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Patent US5336737 - Process for the preparation of random copolymers of conjugated dienes and ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign in<nobr>Advanced Patent Search</nobr>PatentsA process for the preparation of a random copolymer of at least one conjugated diene and at least one vinyl aromatic compound comprising reacting the monomers with the aid of an initiator based on lithium in the presence of an essentially inert solvent wherein said solvent consists of at least 60 per...http://www.google.com/patents/US5336737?utm_source=gb-gplus-sharePatent US5336737 - Process for the preparation of random copolymers of conjugated dienes and vinyl aromatic compoundsAdvanced Patent SearchPublication numberUS5336737 APublication typeGrantApplication numberUS 07/567,843Publication dateAug 9, 1994Filing dateAug 15, 1990Priority dateAug 16, 1989Fee statusPaidAlso published asCA2023218A1, CA2023218C, DE69033196D1, DE69033196T2, EP0413403A1, EP0413403B1Publication number07567843, 567843, US 5336737 A, US 5336737A, US-A-5336737, US5336737 A, US5336737AInventorsHendrik Van Ballegooijen, Joseph P. M. Peters, Johannes T. A. PlumOriginal AssigneeShell Oil CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (19), Referenced by (11), Classifications (18), Legal Events (9) External Links: USPTO, USPTO Assignment, EspacenetProcess for the preparation of random copolymers of conjugated dienes and vinyl aromatic compoundsUS 5336737 AAbstract A process for the preparation of a random copolymer of at least one conjugated diene and at least one vinyl aromatic compound comprising reacting the monomers with the aid of an initiator based on lithium in the presence of an essentially inert solvent wherein said solvent consists of at least 60 per cent by weight of cyclopentane and the heat of reaction is withdrawn by means of reflux cooling.
We claim: 1. An improved process for the preparation of a random copolymer of at least one conjugated diene and at least one vinyl aromatic compound wherein the monomers are reacted with the aid of an initiator based on lithium in the presence of an essentially inert solvent, the improvement comprising reacting the monomers in a solvent comprising at least 60 percent by weight of cyclopentane and withdrawing the heat of reaction by reflux cooling.
2. The process of claim 1 wherein the solvent comprises at least 80 per cent by weight of cyclopentane.
3. The process of claim I wherein the solvent comprises at least 95 per cent by weight of cyclopentane.
4. The process of claim 1 wherein the solvent consists of one or more compounds which are selected from the group consisting of aliphatic, cycloaliphatic, and aromatic compounds and contain 6 or less carbon atoms.
5. The process of claim 4 wherein the solvent consists of cyclopentane and isopentane.
6. The process of claim 1 wherein the copolymerization is carried out at a temperature of up to 95� C.
7. A process for the preparation of a random copolymer of at least one conjugated diene and at least one vinyl aromatic comprising the steps of:preparing a starting mixture of a conjugated diene monomer and a vinyl aromatic monomer in an essentially inert solvent, the solvent comprising at least 60 percent by weight of cyclopentane; contacting the initial mixture with a reaction initiator based on lithium; withdrawing the heat of reaction by reflux cooling; adding amounts of each of the monomers to maintain a constant ratio of the conjugated diene monomer to the vinyl aromatic monomer; and recovering a random copolymer from the inert solvent. 8. The process of claim 7 wherein the starting mixture contains less than 90 per cent by weight of the total quantity of the vinyl aromatic monomer used prior to recovery of the random polymer.
9. The process of claim 7 wherein the starting mixture contains less than 50 per cent by weight of the total quantity of the vinyl aromatic monomer used prior to recovery of the random copolymer.
10. The process of claim 7 wherein the constant ratio of the monomers is maintained by continuous addition of each of the monomers at rates about equal to consumption of the monomers.
11. The process of claim 7 wherein the reflux cooling maintains a constant polymerization temperature.
12. The process of claim 7 wherein the starting mixture contains the monomers in a weight ratio of conjugated diene to vinyl aromatic of from 50:50 to 5:95.
13. The process of claim 7 wherein the conjugated diene monomer consists of 1,3-butadiene and the vinyl aromatic monomer consists of styrene.
14. The process of claim 13 wherein the total amount of 1,3-butadiene and styrene in the starting mixture amounts to at least 0.05 per cent by weight of the starting mixture.
