WO2017040505A1 - Polyols à teneur réduite en oligomère cyclique et leurs compositions de polyuréthane thermoplastique - Google Patents

Polyols à teneur réduite en oligomère cyclique et leurs compositions de polyuréthane thermoplastique Download PDF

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Publication number
WO2017040505A1
WO2017040505A1 PCT/US2016/049455 US2016049455W WO2017040505A1 WO 2017040505 A1 WO2017040505 A1 WO 2017040505A1 US 2016049455 W US2016049455 W US 2016049455W WO 2017040505 A1 WO2017040505 A1 WO 2017040505A1
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WIPO (PCT)
Prior art keywords
hydroxyl
terminated polyester
polyester intermediate
enzyme
thermoplastic polyurethane
Prior art date
Application number
PCT/US2016/049455
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English (en)
Inventor
Julius Farkas
Roger W. Day
Richard A. Gross
Manoj GANESH
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Lubrizol Advanced Materials, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Publication of WO2017040505A1 publication Critical patent/WO2017040505A1/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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes

Definitions

  • the present invention relates to polyester polyols having reduced cyclic oligo- mer content and thermoplastic polyurethane compositions made with such polyols.
  • the reduced cyclic oligomer content is believed to result in reduced blooming in the thermoplastic polyurethane compositions.
  • Polyester polyols such as poly(tetramethylene adipate) glycol
  • Cyclic oligomers are formed as by-products of this process.
  • the cyclic oligomers have no hydroxyl groups to react with diisocyanate during synthesis of the thermoplastic polyurethane.
  • These cyclic oligomers can migrate to the surface of thermoplastic polyurethanes produced with the polyester polyol. This migration is also referred to as "bloom”. This bloom manifests itself as haze or visible surface residue on the thermoplastic polyurethane.
  • One embodiment of the present invention provides a hydroxyl-terminated polyester intermediate having reduced cyclic oligomer content wherein the hydroxyl- terminated polyester intermediate comprises the reaction product of one or more C 2 to C 12 linear diols with one or more C 2 to C 12 linear diacids in the presence of an enzyme.
  • the diols may include, in some embodiments, diethylene glycol or triethylene glycol.
  • the hydroxyl-terminated polyester intermediate comprises the reaction product of 1,4-butanediol and adipic acid.
  • Another embodiment of the invention provides a method for reducing the cyclic oligomer content of a hydroxyl-terminated polyester intermediate.
  • the method includes reacting one or more C 2 to C 12 linear diols with one or more C 2 to C 12 linear diacids to form a hydroxyl-terminated polyester intermediate and treating the resulting hydroxyl-terminated polyester intermediate with an enzyme to reduce the cyclic oligomer content.
  • Another embodiment of the invention provides a method of making a hydroxyl- terminated polyester intermediate with reduced cyclic oligomer content comprising reacting one or more C 2 to C 12 linear diols with one or more C 2 to C 12 linear diacids in the presence of an enzyme.
  • thermoplastic polyurethane composition comprising the reaction product of (a) hydroxyl-terminated polyester intermediate comprising the reaction product of one or more C 2 to C 12 linear diols with one or more C 2 to C 12 linear diacids in the presence of an enzyme; (b) a polyisocyanate; and (c) a chain extender.
  • thermoplastic polyurethane composition comprising the reaction product of (a) hydroxyl-terminated polyester intermediate comprising the reaction product of one or more C 2 to C 12 linear diols with one or more C 2 to C 12 linear diacids, wherein the hydroxyl-terminated polyester intermediate has been treated with an enzyme; (b) a polyisocyanate; and (c) a chain extender.
  • the enzymes useful in the various embodiments of this invention include lipase and cutinase enzymes.
  • Hydroxyl-terminated polyester intermediates may be produced by (1) an ester- ification reaction of one or more glycols with one or more dicarboxylic acids or anhydrides or (2) by transesterification reaction, i.e., the reaction of one or more glycols with esters of dicarboxylic acids. Mole ratios generally in excess of more than one mole of glycol to acid are preferred so as to obtain linear chains having a preponderance of terminal hy- droxyl groups.
  • Hydroxyl-terminated polyester intermediates include linear polyesters having a number average molecular weight (Mn) of from about 500 to about 10,000, from about 700 to about 5,000, or from about 700 to about 4,000, and generally have an acid number less than 1.3 or less than 0.5.
  • Mn number average molecular weight
  • the molecular weight is determined by assay of the terminal functional groups and is related to the number average molecular weight.
  • the dicarboxylic acids of the desired polyester can be aliphatic, cycloaliphatic, aromatic, or combinations thereof.
  • Suitable dicarboxylic acids which may be used alone or in mixtures generally have a total of from 2 to 20, for example, 2 to 12 carbon atoms and include: succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, dodecanedioic, isophthalic, terephthalic, cyclohexane dicarboxylic, and the like.
