CN100341914C - Heat resistant high moisture vapor transmission thermoplastic polyurethane - Google Patents
Heat resistant high moisture vapor transmission thermoplastic polyurethane Download PDFInfo
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- CN100341914C CN100341914C CNB2003801027887A CN200380102788A CN100341914C CN 100341914 C CN100341914 C CN 100341914C CN B2003801027887 A CNB2003801027887 A CN B2003801027887A CN 200380102788 A CN200380102788 A CN 200380102788A CN 100341914 C CN100341914 C CN 100341914C
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- Prior art keywords
- hydroxy
- thermoplastic polyurethane
- end capped
- polyurethane polymer
- aromatic
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- 230000005540 biological transmission Effects 0.000 title claims abstract description 12
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims description 132
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims description 132
- 229920000570 polyether Polymers 0.000 claims abstract description 66
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 61
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000835 fiber Substances 0.000 claims abstract description 45
- 239000004970 Chain extender Substances 0.000 claims abstract description 43
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 239000004744 fabric Substances 0.000 claims abstract description 26
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 229920002635 polyurethane Polymers 0.000 claims abstract 5
- 239000004814 polyurethane Substances 0.000 claims abstract 5
- 239000000126 substance Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 28
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- -1 polyoxyethylene Polymers 0.000 claims description 17
- 239000000654 additive Substances 0.000 claims description 14
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 11
- 235000010290 biphenyl Nutrition 0.000 claims description 11
- 239000004305 biphenyl Substances 0.000 claims description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 7
- 229920002313 fluoropolymer Polymers 0.000 claims description 6
- 239000004811 fluoropolymer Substances 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 6
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
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- 239000005059 1,4-Cyclohexyldiisocyanate Substances 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 229920002334 Spandex Polymers 0.000 description 2
- 241001586224 Visnea mocanera Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 150000002009 diols Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 210000004177 elastic tissue Anatomy 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
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- 210000001519 tissue Anatomy 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 1
- JRQLZCFSWYQHPI-UHFFFAOYSA-N 4,5-dichloro-2-cyclohexyl-1,2-thiazol-3-one Chemical compound O=C1C(Cl)=C(Cl)SN1C1CCCCC1 JRQLZCFSWYQHPI-UHFFFAOYSA-N 0.000 description 1
- 229920002955 Art silk Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- DSSXKBBEJCDMBT-UHFFFAOYSA-M lead(2+);octanoate Chemical compound [Pb+2].CCCCCCCC([O-])=O DSSXKBBEJCDMBT-UHFFFAOYSA-M 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
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- AKTIAGQCYPCKFX-FDGPNNRMSA-L magnesium;(z)-4-oxopent-2-en-2-olate Chemical compound [Mg+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AKTIAGQCYPCKFX-FDGPNNRMSA-L 0.000 description 1
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- OOCYPIXCHKROMD-UHFFFAOYSA-M phenyl(propanoyloxy)mercury Chemical compound CCC(=O)O[Hg]C1=CC=CC=C1 OOCYPIXCHKROMD-UHFFFAOYSA-M 0.000 description 1
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Abstract
A thermoplastic polyether polyurethane having high moisture vapor transmission, high melting point and static dissipative properties is disclosed. The thermoplastic polyether polyurethane is prepared by reacting a hydroxyl terminated polyether intermediate, an aromatic chain extender glycol, and a polyisocyanate. The polymers formed are useful for melt-spun fibers, fabric coatings for breathable garments, house wrap, roofing membranes, and other applications requiring high vapor transmission and high melting points.
Description
Cross reference
According to the provisional application No.60/424 that submitted on November 8th, 2002,884 submit this patent application to.
Invention field
The present invention relates to heat resistant thermoplastic polyurethane (TPU) composition, said composition has high moisture vapor permeability, does not see through liquid water simultaneously.TPU composition of the present invention also has electrostatic dissipative properties.This TPU composition can be used for the application of requirement high moisture vapor permeability, as house wrap (house wrap), the roof liner underbed of putting up a house, various fabric coatings, and melt spun fibre.The end-use goods that the present invention also relates to produce described TPU method for compositions and comprise this TPU composition.