15. The process of claim 10 wherein the copolymerization reaction is discontinued as soon as the addition of monomers is discontinued.
BACKGROUND The invention relates to solution polymerization of conjugated dienes and vinyl aromatic compounds. The invention further relates to random copolymers of the conjugated dienes and vinyl aromatic compounds in which more than 60% of the monomer units are arranged in an arbitrary manner.
Many processes for the preparation of substantially random copolymers of conjugated dienes and vinyl aromatic compounds are well known in the art. Typically, the solvents described for the known polymerization processes include essentially any aliphatic, cycloaliphatic or aromatic compound or a mixture of these compounds, provided that the compound is essentially inert. Cyclohexane alone or in combination with another compound is a highly preferred solvent in prior art processes. Cyclopentane can be found among the compounds actually mentioned as suitable solvents although not exemplified.
An obvious reason for selection of cyclohexane is the well known dissolving ability of cyclohexane for the reaction components and the reaction products of polymerization processes of aromatic vinyl compounds and conjugated dienes. Furthermore the use of cyclohexane as solvent is an economical attractive choice because of its ready availability and its relatively low price.
The random copolymerization processes referred to above are suitably carried out at temperatures in the range of from 50� C. to 110� C. Often compounds having a lower boiling point than cyclohexane, i.e. lower than 80� C., are added to the cyclohexane containing polymerization medium, in such concentrations that the solvency power is still sufficient, in order to provide enough vapor pressure to be able to remove the heat of polymerization by means of evaporative cooling.
Isopentane and n-hexane are known to be suitable for lowering the boiling point of cyclohexane.
It is an object of the present invention to replace a major part of the cyclohexane component of the solvent used in prior art processes for the preparation of substantially random copolymers of conjugated dienes and vinyl aromatic compounds, by a more volatile component while maintaining sufficient solvency during all stages of the polymerization. This was thought to be attractive since it was assumed that this would lead to considerable savings in the steam coagulation of the cement, the solvent recovery and the polymer drying operation. Moreover if a lower boiling solvent were used as the sole solvent in the entire polymerization process further savings could be achieved in solvent storage handling and purification.
SUMMARY A process for the preparation of a random copolymer of at least one conjugated diene and at least one vinyl aromatic compound comprising reacting the monomers with the aid of an initiator based on lithium in the presence of an essentially inert solvent wherein said solvent consists of at least 60 per cent by weight of cyclopentane and the heat of reaction is withdrawn by means of reflux cooling.
DETAILED DESCRIPTION OF THE INVENTION As a result of extensive research and experimentation a process has now surprisingly been found in which the random polymerization of conjugated dienes and vinyl aromatic compounds is carried out in a solvent which consists of at least 60% by weight of cyclopentane and in which process the heat of reaction is withdrawn by means of reflux cooling.
In the process according to the present invention polymerization rate constants have been found to be significantly higher than in similar polymerization processes using n-hexane/cyclohexane mixtures as the solvent, which under similar conditions results in higher polymerization rates or alternatively results in a reduction of the monomer concentration in the reaction mixture.
The solvency power of solvents consisting of at least 60% by weight of cyclopentane was found to be at least as well as that of solvents consisting of at least 50% by weight of cyclohexane during all stages of the polymerization process.
Since the generally applied reaction temperature lies in the range up to 95� C. and since cyclopentane has a boiling point of 49� C., i.e. 32� C. lower than cyclohexane, polymerization processes carried out using a solvent according to the present invention can be easily cooled by means of reflux cooling only.
Since the polymerization process according to the present invention can be carried out at relatively low temperatures the danger of thermal decomposition of the living polymer chain end is lowered as well as the chance that when styrene is applied as the vinyl aromatic compound a high polymerization temperature causes the thermal homopolymerization of the monomer by free radicals.
Cyclopentane is readily available and can be obtained in industrial quantities from for instance naphtha streams by distillation after complete hydrogenation of the C5 fraction, from distillation of refinery crude distiller C5 streams or by hydrogenation of dicyclopentadiene.
The unexpectedness of the finding that cyclopentane is particularly suitable for use as a solvent in processes for the preparation of random copolymers of conjugated dienes and vinyl aromatic compounds is stressed by the fact that cyclopentane has been readily available for a respectable length of time.
