WO1995018164A1 - Copolymeres trisequences d'oxydes d'alkylene et d'hydrocarbures, et polyurethanes prepare a partir de ces copolymeres - Google Patents

Copolymeres trisequences d'oxydes d'alkylene et d'hydrocarbures, et polyurethanes prepare a partir de ces copolymeres Download PDF

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Publication number
WO1995018164A1
WO1995018164A1 PCT/US1994/014905 US9414905W WO9518164A1 WO 1995018164 A1 WO1995018164 A1 WO 1995018164A1 US 9414905 W US9414905 W US 9414905W WO 9518164 A1 WO9518164 A1 WO 9518164A1
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Prior art keywords
copolymer
alkylene
alkylene oxide
percent
weight
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PCT/US1994/014905
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English (en)
Inventor
Johan A. Thoen
Thomas H. Kalantar
Daniel P. Green
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The Dow Chemical Company
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Publication of WO1995018164A1 publication Critical patent/WO1995018164A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes

Definitions

  • This invention relates to functional hydrocarbons and, more particularly, to functional polybutadienes and polyurethanes prepared therefrom.
  • this invention is a triblock copolymer of the formula A-B-A wherein each A block is a poly(alkylene oxide) or poly(alkylene sulfide) group and B is a polymeric hydrocarbon group with a molecular weight in the range of from 1 ,000 to 25,000, wherein the A blocks comprise from 5 to 50 percent by weight of the copolymer.
  • this invention is a process forthe preparation of a functional triblock copolymer which comprises the sequential steps of:
  • step (3) contacting the product of step (2) with a proton-donating compound under reaction conditions sufficientto provide a terminal hydroxyl or thiol group on each end of the copolymer.
  • this invention is a polyurethane polymer prepared by the reaction of the copolymer of the first aspect of the invention and at least one polyisocyanate.
  • copolymers of the invention are useful as an isocyanate-reactive compound in processes for the preparation of p ⁇ lyurethane/urea polymers and, when so used, advantageously provide a polyurethane with increased resistance to hydrolysis and weatherability, relative to polyurethanes prepared from polyether and polyester polyols.
  • polyurethanes prepared with the copolymer of the invention and difunctional isocyanates and chain extenders have been discovered to advantageously provide a thermoplastic material with improved thermal processing characteristics (such as melt flow), less phase separation, and improved physical properties, such as tensile strength, tear strength, and elongation, relative to thermoplastic materials prepared from functionalized polydienes which do not contain terminal block segments of an alkylene oxide or alkylene sulfide.
  • thermal processing characteristics such as melt flow
  • phase separation such as tensile strength, tear strength, and elongation
  • the hydroxy-terminated polybutadiene tends to undergo gross phase separation and forms relatively low molecular weight polyurethane polymers. Accordingly, the thermal processing characteristics and physical properties of such product would be less than desirable.
  • the triblock copolymer of the first aspect of the invention may be prepared by contacting a polymeric hydrocarbon dianion with an alkylene oxide or alkylene sulfide, in an amount and under reaction conditions sufficient to provide a block segment comprised of at least two repeat units derived from the alkylene oxide or alkylene sulfide on each end of the polymer; and then contacting the resulting block copolymer with a proton-donating compound under reaction conditions sufficientto provide a terminal hydroxyl orthiol group on each end of the copolymer.
  • the process of the second aspect of the invention is directed to a method for the preparation of such copolymers wherein the "B" block is a polydiene.
  • the polymeric hydrocarbon dianion (polymeric dianion) used to prepare the copolymer of the first aspect of the invention may be prepared by any of several methods.
  • the polymeric dianion may be a polydiene dianion prepared by polymerizing a con- jugated 1 ,3-diene in the presence of an initiator compound at a suitable temperature and pressure.
  • the polydiene dianion is most preferably polybutadiene.
  • polydiene refers to a polymer of a conjugated 1,3-diene.
  • An alternative method is to contact a functionalized hydrocarbon polymer with sodium, potassium, a hydroxide, alkoxide, or hydride of either, or a mixture thereof, to obtain a polymeric dianion.
