyolefins
EP0771641A2Oct 31, 1996May 7, 1997Shell Internationale Research Maatschappij B.V.Process to prepare a blown film of a block copolymer composition
EP0781605A1Dec 18, 1996Jul 2, 1997Shell Internationale Research Maatschappij B.V.Removal of metal compounds from an acid solution
EP0781782A1Dec 18, 1996Jul 2, 1997Shell Internationale Research Maatschappij B.V.Removal of alkali metal compounds from polymer cements
EP0781784A1Dec 18, 1996Jul 2, 1997Shell Internationale Research Maatschappij B.V.Removal of an alkali metal compound from a polymer cement
EP1493800A1Jun 8, 2004Jan 5, 2005Infineum International LimitedViscosity index improvers for lubricating oil compositions
EP2083063A1Jan 14, 2009Jul 29, 2009Infineum International LimitedLubricating oil composition
EP2428534A1Mar 1, 2005Mar 14, 2012Kraton Polymers US LLCElastomeric bicomponent fibers comprising block copolymers having high flow
EP2586803A1Mar 1, 2005May 1, 2013Kraton Polymers US LLCBlock copolymers having high flow and high elasticity
EP2607466A2Dec 20, 2012Jun 26, 2013Infineum International LimitedViscosity index improvers for lubricating oil compositions
EP2712808A1Oct 20, 2008Apr 2, 2014Lord CorporationSuspension system for aircraft auxiliary power unit with elastomeric member
EP2712809A1Oct 20, 2008Apr 2, 2014Lord CorporationSuspension system for aircraft auxilliary power unit with elastomeric member
WO1999005185A1 *Jul 20, 1998Feb 4, 1999Shell Int ResearchEnhanced hydrogenation catalyst removal from block copolymers by reduction in polymer cement viscosity by increasing the vinyl content of the block copolymers
WO2004106399A2May 5, 2004Dec 9, 2004Kraton Polymers Res BvProcess for making a coupled block copolymer compositon
WO2004108784A1Jun 3, 2004Dec 16, 2004Kraton Polymers Res BvArticles prepared from hydrogenated block copolymers
WO2005092979A1Mar 1, 2005Oct 6, 2005Kraton Polymers Res BvElastomeric bicomponent fibers comprising block copolymers having high flow
WO2007000191A1Dec 20, 2005Jan 4, 2007Kraton Polymers Res BvHigh melt strength thermoplastic elastomer composition
WO2007010039A1Jul 21, 2006Jan 25, 2007Kraton Polymers Res BvSulfonated block copolymers, method for making same, and various uses for such block copolymers
WO2007106346A2Mar 7, 2007Sep 20, 2007Kraton Polymers Us LlcViscosity index improver for lubricating oils
WO2007111849A2Mar 16, 2007Oct 4, 2007Robert C BeningNovel block copolymer compositions
WO2007111852A2Mar 16, 2007Oct 4, 2007Dale L HandlinNovel unhydrogenated block copolymer compositions
WO2007111853A2Mar 16, 2007Oct 4, 2007Robert C BeningNovel hydrogenated block copolymer compositions
WO2009082685A1Dec 19, 2008Jul 2, 2009Kraton Polymers Us LlcSoft elastomeric films
WO2010077799A1Dec 14, 2009Jul 8, 2010Kraton Polymers Us LlcHydrogenated styrenic block copolymers blends with polypropylene
WO2012050740A1Sep 19, 2011Apr 19, 2012Kraton Polymers U.S. LlcElastic, moisture-vapor permeable films, their preparation and their use
WO2012050860A1Sep 28, 2011Apr 19, 2012Kraton Polymers U.S. LlcEnergy recovery ventilation sulfonated block copolymer laminate membrane
WO2012054325A1Oct 14, 2011Apr 26, 2012Kraton Polymers U.S. LlcMethod for producing a sulfonated block copolymer composition
Classifications
U.S. Classification525/272, 525/258, 525/314, 525/261, 525/259, 525/914, 525/339
International ClassificationC08F8/04
Cooperative ClassificationC08F8/04
European ClassificationC08F8/04