Any other inert aliphatic, cycloaliphatic or aromatic compound being mixable with cyclopentane and not interfering with the solvency power may constitute the remaining 40 or less percentages of the solvent, aliphatic and/or cycloaliphatic and/or aromatic compounds containing 6 or less carbon atoms being preferred, isopentane being the most preferred.
In a preferred embodiment of the present invention the solvent consists of more than 80%, more preferably of more than 95%, by weight of cyclopentane.
The solvent according to the present invention can be used in virtually any solution polymerization process for the preparation of substantially random copolymers of conjugated dienes and vinyl aromatic compounds. By choosing a specific process applying specific reaction conditions substantially random copolymers having the desired specific characteristics can be produced.
Cyclopentane can be conveniently applied in known random polymerization processes. However, of all random polymerization processes, the one as disclosed in British patent specification No. 1,283,327, is particularly preferred. Therefore according to a preferred embodiment of the present invention random copolymers are prepared by batch copolymerization of a conjugated diene and a vinyl aromatic compound with the aid of an initiator based on lithium in the presence of a solvent consisting for at least 60% by weight of cyclopentane, in which embodiment (a) first a starting mixture is prepared from the solvent and part of the totally needed quantity of each of the monomers (b) subsequently the copolymerization is initiated by contacting this mixture with the initiator, and (c) during copolymerization the monomer ratio in the reaction mixture is kept constant (as hereinafter described) by addition of the remaining part of each of the monomers, while the heat of reaction is withdrawn by means of reflux cooling.
The copolymerization reaction is preferably terminated by means of substances which kill the living polymer; this can be a proton releasing compound, for instance water, an alcohol, an amine or protonic acid, or, which is preferred, a coupling agent.
The coupling can be effected conveniently by use of a difunctional coupling agent, for example 1,2 dibromoethane, or a diisocyanate providing a linear coupled copolymer or a tri-, tetra-, or other polyfunctional coupling agent for example the tetra-functional compounds silicon tetrachloride, stannic chloride, dimethyladipate and diethyladipate providing a non-linear or branched coupled copolymer. Where the coupling is only partly complete for example at 50% of the theoretical amount, the product of the coupling reaction consists partly of coupled copolymer and partly of uncoupled copolymer.
The aromatic vinyl compound is preferably styrene, but may consist of another mono-vinyl aromatic compound for example: 1-vinylnaphthalene, 3,5-diethylstyrene, 4-n-propylstyrene, 2,4,6-trimethylstyrene, 4-phenylstyrene, 4-methylstyrene, 3,5-diphenylstyrene, 3-ethyl-1-vinylnaphthalene 8-phenyl-1-vinylnaphthalene or a mixture thereof or mixtures containing predominantly styrene.
In the preferred process two different preselected monomer ratios are applied: the monomer ratio in the mixture prepared beforehand in which the copolymerization is initiated and that in which the monomers are supplied after the initiation of the copolymerization. The monomer supplementation can take place by addition either of the monomers as a mixture prepared beforehand or of each monomer separately. Also the addition can be carried out continuously or portionwise. As a result of the measures mentioned, during the polymerization the monomer ratio and the monomer concentration in the reactor is kept constant or substantially constant which facilitates the control of the process. It is recommended that less than 90% by weight of the totally needed quantity of the aromatic vinyl compound is used in the preparation of the starting mixture, the application of quantities smaller than 50% by weight of the totally needed quantity of the aromatic vinyl compound being particularly preferred.
Also special preference is given to the addition of the remaining part of each of the monomers during the copolymerization at a rate equal to the rate at which the concerning monomer is consumed. Here "equal" includes substantially equal. Fulfillment of this condition results in that in the reactor not only the monomer ratio but also the absolute quantity of each of the monomers remains constant or substantially constant. In this case the decrease of the monomer concentration does no exceed a value determined by the increase of the polymer concentration. Under these conditions the rate at which the monomers are applied during the copolymerization can be kept constant or substantially constant at a value calculated beforehand and the heat development also remains constant or substantially constant throughout the polymerization.
For obtaining a suitable polymerization rate there is no need to carry out the reaction at a high temperature, however the temperature should be sufficiently high to be able to withdraw the heat of the polymerization process by means of evaporative cooling. Therefore reaction temperatures up to 95� C. are preferred.