  • the term "functionalized hydrocarbon polymer” as used herein means a hydrocarbon polymer with the following terminal groups: hydroxyl (-OH), thiol (-SH), primary amine (-NH 2 ), secondary amine (-NHR, wherein R is a C ⁇ _ 2 o organic moiety), sulfonic acid (-S0 3 H), and carboxyl (-COOH), or combinations thereof.
  • the particular dianion species generated will, of course, depend on its method of preparation.
  • a dihydroxy-terminated polymer will form a dialkoxide; a dithiol-terminated polymerwill form a dithiolate, and so forth.
  • suitable hydrocarbon polymers include polyethylene, poly(isobutylene), and polydienes. Most preferably, the hydrocarbon polymer is polybutadiene.
  • suitable initiator compounds include alkali metal compounds which are preferably sodium- or lithium-containing organic compounds, or mixtures of sodium- or lithium-containing organic compounds and alkali metal alkoxides or aryloxides.
  • alkali metal compounds which are preferably sodium- or lithium-containing organic compounds, or mixtures of sodium- or lithium-containing organic compounds and alkali metal alkoxides or aryloxides.
  • the polymerization process is carried out as described in copending application "A Process For The Preparation Of Polyfunctional Polydienes," by Johan Thoen et al., describes certain sodium salts and alkali metal alkoxides and aryloxides.
  • Suitable conjugated 1 ,3-dienes which are useful in the preparation of the polydiene dianion include any 1 ,3-diene containing 4 to 12 carbon atoms, preferably 4 to 8 carbon atoms.
  • suitable compounds include 1,3-butadiene; isoprene; myrcene; 2,3-dimethyl-1,3-butadiene; 1 ,3-pentadiene; 2-methyl-3-ethyl-1,3-butadiene; 2-methyl-3-ethyl-1 ,3-pentadiene; 2-ethyl-1 ,3-pentadiene; 1,3-hexadiene; 2-methyl- -1,3-hexadiene, 1,3-heptadiene; 3-methyl-1,3-heptadiene; 1,3-octadiene; 3-butyl- -1 ,3-octadiene; 3,4-dimethyl-1 ,3-hexadiene; 3-n-propyl-1
  • the alkyl groups contain from 1 to 3 carbon atoms.
  • 1 ,3-butadiene, isoprene, myrcene, 2,3-dimethyl-1 ,3-butadiene and 1 ,3-pentadiene are preferred, with 1 ,3-butadiene being particularly preferred.
  • the 1 ,3-conjugated dienes may be polymerized alone, or in a mixture with each other to form copolymers.
  • compositions may contain amounts of other anionically polymerizable monomers such as styrene, ⁇ -methylstyrene, and stilbene.
  • such comonomers are preferably employed i n an amount such that they comprise less than about 50 weight percent of the polydiene dianion, more preferably less than about 20 weight percent.
  • the copolymer of the invention is prepared by reacting a polymeric dianion with an alkylene oxide or alkylene sulfide, wherein the alkylene oxide or alkylene sulfide is employed in an amount sufficient to provide terminal block segments comprising at least two repeat units derived from the alkylene oxide or alkylene sulfide.
  • the polymeric dianion is a polydiene dianion.
  • Suitable alkylene oxides and alkylene sulfides include ethylene oxide, ethylene sulfide, propylene oxide, 1,2- or
  • the block segment is of the formula: -(CH 2 -CH 2 -0) x -, wherein x is a number from 2 to 20.
  • the alkylene oxide or sulfide is used in an amount sufficientto provide a block segment on each end of the polymer with an average number of repeat units of at least about 2, more preferably at least about 4, most preferably at least about 10; and is preferably no greater than about 20, and more preferably no greater than about 15.
  • the alkylene oxide or alkylene sulfide may simply be combined with the solution at a temperature of less than about 40°C and slowly heated to a temperature in the range of from 80°C to 130°C to obtain polymerization.
  • the process to add the terminal block segment of alkylene oxide or alkylene sulfide may be carried out under any suitable reaction conditions typically employed for the polymerization of alkylene oxide or alkylene sulfide in the presence of an initiator compound, with the functionalized hydrocarbon polymer serving as the initiator.
  • the functionalized hydrocarbon polymer may first be contacted with sodium, potassium, or a hydroxide, alkoxide, or hydride thereof, or a mixture thereof, to obtain a polymeric dianion.
  • any water generated by such procedure is preferably removed from the reaction mixture so that it is present in an amount of less than about 200 ppm, so that it will not initiate with the alkylene oxide or alkylene sulfide to any great extent.
  • the solution of polymeric dianion may then be combined with the alkylene oxide or alkylene sulfide and heated to obtain polymerization.
  • the process is carried out at a temperature in the range of from 80°C to 130°C, more preferably in the range of from 90°C to 120°C.