  • Anhydrides of the above dicarboxylic acids such as phthalic anhydride, tetrahydrophthalic anhydride, or the like, can also be used.
  • Adipic acid is a preferred acid.
  • the glycols which are reacted to form a desirable polyester intermediate can be aliphatic, aromatic, or combinations thereof, including any of the glycols described above in the chain extender section, and have a total of from 2 to 20 or from 2 to 12 carbon atoms.
  • Suitable examples include ethylene glycol, 1,2-propane- diol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-l,3-propanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, dodec- amethylene glycol, dietheylene glycol, triethylene glycol, and mixtures thereof.
  • the hydroxyl-terminated polyester intermediate comprises (or consists essentially of or even consists of) the reaction product of one or more C 2 to C 12 linear diols with one or more C 2 to C 12 linear diacids.
  • a molar excess of the linear diol is used so that all of the acid is consumed and the oligomers formed are capped at both ends by the diol units.
  • the hydroxyl-terminated polyester intermediate is made by the reaction of one or more C 2 to C 12 linear diols with one or more C 2 to C 12 linear diacids in the presence of an enzyme.
  • the reaction may be conducted using methods and procedures known to those of ordinary skill in the art. Some processes for making polyols, such as hydroxyl-terminated polyesters, using enzymes are described in U.S. Pat. No. 6,972,315 to Gross, which is hereby incorporated by reference. As shown herein, preparation of the hydroxyl-terminated polyester intermediate in the presence of an enzyme has been demonstrated to reduced the cyclic oligomer content of the hydroxyl- terminated polyester intermediate.
  • the hydroxyl-terminated polyester intermediate can be treated with an enzyme prior to being used to make a thermoplastic polyurethane composition.
  • an enzyme for example, when treating the hydroxyl-terminated polyester intermediate with an enzyme, a mixture of a hydroxyl-terminated polyester intermediate and the immobilized enzyme are stirred at elevated temperature (e.g, about 70°C - 90°C) for up to about 24 hours. The immobilized enzyme may then be recovered by filtration.
  • the enzymes useful for preparing or treating the hydroxyl-terminated polyester intermediate include immobilized lipase and cutinase enzymes.
  • An immobilized enzyme is an enzyme that is attached to an inert, insoluble material. Exemplary enzymes are commercially available and include NOVOZYMTM 435, LIPOZYMETM RMEVI, LIPOZYMETM TLEVI.
  • Thermoplastic polyurethanes are obtained by the reaction of the hydroxyl- terminated polyester intermediate described above with a diisocyanates and a chain lengthening or extending reagent. In this reaction, an optional urethane polymerization catalyst (as described below) is used if needed.
  • the polyisocyanate and/or polyisocyanate component includes an ⁇ , ⁇ -alkylene diisocyanate having from 5 to 20 carbon atoms.
  • Suitable polyisocyanates include aromatic diisocyanates, aliphatic diisocyanates, or combinations thereof.
  • the polyisocyanate component includes one or more aromatic diisocyanates.
  • the polyisocyanate component is essentially free of, or even completely free of, aliphatic diisocyanates.
  • the polyisocyanate component includes one or more aliphatic diisocyanates.
  • the polyisocyanate component is essentially free of, or even completely free of, aromatic diisocyanates.
  • polyisocyanates examples include aromatic diisocyanates such as 4,4 ' -methylenebis(phenyl isocyanate) (MDI), m-xylene diisocyanate (XDI), phenylene- 1,4-diisocyanate (PDI), naphthalene- 1,5 -diisocyanate ( DI), 3,3'-dimethyl-4,4'-bi- phenylene diisocyanate (TODI), and toluene diisocyanate (TDI); as well as aliphatic diisocyanates such as isophorone diisocyanate (IPDI), 1,4-cyclohexyl diisocyanate (CHDI), decane-l, 10-diisocyanate, lysine diisocyanate (LDI), 1,4-butane diisocyanate (BDI), and dicyclohexylmethane-4,4 ' -diisocyanate (H
  • MDI 4,
  • polyisocyanate is MDI and/or H12MDI. In some embodiments, the polyisocyanate includes MDI. In some embodiments, the polyisocyanate includes H12MDI.
  • the polyisocyanate used to prepare the TPU and/or TPU compositions described herein includes hexamethylene-l,6-diisocyanate, 1, 12-dodecane diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, 2,4,4-trimethyl-hexameth- ylene diisocyanate, 2-methyl-l,5-pentamethylene diisocyanate, or combinations thereof.
  • the TPU compositions described herein are made using c) a chain extender component. Chain extenders include diols, diamines, and combination thereof.
  • Suitable chain extenders include relatively small polyhydroxy compounds, for example lower aliphatic or short chain glycols having from 2 to 20, or 2 to 12, or 2 to 10 carbon atoms.
  • Suitable examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol (BDO), 1,6-hexanediol (HDO), 1,3-butanediol, 1,5-pentanediol, neopentylglycol, 1,4-cyclohexanedimethanol (CHDM), 2,2-bis[4-(2-hy- droxyethoxy) phenyljpropane (HEPP), heptanediol, nonanediol, dodecanediol, 3-methyl- 1,5-pentanediol, ethylenediamine, butanediamine, hexamethylenediamine, hydroquinone bis(2-hydroxy ethy
  • the chain extender includes BDO, HDO, 3-methyl-l,5-pentanediol, or a combination thereof. In some embodiments, the chain extender includes BDO. Other glycols, such as aromatic glycols could be used, but in some embodiments the TPUs described herein are essentially free of or even completely free of such materials.