Though in principle in the mixture in which the copolymerization is initiated any monomer concentration can be applied preferably a total amount of monomer of at least 0.05% by weight is used, total amounts of from 0.1 to 10.0% by weight being particularly recommended.
The amount of initiator used in the process according to the present invention may vary within wide limits. In general 0.001-1.0 g of metallic or bound lithium per 100 g of monomer is applied.
If required the copolymerization can be carried out in the presence of a slight amount of divinylbenzene or other substance that causes branching or cross-linking of the copolymer, prior to, together with or subsequent to the use of a coupling agent such as silicon tetrachloride, stannic chloride, a dihalogen hydrocarbon, a monoester such as ethylacetate, ethylacrylate or phenyl benzoate or a diester obtained by the reaction of a dicarboxylic acid with a monovalent alcohol, such as diethyladipate. In addition the process can be applied in combination with the use of polar organic compound for example as described in the British patent specification No. 884,490, which modifies the initiator in such a way that statistic copolymerization is promoted. In this way the microstructure of the diene part of the copolymer is changed to the effect that the 1,2-addition structure increases.
The invention further provides an unvulcanized composition comprising a blend of a copolymer produced according to the process of the present invention with vulcanization compounding ingredients and articles which have been formed by vulcanizing such compositions.
Usual compounding ingredients are vulcanizing agents, vulcanization accelerating agents, vulcanization activating agents, antioxidants, fillers and extender oils which may be naphthenic, paraffinic or, which is preferred aromatic. The preferred vulcanizing agent is sulphur and the preferred filler is carbon black. Other examples of vulcanizing agents are 4,4'-dithiomorpholine and alkenyl phenoldisulphides. Examples of vulcanization activating agents which may be present are zinc oxide and stearic acid. Examples of vulcanization accelerating agents are cyclohexyl-2-benzothiazyl sulphenamide and 2-(4-morpholinyl-mercapto-)benzothiazole. The copolymer composition may further contain other inorganic fillers for example silica, bentonite, clay, titanium oxide, talc, diatomaceous earth, chalk and china clay.
EXAMPLE 1 1,3-Butadiene and styrene were copolymerized by means of sec-butyllithium as the initiator with the use of a purified diluent, consisting of a mixture of 80 pbw of cyclopentane and 20 pbw of other aliphatics and cycloaliphatics containing 5 or 6 carbon atoms. The copolymerization was carried out in a reactor of 9 liters capacity, which was provided with an vigorous stirrer and which had been washed beforehand with the diluent, the air in the reactor having been displaced by dry oxygen free nitrogen. The reactor was filled with 5000 grams of the diluent mixture, 87.9 grams of styrene and 14.7 grams of butadiene. After the reactor charge had been heated to the required temperature (75� C.) while stirring intensively, the traces of initiator poison still present were rendered harmless by the slow addition of a small amount of sec-butyllithium solution to be used for the copolymerization till the start of an increase in temperature of the mixture could be observed. This initiator solution contained 200 mmol of sec-butyllithium per liter; the said small amount corresponds to 0.2 mmol of lithium compound. The aforementioned amount of initiator solution needed for the copolymerization (40 ml) was subsequently added, intensive stirring still being continued, as a result of which the copolymerization was initiated. Immediately after the addition of the stoichiometric amount of sec-butyllithium, both styrene and butadiene were supplied, each of them in a rate equal to their consumption, i.e. 1.00 gram of styrene and 3.18 gram of butadiene per minute. After 240 minutes the monomers supply was stopped and 2 mmol of diethyladipate was added to the reactor to terminate the polymerization as well as couple the copolymer molecules formed. During the whole process the stirring was still continued and the temperature was kept at the same level of 75� C. Twenty minutes after the addition of the diethyladipate, the polymer solution thus obtained was carried off from the reactor and the polymer was recovered by steam stripping and drying. Details of the experimental conditions, as well as data on the copolymer formed are presented in Table I.
EXAMPLES 2-4 AND COMPARATIVE EXAMPLES A AND B Examples 2, 3 and 4 and comparative examples A and B were carried out in the same manner as example 1, with the exception of variations in the process as can be derived from tables II, III, IV, V and VI respectively, showing details of experimental conditions as well as the data on the copolymers formed.