Background of invention
Typically pass through hydroxy-end capped polyethers or polyester, chainextender and isocyanate compound react and preparation TPU polymkeric substance.The various types of compounds that is used for every kind of three kinds of reactant is disclosed in the literature.Can use various fields from the TPU polymkeric substance of this three kinds of reactants preparation, wherein prepare product by following mode: melt TPU also is configured as different shape by technology as extruding with molding.The important use of TPU is to be called in the field of melt spun elastic fibers of Spandex (Spandex) in preparation.The TPU fiber can combine with preparation clothes and some other kind consumer's goods and Industrial products with other natural and synthon.
TPU is the multi-block polymer that contains soft chain segment and hard segment.This characteristic explain the reason of excellent resilience performance of TPU.Soft chain segment is generally polyethers or polyester and is formed by hydroxy-end capped intermediate.Hard segment is made up of chain extender glycol and isocyanic ester.
U.S. patent 5,959, and 059 discloses from hydroxyl terminated polyether, the TPU of diol chain-extension agent and vulcabond preparation.This TPU can be used for preparing fiber, golf ball core, recreational wheels and other purposes.
A defective of the TPU fiber of previously known is their low temperature tolerance.If people wish to prepare goods such as clothes by in conjunction with TPU fiber and synthon as trevira, then temperature tolerance is very important.These synthon must dye and thermal-setting at high temperature with prevent from they the preparation clothes the washing and dry recycle during shrink.Reason thus, lower temperature TPU fiber closes use with natural fiber such as cotton knot always, and this natural fiber does not require that high temperature thermo-setting handles.
Also in using, fabric coating expects the TPU of anti-comparatively high temps.It is in clothes that a kind of fabric coating is used, and wherein the TPU lining can use with fluoropolymer coating, heats this fluoropolymer coating with drying and crosslinked fluoropolymer after usually on being applied to fabric.This TPU need tolerate this heat-processed.
The TPU polymkeric substance also can be used for wherein very important use of antistatic property, as is used for the packing of sensitive electronic components.
U.S. patent 6,140, and 405; 5,863,466; 6,284,839; 5,574,104; 5,159,053; 6,207,361 and 6,197,486 all disclose the TPU that is used to prepare the goods with antistatic or electrostatic dissipative properties.
The another kind of key property of the TPU that uses for the present invention is its moisture transmission (MVT) performance.The MVT performance of TPU is being used as fabric coating, fiber, and the teleblem of putting up a house, house wrap and other are very important in using.The TPU of high MVT allows moisture to overflow but does not allow penetration by liquid water.This feature makes that clothes is more comfortable and keeps the building structure drying.
Have high temperature tolerance, the TPU of high MVT and antistatic property be expect very much and at product such as fabric, fabric coating, house wrap can realize the enhanced performance in put up a house top product and the clothes.
Summary of the invention
From with following substance reaction deutero-heat resistant high moisture vapor transmission (MVT) thermoplastic polyurethane (TPU) polymkeric substance: (1) at least a hydroxy-end capped polyether intermediate, wherein this intermediate comprises the alkylene oxide with following general formula:
Wherein x is the integer of 1-10 and the integer that y is 11-115; (2) the end capped chainextender of at least a aromatic hydroxy; With at least a polyisocyanates.Alkylene oxide unit in the polyether intermediate can be in main chain or in side chain or side chain.
The fusing point of TPU polymkeric substance of the present invention is about 150 ℃-Yue 220 ℃, preferred about 160 ℃-Yue 200 ℃ and more preferably from about 165 ℃-Yue 180 ℃.The MVT that TPU polymkeric substance of the present invention is measured on 1.0 mil thick samples is greater than about 4500g/m
2It and be preferably greater than about 5500g/m
2My god.Equally, the surface resistivity of TPU polymkeric substance of the present invention is less than about 1.0 * 10
11Ohm-sq (square).
The objective of the invention is to use above-mentioned TPU to comprise the melt spun elastic fibers of TPU, apply textiles and other end-use goods with preparation.
Another object of the present invention is the method for production TPU of the present invention.
Other purpose of the present invention be the preparation can with synthon, as the woven together melt spun fibre of trevira.
Detailed description of the preferred embodiments
From at least a hydroxy-end capped polyether intermediate, at least a aromatic chain extender glycol and at least a polyisocyanates prepare TPU polymkeric substance of the present invention.