  • the chain extender used to prepare the TPU includes a cyclic chain extender. Suitable examples include CHDM, HEPP, HER, and combinations thereof. In some embodiments, the chain extender used to prepare the TPU includes an aromatic cyclic chain extender, for example HEPP, HER, or a combination thereof. In some embodiments, the chain extender used to prepare the TPU includes an aliphatic cyclic chain extender, for example CHDM. In some embodiments, the chain extender used to prepare the TPU is substantially free of, or even completely free of aromatic chain extenders, for example aromatic cyclic chain extenders. In some embodiments, the chain extender used to prepare the TPU is substantially free of, or even completely free of polysiloxanes.
  • the chain extender component includes 1,4-butanediol, 2-ethyl-l,3-hexanediol, 2,2,4-trimethyl pentane-l,3-diol, 1,6-hexanediol, 1,4-cyclohexane dimethylol, 1,3 -propanediol, 3-methyl-l,5-pentanediol or combinations thereof.
  • the chain extender component includes 1,4-butanediol, 3-methyl-l,5-pen- tanediol or combinations thereof.
  • the chain extender component includes 1,4-butanediol.
  • the three reactants may be reacted together to form the TPU useful in this invention. Any known processes to react the three reactants may be used to make the TPU. In one embodiment, the process is a so-called "one-shot" process where all three reactants are added to an extruder reactor and reacted.
  • the equivalent weight amount of the diisocyanate to the total equivalent weight amount of the hydroxyl containing components, that is, the polyol intermediate and the chain extender glycol can be from about 0.95 to about 1.10, or from about 0.96 to about 1.02, and even from about 0.97 to about 1.005.
  • Reaction temperatures utilizing a urethane catalyst can be from about 175 to about 245°C, and in another embodiment from 180 to 220°C.
  • the TPU can also be prepared utilizing a pre-polymer process.
  • the polyol intermediates are reacted with generally an equivalent excess of one or more diisocyanates to form a pre-polymer solution having free or unreacted diisocyanate therein.
  • the reaction is generally carried out at temperatures of from about 80 to about 220°C, or from about 150 to about 200°C in the presence of a suitable urethane catalyst.
  • a chain extender as noted above, is added in an equivalent amount generally equal to the isocyanate end groups as well as to any free or unreacted diisocyanate compounds.
  • the overall equivalent ratio of the total diisocyanate to the total equivalent of the polyol intermediate and the chain extender is thus from about 0.95 to about 1.10, or from about 0.96 to about 1.02 and even from about 0.97 to about 1.05.
  • the chain extension reaction temperature is generally from about 180 to about 250°C or from about 200 to about 240°C.
  • the pre-polymer route can be carried out in any conventional device including an extruder.
  • the polyol intermediates are reacted with an equivalent excess of a diisocyanate in a first portion of the extruder to form a pre-polymer solution and subsequently the chain extender is added at a downstream portion and reacted with the pre-polymer solution.
  • Any conventional extruder can be utilized, including extruders equipped with barrier screws having a length to diameter ratio of at least 20 and in some embodiments at least 25.
  • the ingredients are mixed on a single or twin screw ex- truder with multiple heat zones and multiple feed ports between its feed end and its die end.
  • the ingredients may be added at one or more of the feed ports and the resulting TPU composition that exits the die end of the extruder may be pelletized.
  • the preparation of the various polyurethanes in accordance with conventional procedures and methods and since as noted above, generally any type of polyurethane can be utilized, the various amounts of specific components thereof, the various reactant ratios, processing temperatures, catalysts in the amount thereof, polymerizing equipment such as the various types of extruders, and the like, are all generally conventional, and well as known to the art and to the literature.
  • the described process for preparing the TPU of the invention includes both the "pre-polymer” process and the "one shot” process, in either a batch or continuous manner. That is, in some embodiments the TPU may be made by reacting the components together in a "one shot” polymerization process wherein all of the components, including reactants are added together simultaneously or substantially simultaneously to a heated extruder and reacted to form the TPU. While in other embodiments the TPU may be made by first reacting the polyisocyanate component with some portion of the polyol component forming a pre-polymer, and then completing the reaction by reacting the pre-polymer with the remaining reactants, resulting in the TPU.
  • the composition After exiting the extruder, the composition is normally pelletized and stored in moisture proof packaging and is ultimately sold in pellet form. It being understood that the composition would not always need to be pelletized, but rather could be extruded directly from the reaction extruder through a die into a final product profile.