  • the product containing terminal block segments is contacted with a proton-donating compound under reaction conditions sufficient to provide a terminal hydroxyl orthiol group on each end of the copolymer.
  • the product containing terminal block segments is the product of step (2).
  • examples of such compounds include HCI or glacial acetic acid.
  • amine-terminated copolymers may be prepared by reductive amination of the hydroxy- or thiol-terminated copolymer, or by reaction with acrylonitrile, followed by a reduction step.
  • Sulfonic acid-terminated (-SO3H) copolymers may be prepared by the oxidation of a thiol-terminated copolymer.
  • carboxyl-terminated copolymers may be prepared by reacting the hydroxy- or thiol-terminated copolymer with an acryiate ester, followed by a hydrolysis step, and so forth.
  • the copolymer contains unsaturation, it is preferably hydrogenated under standard conditions and in the presence of a suitable catalyst in order to hydrogenate such groups.
  • a suitable catalyst Any suitable hydrogenation catalyst may be used, but generally preferred are noble metal catalysts such as platinum, palladium, or ruthenium on activated carbon or transition metals such as nickel on kieselguhr.
  • the temperature of the hydrogenation reaction is preferably in the range of from 50°C to 300°C, and is preferably less than about 100°C.
  • the duration of the reaction may vary, for example, from 6 to 24 hours, or longer, depending on the specific reactants, temperature and pressure.
  • the reaction pressure may vary from 15 psig to 2,500 psig.
  • the copolymer of the first aspect of the invention and the copolymer prepared by the process of the second aspect of the invention have an internal polymeric hydrocarbon block "B" which has a molecular weight which is preferably in the range of from 1 ,000 to 25,000, but is more preferably less than about 3,000.
  • the "A" blocks derived from the alkylene oxide or alkylene sulfide preferably comprise at least about 5 percent, more preferably at least about 10 percent, most preferably at least about 15 percent; and is preferably no greater than about 30 percent, and more preferably no greater than about 25 percent by weight of the copolymer.
  • this invention is a polyurethane polymer prepared by the reaction of the copolymer of the first aspect of the invention and at least one polyisocyanate.
  • Any reaction mixture used to prepare the polyurethane should contain from 1 to 99 percent by weight of the copolymer.
  • Suitable isocyanates include aromatic, aliphatic and cyclo-aliphatic diisocyanates and combinations thereof.
  • Representatives of these types are m-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, hexamethylene- -1 ,6-diisocyanate, tetramethylene-1 ,4-diisocyanate, cyclohexane-1 ,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 4,4'-biphenylene diisocyanate and other diisocyanates disclosed in U.S. Patent 4,731 ,416, column 5, lines 13-37.
  • isocyanate- -terminated prepolymers such as those prepared by reacting an excess of stoichiometry of a diisocyanate with a polyol.
  • Aromatic diisocyanates such as tolylene diisocyanate, 4,4'-methyldiphenyl diisocyanate and polymethylene polyphenyl isocyanate and liquid forms thereof (such as carbodiimide-modified MDI) are preferred, with diphenylmethane-
  • the polyisocyanate is preferably used in an amount such that the "index", or ratio of isocyanate groups to active hydrogen groups in the reaction mixture to prepare the polyurethane is at least 0.60: 1.00, more preferably at least 1.00: 1.00; and is preferably no greater than 2.00: 1.00, more preferably no greater than 1.20: 1.00.
  • reaction mixture to prepare the polyurethane may also contain chain extenders which, if a thermoplastic polymer is to be prepared, are preferably mostly difunctional.
  • chain extender as used herein means any compound having 2 or 3 pendant or terminal hydroxyl or primary or secondary amine groups and an equivalent weight of less than about 500.
  • the chain extender is difunctional.
  • chain extenders include aliphatic (straight- or branched-chain) diols ortriols, cycloalkane diols or triols, or cycloalkane dialkanols or trialkanols, having from 2 to 10 carbons in the chain.
  • Examples of such include ethylene glycol, 1,3-propanediol, 1 ,4-butanediol, 1 ,3- and 1,5-pentanediol, 1 ,2- and 1 ,6-hexanediol, 1 ,2-propanediol, 1,3- and 2,3-butanediol, 3-methylpentane-1 ,5-diol, 1 ,9-nonanediol, 2-methyloctane-1 ,8-diol, 1,2-, 1 ,3- and
  • 1 ,4-cyclohexanedimethanol 1 ,2-, 1 ,3-, and 1 ,4-cyclohexanediol, 1,3-cyclobutanediol and 1,3-cyclopentanediol, as well as mixtures of two or more of such diols.