The first kind of neccessary composition that is used to prepare TPU is at least a hydroxy-end capped polyether intermediate.This hydroxy-end capped polyether intermediate comprises the alkylene oxide with following general formula:
Wherein x is the integer of 1-10, and preferred 2-6 and y are the integers of 11-115, the integer of preferred 20-80.The most preferred embodiment be when x be 2 and y when being the integer of about 28-38.Alkylene oxide unit in the polyether intermediate can be in main chain or in side chain or side chain or can be in main chain and side chain.Hydroxy-end capped polyether intermediate is the polyether glycol derived from following material: contain the glycol or the polyvalent alcohol that amount to 1-10 carbon atom, preferred alkyl glycol or glycol, it and the ether that comprises alkylene oxide, typically oxyethane or tetrahydrofuran (THF) or its mixture reaction with 2-6 carbon atom.For example, can produce the polyethers of hydroxyl-functional subsequently with reacting ethylene oxide by at first with propylene glycol and propylene oxide reaction.The primary hydroxyl that derives from oxyethane is more more reactive and be preferred therefore than secondary hydroxyl.Useful commercial polyether glycol comprises following material: comprise poly-(ethylene glycol) with the oxyethane of glycol reaction, comprise poly-(propylene glycol) with the propylene oxide of propylene glycol reaction.Copolyether also can be used for the present invention.Copolyether can be segmented copolymer or random copolymers.Poly-(ethylene glycol) is preferred polyether intermediate.It is about 10,000 that the number-average molecular weight of various polyether intermediate (Mn) is generally about 350-, desirably is about 500-about 5,000, with preferred about 700-about 3,000 and most preferably from about 1,000-about 2,000, this number-average molecular weight is determined by the analysis of functional end-group, and is molecular-weight average.The blend of the polyether intermediate that two or more are hydroxy-end capped can be used for preparing TPU of the present invention.
The second kind of neccessary composition that is used to prepare TPU of the present invention is aromatic chain extender glycol.Benzenediol and Xylene glycol are the suitable chain extenders that is used to prepare TPU of the present invention.Xylene glycol is 1,4-two (methylol) benzene and 1, the mixture of 2-two (methylol) benzene.Benzenediol is a preferred chainextender and particularly including Resorcinol, promptly be also referred to as 1, two (beta-hydroxyethyl) ethers of 4-two (2-hydroxyl-oxethyl) benzene, Resorcinol promptly is also referred to as 1, two (beta-hydroxyethyl) ethers of 3-two (2-hydroxyethyl) benzene, catechol, promptly be also referred to as 1, two (beta-hydroxyethyl) ethers of 2-two (2-hydroxyl-oxethyl) benzene, and combination.Can use the blend of two or more aromatic glycol chain extender.
The aromatic glycol chain extender quantity that is used to prepare TPU generally is that about 1.0-is about 2.0, the about 1.8 moles/mole hydroxyl terminated polyether intermediate of preferably about 1.2-.
The third neccessary composition that is used to prepare TPU of the present invention is at least a polyisocyanates.Preferably, polyisocyanates is a vulcabond.Although can adopt aliphatic vulcabond, very preferably aromatic diisocyanate.In addition, generally avoid using to cause crosslinked polyfunctional isocyanate's compound, i.e. triisocyanate etc. and therefore if you are using, then the quantity of Shi Yonging is generally less than 4mol% and preferably less than 2mol%, based on the total mole number of all various isocyanic ester that use.Suitable vulcabond comprise aromatic diisocyanate as: 4,4 '-methylene-bis (phenyl isocyanate) (MDI), m xylene diisocyanate (XDI), phenylene-1,4-vulcabond, naphthalene-1,5-vulcabond, ditan-3,3 '-dimethoxy-4 ', 4 '-vulcabond and tolylene diisocyanate (TDI); And aliphatic vulcabond such as isophorone diisocyanate (IPDI), 1,4-cyclohexyl diisocyanate (CHDI), decane-1,10-vulcabond and dicyclohexyl methyl hydride-4,4 '-vulcabond.The blend that also can use the dimer of above vulcabond and tripolymer and can use two or more vulcabond.