  • One or more urethane polymerization catalysts may be present during the polymerization reaction for forming the thermoplastic polyurethane.
  • any conventional catalyst can be utilized to react the diisocyanate with the polyol intermediates or the chain extender.
  • suitable catalysts which in particular accelerate the reaction between the NCO groups of the diisocyanates and the hydroxy groups of the polyols and chain extenders are the conventional tertiary amines known from the prior art, e.g.
  • organometallic compounds such as titanic esters, iron compounds, e.g. ferric acet- ylacetonate, tin compounds, e.g. stannous diacetate, stannous dioctoate, stannous dilaurate, or the dialkyltin salts of aliphatic carboxylic acids, e.g. dibutyltin diacetate, dibutyltin dilaurate, or the like.
  • the amounts usually used of the catalysts are from 0.0001 to 0.1 part by weight per 100 parts by weight of polyhydroxy compound (b).
  • Various types of optional components can be present during the polymerization reaction, and/or incorporated into the TPU elastomer described above to improve processing and other properties.
  • antioxidants such as phenolic types, organic phosphites, phosphines and phosphonites, hindered amines, organic amines, organo sulfur compounds, lactones and hydroxylamine compounds, biocides, fungicides, antimicrobial agents, compatibilizers, electro- dissipative or anti-static additives, fillers and reinforcing agents, such as titanium dixide, alumina, clay and carbon black, flame retardants, such as phosphates, halogenated materials, and metal salts of alkyl benzenesulfonates, impact modifiers, such as methacrylate-butadiene-styrene (“MBS”) and methylmethacrylate butylacrylate (“MBA”), mold release agents such as waxes, fats and oils, pigments and colorants, plasticizers, polymers, rheology modifiers such as monoamines, polyamide waxes, silicones, and polysiloxanes, slip
  • antioxidants such as phenolic
  • TPU compositions described above are highly useful materials that can provide an attractive combination of physical properties. Whether for its outstanding toughness, durability or processing ease, TPU is a versatile material that bridges the gap between rubber and plastics. Accordingly, TPU compositions find use in many different applications.
  • the TPU compositions of the invention and any blends thereof may be used for any TPU applications known in the art or hereafter developed. Because of the inclusion of the hydroxyl-terminated polyester described herein in the TPU composition, TPU compositions in accordance with the present invention will have reduced blooming, which provides additional utility to the TPUs of the invention.
  • TPU compositions and any blends thereof may be used to make films, including but not limited to multi-layer films and laminates, fibers, and extruded sheets.
  • the compositions of the invention or any blends thereof may also be used to prepare molded products in a variety of molding processes.
  • the molding processes are well-known to those of ordinary skill in the art and include but are not limited to, cast molding, cold forming matched-die molding, compression molding, foam molding, injection molding, gas-assisted injection molding, profile co-extrusion, profile extrusion, rotational molding, sheet extrusion, slush molding, spray techniques, thermoforming, transfer molding, vacuum forming, wet lay-up or contact molding, blow molding, extrusion blow molding, injection blow molding, and injection stretch blow molding or combinations thereof.
  • TPU compositions may also be useful in a variety of other applications, including adhesives, sealing applications, conveyor belts, shock pads, wire and cable jacketing, electronics, and recreation equipment.
  • PTMAG (5 grams) was stirred with Novozyme® 435 (500 mg) at 80°C for 8 hours. After filtration, the resulting treated polyol had cyclic oligomer content of 0.22%.
  • PTMAG (5 grams) was stirred with Novozyme® 435 (500 mg) at 90°C for 8 hours. After filtration, the resulting treated polyol had cyclic oligomer content of 0.17%.
  • PTMAG (5 grams) was stirred with Lipozyme® RMFM (500 mg) at 70°C for 8 hours. After filtration, the resulting treated polyol had cyclic oligomer content of 0.84%.
  • 2000 Mn PTMAG was synthesized by heating together 1,4-butane diol and adipic acid (mol ratio 1.1/1) at 150°C for 30 minutes under nitrogen atmosphere. The reaction mixture was cooled to 90°C, then Novozyme® 435 (10% by weight) was added and the reaction mixture was heated for 2 hours at 90°C under nitrogen. Vacuum was then applied. After heating 2 hours at 90°C under vacuum (20 torr), the cyclic oligomer content was 1.27%). After heating 4 hours at 90°C under vacuum (20 torr), the cyclic oligomer content was 0.82%.
  • 2000 Mn PTMAG was synthesized by heating together 1,4-butane diol and adipic acid (mol ratio 1.1/1) at 150°C for 30 minutes under nitrogen atmosphere. The reaction mixture was cooled to 90°C, then Novozyme® 435 (10%> by weight) was added and the reaction mixture was heated for 2 hours at 90°C under nitrogen. Vacuum was then applied. After heating 6 hours at 90°C under vacuum (10 torr), the cyclic oligomer content was 0.45%.
  • each chemical component described is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, that is, on an active chemical basis, unless otherwise indicated.
  • each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade.