  • Trifunctional extenders such as glycerol and trimethylol propane can also be employed.
  • the chain extender is 1 ,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, ethylene glycol, and diethylene glycol, or mixtures thereof.
  • the polyurethane may be prepared by any suitable method, depending on the type of material to be prepared, using the copolymer of the invention as a "polyol", or high equivalent-weight isocyanate-reactive component.
  • polyol or high equivalent-weight isocyanate-reactive component.
  • other types of polyols such as polyether or polyester polyols, may be employed in combination with the copolymer of the invention.
  • thermoset elastomers may be prepared by hand-casting or reaction injection molding (RIM) techniques; polyurethane foams may be prepared by combining the reactants in the presence of a suitable blowing agent; thermoplastic polyurethanes may be prepared by combining the reactants in either a "one-shot” technique, where the reactants are fed directly into an extruder or mixing head, or by the preparation of isocyanate-functional prepolymers which are then reacted with a chain-extruder; and polyurethane sealants may be prepared from lower equivalent weight isocyanate- and/or active hydrogen-functional prepolymers.
  • suitable urethane catalysts may also be employed in the preparation of such compositions.
  • compositions of the invention can also incorporate various additives such as fillers, fiberglass, antioxidants, pigments, fire retardants, plasticizers, reinforcing agents and wax lubricants commonly employed in the art in such compositions.
  • the polyurethane is a thermoplastic polyurethane, preferably it is thermally processable at a temperature of less than about 215°C.
  • the thermal processability, tensile strength (and elongation), and tear strength of the polyurethane polymer may be evaluated by the following test methods, respectively: ASTM D-638, ASTM D- 1938, and ASTM D-1238.
  • hydrolytic stability of a polyurethane elastomer may be tested by soaking the elastomer in water at 70°C for one week, and then testing its tensile strength and tear strength using the procedures set forth above.
  • the following examples are given to illustrate the invention and should not be interpreted as limiting it in any way. Unless stated otherwise, all parts and percentages are given by weight.
  • Example 1 Preparation Of Polyethylene Oxide-Polybutadiene-Polyethylene Oxide Triblock Copolymer Butadiene was added to a reactor vessel containing 1 ,200 ml of a mixture of anhydrous cyclohexane and tetrahydrofuran (THF) (9/1 volume/volume ratio) at about 15°C. To that was added a predetermined amount (10 to 40 mL, according to the desired molecular weight) of a previously prepared THF solution of sodium napthalenide (1 N solution), mixed with potassium t-butoxide. The molar ratio of Na: K was 1 : 1. The green-blue color changed to a deep red color and an exothermic reaction occurred.
  • THF tetrahydrofuran
  • a reaction temperature of 30°C was reached within a few minutes, after which the reactor contents were cooled to take a sample from the reactor for analysis.
  • the molecular weight of the polybutadiene was determined using a gel permeation chromatography technique and 1 H-NMR was used to determine the microstructure (percentage of repeat units containing a pendant vinyl group).
  • To the solution of the polybutadiene anion was added a predetermined amount of anhydrous ethylene oxide. The temperature was raised to 35°C for 30 minutes and subsequently to 90°C to complete the polymerization. After 4 to 8 hours, the mixture of polymer in solvent was cooled to room temperature and protonated with glacial acetic acid.
  • the acetate salt was removed by filtration and the solvent was evaporated at 80 C C under reduced pressure.
  • the product was analyzed by 1 H-NMR to determine the percent ethylene oxide content in the polymer.
  • the weight ratio of ethylene oxide blocks to polybutadiene was 44/100.
  • the average molecular weight (M n ) was 11,661, and the polydispersity index (M w /M n ) was 1.21.
  • the vinyl content (percentage of 1 ,2-polybutadiene units) of the polydiene block copolymer was 58.7 percent.
  • Example 2 Preparation Of Polyethylene Oxide-Butadiene-Polyethylene Oxide A-B-A Triblock Copolymers.
  • Butadiene 100 g was added to a reactor vessel containing 1,200 g of a mixture of anhydrous cyclohexane and tetrahydrofuran (9: 1 volume/volume ratio) at 1 1°C.
  • a THF solution of sodium napthalenide (1.0 molar) mixed with potassium-tert-butoxide (1.0 molar) was then added.
  • the green-blue color changes to deep red color and an exothermic reaction occurs.