TABLE I______________________________________(Example 1)______________________________________1- Composition of the reactor charge at the moment when thepolymerization was initiated:diluent (cyclopentane (80%))                  5000     gstyrene                87.9     gbutadiene              14.7     gsec-butyllithium       8        mmol2- Polymerization conditionsreaction temperature   75�                           C.rate of styrene supply 1.0      g/minrate of butadiene supply                  3.18     g/minpolymerization time    240      min3- Coupling reactiondiethyladipate (DEAP)  2        mmolcoupling time          20       min4- Copolymer formedMolecular weight (before coupling)                  2150001)Molecular weight (after coupling)                  720000Coupled portion of the copolymer                  77%Content of copolymerized styrene                  23.8%    w(after coupling)Microstructure of the butadiene part                  34.7%    wof the copolymer cis-1,4 contenttrans-1,4 content      55.3%    w1,2 content            10.0%    w______________________________________ 1) Molecular weights were determined by GPC, calibrated with polystyrene samples of wellknown molecular weights and narrow molecular weight distribution.
TABLE II______________________________________(Example 2)______________________________________1- Composition of the reactor charge at the moment when thepolymerization was initiated:diluent (cyclopentane (80%))                  5000     gstyrene                149.0    gbutadiene              25.0     gsec-butyllithium       8        mmol2- Polymerization conditionsreaction temperature   75�                           C.rate of styrene supply 1.69     g/minrate of butadiene supply                  5.36     g/minpolymerization time    142      min3- Coupling reactiondiethyladipate (DEAP)  2        mmolcoupling time          20       min4- Copolymer formedMolecular weight (before coupling)                  2290001)Molecular weight (after coupling)                  767000Coupled portion of the copolymer                  77%Content of copolymerized styrene                  23.6%    w(after coupling)Microstructure of the butadiene part                  36.7%    wof the copolymer cis-1,4 contenttrans-1,4 content      55.5%    w1,2 content            7.8%     w______________________________________ 1) Molecular weights were determined by GPC, calibrated with polystyrene samples of wellknown molecular weights and narrow molecular weight distribution.
TABLE III______________________________________(Example 3)______________________________________1- Composition of the reactor charge at the moment when thepolymerization was initiated:diluent (cyclopentane (80%))                  5000     gstyrene                26.7     gbutadiene              4.4      gsec-butyllithium       8        mmol2- Polymerization conditionsreaction temperature   90�                           C.rate of styrene supply 1.0      g/minrate of butadiene supply                  3.18     g/minpolymerization time    240      min3- Coupling reactiondiethyladipate (DEAP)  2        mmolcoupling time          20       min4- Copolymer formedMolecular weight (before coupling)                  2350001)Molecular weight (after coupling)                  748000Coupled portion of the copolymer                  70%Content of copolymerized styrene                  24.9%    w(after coupling)Microstructure of the butadiene part                  34.3%    wof the copolymer cis-1,4 contenttrans-1,4 content      56.6%    w1,2 content            9.1%     w______________________________________ 1) Molecular weights were determined by GPC, calibrated with polystyrene samples of wellknown molecular weights and narrow molecular weight distribution.
TABLE IV______________________________________(Example 4)______________________________________1- Composition of the reactor charge at the moment when thepolymerization was initiated:diluent (cyclopentane (80%))                  5000     gstyrene                58.5     gbutadiene              9.7      gsec-butyllithium       8        mmol2- Polymerization conditionsreaction temperature   90�                           C.rate of styrene supply 2.19     g/minrate of butadiene supply                  6.94     g/minpolymerization time    110      min3- Coupling reactiondiethyladipate (DEAP)  2        mmolcoupling time          20       min4- Copolymer formedMolecular weight (before coupling)                  2180001)Molecular weight (after coupling)                  730000Coupled portion of the copolymer                  71%Content of copolymerized styrene                  23.5%    w(after coupling)Microstructure of the butadiene part                  36.0%    wof the copolymer cis-1,4 contenttrans-1,4 content      56.8%    w1,2 content            7.2%     w______________________________________ 1) Molecular weights were determined by GPC, calibrated with polystyrene samples of wellknown molecular weights and narrow molecular weight distribution.