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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)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne un intermédiaire de polyester terminé par un groupe hydroxyle qui comporte le produit réactionnel d'un ou de plusieurs diols linéaires en C2 à C12 avec un ou plusieurs diacides linéaires en C2 à C12 et qui présente une teneur réduite en oligomère cyclique. L'intermédiaire de polyester terminé par un groupe hydroxyle peut être fabriqué en présence d'une enzyme ou traité avec une enzyme pour réduire la teneur en oligomère cyclique. La présente invention concerne également des compositions de polyuréthane thermoplastique fabriquées avec l'intermédiaire de polyester terminé par un groupe hydroxyle présentant une teneur réduite en oligomère cyclique.
PCT/US2016/049455 2015-09-04 2016-08-30 Polyols à teneur réduite en oligomère cyclique et leurs compositions de polyuréthane thermoplastique WO2017040505A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019112743A1 (fr) * 2017-12-07 2019-06-13 Lubrizol Advanced Materials, Inc. Polyuréthanes thermoplastiques présentant une perméabilité à l'humidité élevée et une faible absorption d'eau

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2272904A (en) * 1992-11-30 1994-06-01 Baxenden Chem Ltd Solvent based enzymatic synthesis
US5962624A (en) * 1998-03-10 1999-10-05 Hendel Kommanditgesellschaft Auf Aktien Enzymatic synthesis of polyesters
US20040019178A1 (en) * 2002-07-19 2004-01-29 Gross Richard A. Enzyme-catalyzed polycondensations
US20100239803A1 (en) * 2009-03-18 2010-09-23 Lubrizol Advanced Materials, Inc. Thermoplastic Polyurethane With Reduced Tendency To Bloom

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2272904A (en) * 1992-11-30 1994-06-01 Baxenden Chem Ltd Solvent based enzymatic synthesis
US5962624A (en) * 1998-03-10 1999-10-05 Hendel Kommanditgesellschaft Auf Aktien Enzymatic synthesis of polyesters
US20040019178A1 (en) * 2002-07-19 2004-01-29 Gross Richard A. Enzyme-catalyzed polycondensations
US6972315B2 (en) 2002-07-19 2005-12-06 Gross Richard A Enzyme-catalyzed polycondensations
US20100239803A1 (en) * 2009-03-18 2010-09-23 Lubrizol Advanced Materials, Inc. Thermoplastic Polyurethane With Reduced Tendency To Bloom

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019112743A1 (fr) * 2017-12-07 2019-06-13 Lubrizol Advanced Materials, Inc. Polyuréthanes thermoplastiques présentant une perméabilité à l'humidité élevée et une faible absorption d'eau
CN111433249A (zh) * 2017-12-07 2020-07-17 路博润先进材料公司 具有高湿气穿透率与低吸水率的热塑性聚氨酯
US11827737B2 (en) 2017-12-07 2023-11-28 Lubrizol Advanced Materials, Inc. Thermoplastic polyurethanes with high moisture vapor transmission and low water absorption
US20240043603A1 (en) * 2017-12-07 2024-02-08 Lubrizol Advanced Materials, Inc. Thermoplastic polyurethanes with high moisture vapor transmission and low water absorption

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