  • a reaction temperature of 48°C was reached within a few minutes.
  • the reaction mixture was cooled to 1 1 °C.
  • a sample was taken from the reactor for analysis.
  • the number average molecular weight of the polybutadiene was determined by gel permeation chromatography (using polybutadiene standards) to be 6,441.
  • M w /M n was determined to be 1.18.
  • the vinyl content in the polybutadiene was determined by 'H-NMR to be 53 percent.
  • Ethylene oxide (6 g) dissolved in 10 mL THF was added to a 600 mL portion of the polybutadiene solution prepared above. The red color of the polybutadiene solution disappeared quickly, indicating the reaction with the ethylene oxide was occurring.
  • the temperature of the mixture was increased to 80°C and maintained there for 60 minutes.
  • the product was neutralized with dilute HCI, washed with water and dried over MgS0 .
  • the solvent was evaporated at 80°C under reduced pressure.
  • the product was analyzed by 13 C-NMR to determine the average ethylene oxide cap block length.
  • the average cap block length for the product was 2.3 ethylene oxide units per end block.
  • Example 3 Polymerization Of Polythylene Oxide End Blocks Onto Hydroxy-Functional Polybutadiene A. Preparation of Dianion: To a round-bottomed flask was added hydrogenated hydroxyl-terminated polybutadiene (available from Nippon Soda) dissolved in toluene and a stoichiometric amount (relative to the hydroxyl groups of the polybutadiene) of potassium hydroxide, to prepare a bis-potassium salt. The flask was fitted with a reflux condenser and Dean Stark trap, and the solution was refluxed for between 5 hours and 2 days until sufficient water was removed such that the final solution contained no more than 200 ppm water.
  • hydrogenated hydroxyl-terminated polybutadiene available from Nippon Soda
  • potassium hydroxide potassium hydroxide
  • the product mixture was carefully washed sequentially with dilute aqueous hydrochloric acid and saturated aqueous sodium chloride to wash out the potassium salts.
  • the organic layer was dried over anhydrous sodium sulfate and concentrated in vacuo to yield a polyethylene oxide/hydrogenated polybutadiene/polyethylene oxide triblock copolymer.
  • Example 4 Preparation of Polyethylene Oxide-(Hydrogenated-Polybutadiene)-Polyethylene Oxide Triblock Copolymer Using Aluminum-Porphyrin Catalyst
  • the reactor was evacuated and repressurized with 1 atmosphere of dry nitrogen.
  • Toluene (300 mL) was added to the reactor and the solution was stirred for 30 minutes.
  • Triethylaluminum (10.00 mL, 1.00 M, 10.0 mmol, 1.00 equivalent) was added via syringe and the reactor contents were stirred for 1 hour.
  • Example 5 Preparation of Polyurethane Polymer
  • 1 drop commercial dibutyltin dilaurate catalyst were dissolved in 200 mL dry tetrahydrofuran and the solution heated to reflux.
  • Molten purified monomeric MDI 8.901 g was added. After 1 hour, 1 ,4-butanediol (2.44 g) was added.
  • the solution was cast into a 36 mil film, with ultimate tensile strength 3,400 psi, ultimate elongation 580 percent, and tear strength 230 lb/inches.
  • the elastomer showed melt flow beginning at 200°C, without macrophase segregation, as shown by the clarity of the melt flow strand.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un copolymère triséquencé de formule A-B-A, dans laquelle A représente un groupe poly(oxyde d'alkylène) ou poly(sulfure d'alkylène) et B représente un groupe hydrocarbure polymère d'une masse moléculaire comprise entre 1000 et 25 000, les séquences A représentant entre 5 et 50 % en poids du copolymère. L'invention concerne également des polymères de polyuréthane préparés à partir dudit copolymère. Est également décrit un procédé permettant la préparation d'un copolymère triséquencé et fonctionnel, comprenant les étapes suivantes: (1) polymérisation d'un 1,3-diène conjugué dans des conditions de réaction suffisantes pour qu'il y ait formation d'un polydiène dianionique; (2) mise en contact du polydiène dianionique avec un oxyde d'alkylène ou un sulfure d'alkylène, en une quantité et dans des conditions de réaction suffisantes pour qu'il y ait formation d'un segment séquencé constitué d'au moins deux unités répétitives dérivées de l'oxyde d'alkylène ou du sulfure d'alkylène, sur chaque extrémité du polymère; et (3) mise en contact du produit obtenu à l'étape (2) avec un composé donneur de protons, dans des conditions de réaction suffisantes pour qu'il ait formation d'un groupe terminale hydroxyle ou thiol sur chaque extrémité du copolymère.
PCT/US1994/014905 1993-12-29 1994-12-23 Copolymeres trisequences d'oxydes d'alkylene et d'hydrocarbures, et polyurethanes prepare a partir de ces copolymeres WO1995018164A1 (fr)