TABLE V______________________________________(Comparative example A)______________________________________1- Composition of the reactor charge at the moment when thepolymerization was initiated:diluent (cyclopentane/n-hexane                  5000     g50/50 w/w)styrene                149.0    gbutadiene              28.8     gsec-butyllithium       8        mmol2- Polymerization conditionsreaction temperature   75�                           C.rate of styrene supply 1.0      g/minrate of butadiene supply                  3.18     g/minpolymerization time    240      min3- Coupling reactiondiethyladipate (DEAP)  2        mmolcoupling time          20       min4- Copolymer formedMolecular weight (before coupling)                  2200001)Molecular weight (after coupling)                  750000Coupled portion of the copolymer                  74%Content of copolymerized styrene                  24.1%    w(after coupling)Microstructure of the butadiene part                  35.4%    wof the copolymer cis-1,4 contenttrans-1,4 content      55.4%    w1,2 content            9.2%     w______________________________________ 1) Molecular weights were determined by GPC, calibrated with polystyrene samples of wellknown molecular weights and narrow molecular weight distribution.
TABLE VI______________________________________(Comparative example B)______________________________________1- Composition of the reactor charge at the moment when thepolymerization was initiated:diluent (cyclopentane/n-hexane                  5000     g50/50 w/w)styrene                58.5     gbutadiene              11.2     gsec-butyllithium       8        mmol2- Polymerization conditionsreaction temperature   90�                           C.rate of styrene supply 1.0      g/minrate of butadiene supply                  3.18     g/minpolymerization time    240      min3- Coupling reactiondiethyladipate (DEAP)  2        mmolcoupling time          20       min4- Copolymer formedMolecular weight (before coupling)                  2270001)Molecular weight (after coupling)                  775000Coupled portion of the copolymer                  72%Content of copolymerized styrene                  24.3%    w(after coupling)Microstructure of the butadiene part                  35.0%    wof the copolymer cis-1,4 contenttrans-1,4 content      55.1%    w1,2 content            9.9%     w______________________________________ 1) Molecular weights were determined by GPC, calibrated with polystyrene samples of wellknown molecular weights and narrow molecular weight distribution.
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS2975160 *May 23, 1958Mar 14, 1961Phillips Petroleum CoPreparation of copolymers in the presence of an organo-lithium catalyst and a solvent mixture comprising a hydrocarbon and an ether, thioether or amineUS3294768 *Nov 14, 1963Dec 27, 1966Phillips Petroleum CoPreparation of conjugated diene polymersUS3953543 *Dec 26, 1973Apr 27, 1976The Firestone Tire & Rubber CompanyPolymerization process and polymer produced therebyUS4061848 *Feb 5, 1976Dec 6, 1977Chemische Werke Huls AktiengesellschaftProcess for cooling a polymerization reactorUS4121031 *Jun 24, 1976Oct 17, 1978Saburo MinekawaButadiene, styrene, alkyllithium catalyst, hydrocarbon solvent, slurryingEP0054911A1 *Dec 16, 1981Jun 30, 1982Asahi Kasei Kogyo Kabushiki KaishaRandom styrene-butadiene copolymer rubberEP0128607A1 *May 16, 1984Dec 19, 1984Shell Internationale Research Maatschappij B.V.Elastomeric copolymers, their preparation and their useEP0162483A1 *Feb 21, 1985Nov 27, 1985Shell Internationale Research Maatschappij B.V.Process for the preparation of polymers of conjugated dienes and optionally monoalkenyl aromatic hydrocarbonsEP0270178A2 *Nov 24, 1987Jun 8, 1988Shell Internationale Research Maatschappij B.V.Elastomers and tyres containing themEP0313164A2 *Oct 18, 1988Apr 26, 1989Shell Internationale Research Maatschappij B.V.Elastomeric compositions, process for the preparation thereof and tyres containing themGB1066667A * Title not availableGB1136189A * Title not availableGB1222325A * Title not availableGB1283327A * Title not availableGB1396630A * Title not availableGB1400497A * Title not availableGB1466183A * Title not availableGB2071117A * Title not availableGB2075521A * Title not available* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS6313216 *Sep 1, 2000Nov 6, 2001The Goodyear Tire & Rubber CompanySynthesis of styrene-isoprene rubberUS7067589Feb 10, 2005Jun 27, 2006Kraton Polymers U.S. LlcBlock copolymers and method for making sameUS7138456Feb 10, 2005Nov 21, 2006Bening Robert CBlock copolymers and method for making sameUS7223816Feb 7, 2003May 29, 2007Handlin Jr Dale LSolvent-free, hot melt adhesive composition comprising a controlled distribution block copolymerUS7244785Feb 10, 2005Jul 17, 2007Bening Robert CBlock copolymers and method for making sameUS7267855Feb 6, 2003Sep 11, 2007Kraton Polymers U.S. LlcArticles prepared from hydrogenated controlled distribution block copolymersUS7332542Feb 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 plasticityUS7737218Dec 29, 2006Jun 15, 2010Bridgestone CorporationReacting with anionic living end; engineering plasticsUS8030410 *Dec 29, 2006Oct 4, 2011Bridgestone CorporationMethod for generating free radical capable polymers using carbonyl-containing compoundsUS8222346Sep 22, 2004Jul 17, 2012Dais-Analytic Corp.Block copolymers and method for making sameUS20130030127 *Apr 18, 2011Jan 31, 2013Nippon Soda Co., Ltd.Star polymer and method of producing same* Cited by examinerClassifications U.S. Classification526/70, 526/89, 526/173, 526/87, 525/386, 526/67, 526/340International ClassificationC08F4/42, C08F4/48, C08F2/10, C08F236/10, C08F2/06, C08F2/04, C08F297/04Cooperative ClassificationC08F297/04, C08F236/10European ClassificationC08F236/10, C08F297/04Legal EventsDateCodeEventDescriptionFeb 24, 2011ASAssignmentEffective date: 20110211Owner name: KRATON POLYMERS U.S. LLC, TEXASFree format text: RELEASE BY SECURED PARTY;ASSIGNOR:UBS AG, STAMFORD BRANCH;REEL/FRAME:025845/0795May 25, 2006ASAssignmentOwner name: KRATON POLYMERS LLC, TEXASFree format text: RELEASE BY SECURED PARTY;ASSIGNOR:JPMORGAN CHASE BANK;REEL/FRAME:018224/0293Effective date: 20010228Feb 3, 2006FPAYFee paymentYear of fee payment: 12Jan 2, 2004ASAssignmentOwner name: UBS AG, STAMFORD BRANCH, CONNECTICUTFree format text: SECURITY INTEREST;ASSIGNOR:KRATON POLYMERS U.S. LLC;REEL/FRAME:014242/0281Effective date: 20031223Owner name: UBS AG, STAMFORD BRANCH 677 WASHINGTON BLVD.STAMFOFree format text: SECURITY INTEREST;ASSIGNOR:KRATON POLYMERS U.S. LLC /AR;REEL/FRAME:014242/0281Jan 22, 2002FPAYFee paymentYear of fee payment: 8Aug 22, 2001ASAssignmentOwner name: SHELL ELASTOMERS LLC, TEXASFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:SHELL OIL COMPANY;REEL/FRAME:012090/0627Effective date: 20010228Owner name: SHELL ELASTOMERS LLC 3333 HWY. 6 SOUTH WESTHOLLOWFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:SHELL OIL COMPANY /AR;REEL/FRAME:012090/0627Mar 15, 2001ASAssignmentOwner name: CHASE MANHATTAN BANK, AS COLLATERAL AGENT, THE, NEFree format text: SECURITY AGREEMENT;ASSIGNOR:KRATON, POLYMERS U.S. LLC, FORMERLY KNOWN AS SHELL ELASTOMERS LLC;REEL/FRAME:011571/0342Effective date: 20010228Owner name: CHASE MANHATTAN BANK, AS COLLATERAL AGENT, THE 270Feb 5, 1998FPAYFee paymentYear of fee payment: 4May 17, 1994ASAssignmentOwner name: SHELL OIL COMPANY, TEXASFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:VAN BALLEGOOIJEN, HENDRIK;PETERS, JOSEPH PETER MARIE;PLUM, JOHANNES THEODORUS ANDREAS;REEL/FRAME:006998/0228;SIGNING DATES FROM 19901008 TO 19901114RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google