Applications Claiming Priority (4)

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US17496993A 1993-12-29 1993-12-29
US08/174,969 1993-12-29
US34094394A 1994-11-17 1994-11-17
US08/340,943 1994-11-17

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997046602A1 (fr) * 1996-06-05 1997-12-11 Forschungszentrum Jülich GmbH Procede de fabrication de copolymeres sequences ab hydrophobes-hydrophiles
WO2010123607A2 (fr) * 2009-01-30 2010-10-28 University Of Tennessee Research Foundation Matières comprenant des polydiènes et des polymères hydrophiles et procédés apparentés
EP3545040A4 (fr) * 2016-09-23 2020-09-09 The University of Massachusetts Polyuréthane, procédé de préparation, et article comprenant le polyuréthane

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4083895A (en) * 1976-06-14 1978-04-11 Mobil Oil Corporation Modified block copolymers and process of preparing the same
US4279798A (en) * 1980-03-28 1981-07-21 The General Tire & Rubber Company Polydiene polyalkylene oxide block copolymers and their use as alcohol hydrocarbon dispersants
US4866120A (en) * 1988-06-09 1989-09-12 Mobil Oil Corporation Elastomeric end difunctional polymers
EP0502839A2 (fr) * 1991-03-04 1992-09-09 Monsanto Company Polymères fonctionnalisés
EP0522658A1 (fr) * 1991-07-09 1993-01-13 Shell Internationale Researchmaatschappij B.V. Copolymères bloc fonctionnalisés durcis avec des isocyanates

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4083895A (en) * 1976-06-14 1978-04-11 Mobil Oil Corporation Modified block copolymers and process of preparing the same
US4279798A (en) * 1980-03-28 1981-07-21 The General Tire & Rubber Company Polydiene polyalkylene oxide block copolymers and their use as alcohol hydrocarbon dispersants
US4866120A (en) * 1988-06-09 1989-09-12 Mobil Oil Corporation Elastomeric end difunctional polymers
EP0502839A2 (fr) * 1991-03-04 1992-09-09 Monsanto Company Polymères fonctionnalisés
EP0522658A1 (fr) * 1991-07-09 1993-01-13 Shell Internationale Researchmaatschappij B.V. Copolymères bloc fonctionnalisés durcis avec des isocyanates

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997046602A1 (fr) * 1996-06-05 1997-12-11 Forschungszentrum Jülich GmbH Procede de fabrication de copolymeres sequences ab hydrophobes-hydrophiles
US6284847B1 (en) 1996-06-05 2001-09-04 Forschungszentrum Julich Gmbh Process for the preparation of hydrophobic/hydrophile AB block copolymers
US8061533B2 (en) 2004-03-19 2011-11-22 University Of Tennessee Research Foundation Materials comprising polydienes and hydrophilic polymers and related methods
WO2010123607A2 (fr) * 2009-01-30 2010-10-28 University Of Tennessee Research Foundation Matières comprenant des polydiènes et des polymères hydrophiles et procédés apparentés
WO2010123607A3 (fr) * 2009-01-30 2011-02-03 University Of Tennessee Research Foundation Matières comprenant des polydiènes et des polymères hydrophiles et procédés apparentés
EP3545040A4 (fr) * 2016-09-23 2020-09-09 The University of Massachusetts Polyuréthane, procédé de préparation, et article comprenant le polyuréthane
US11046806B2 (en) 2016-09-23 2021-06-29 The University Of Massachusetts Polyurethane, method of preparation, and article comprising the polyurethane

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