Be used for polyisocyanates of the present invention and can be low-molecular weight polymer or oligopolymer form, described polymkeric substance or oligopolymer are by isocyanate-terminated.For example, above-described hydroxy-end capped polyether intermediate can be reacted to produce by isocyanate-terminated low-molecular weight polymer with the compound that contains isocyanic ester.In the TPU field, such material is commonly referred to prepolymer.The number-average molecular weight of such prepolymer (Mn) is generally about 500-about 10,000.
The mol ratio of one or more vulcabond generally is the total mole number of about 0.95-about 1.05 and one or more hydroxy-end capped polyether intermediate of about 1.03 moles/mole of preferably about 0.98-and one or more aromatic chain extender.
TPU polymkeric substance of the present invention is made up of hard segment and soft chain segment.Soft chain segment comprises hydroxy-end capped polyethers and hard segment comprises aromatic diol and isocyanic ester.Importantly soft chain segment has the limited solubility in hard segment, makes that soft chain segment concentration on the surface of TPU is higher when forming TPU.Because soft chain segment causes that TPU can transmit moisture, so the soft chain segment of higher concentration from the teeth outwards provides higher MVT.
Also importantly TPU comprises aromatic glycol chain extender, and with conventional straight diol, as 1, the 4-butyleneglycol is relative.Aromatic glycol chain extender causes more pyritous TPU and makes soft chain segment be insoluble to hard segment, therefore increases MVT.
The method of producing TPU polymkeric substance of the present invention can adopt conventional TPU producing apparatus.With above-described hydroxy-end capped polyether intermediate, vulcabond and aromatic chain extender generally add together and react according to any conventional urethane reaction method.Preferably, the group that formation of the present invention TPU is used is at suitable mixing machine, as is called the Banbury mixer of Banbury (Banbury) mixing machine, or melt polymerization in the preferred forcing machine.In a preferred method, join in the forcing machine with hydroxy-end capped polyether intermediate and aromatic glycol chain extender blend and as blend.Vulcabond is joined in the forcing machine separately.The suitable processing of vulcabond or polymerization initiation temperature are about 100 ℃-Yue 200 ℃ and preferred about 100 ℃-Yue 150 ℃.The suitable processing of the hydroxy-end capped polyether intermediate and the blend of aromatic chain extender or polymerization initiation temperature are about 100 ℃-Yue 220 ℃ and preferred about 150 ℃-200 ℃.For the suitable mixing time that makes various components can react and form TPU polymkeric substance of the present invention generally is about 5 minutes of about 10 minutes of about 2-and preferably about 3-.
The preferred method of producing TPU of the present invention is the method that is called one-step polymerization method.In the one-step polymerization method that original position usually takes place, three kinds of components, i.e. one or more hydroxy-end capped polyether intermediate, aromatic diol, and reaction simultaneously takes place between the vulcabond.Reaction generally causes under about 100 ℃-Yue 120 ℃ temperature.Because reaction is heat release, so temperature of reaction generally is increased to about 220 ℃-250 ℃.The TPU polymkeric substance leaves extruder and granulation.The TPU pellet is stored in the container of heating usually to continue reaction and dry TPU pellet.
Often catalyzer such as Ya Xi and other metal carboxylate and tertiary amine are adopted in expectation.The example of metal carboxylates catalysts comprises stannous octoate, dibutyl tin laurate, phenylmercuric propionate, lead octoate 36, ferric acetyl acetonade, magnesium acetylacetonate etc.The example of tertiary amine catalyst comprises triethylenediamine etc.The quantity of one or more catalyzer is very low, is generally the final TPU polymkeric substance that about 100 weight parts of about 50-/1,000,000 weight parts form.
The weight-average molecular weight of TPU polymkeric substance of the present invention (Mw) is about 100, and about 500,000 dalton of 000-are preferred about 150, about 400,000 dalton of 000-and more preferably from about 175, about 300,000 dalton of 000-.Measure the Mw of TPU polymkeric substance according to the relative polystyrene standards of gel permeation chromatography (GPC).
TPU polymkeric substance of the present invention can with various conventional additives or compounding agent, as mixing such as filler, extender, pigment, softening agent, lubricant, UV absorption agents.Filler comprises talcum, silicate, clay, lime carbonate etc.The level of conventional additives depends on the cost of final performance and required final application, as the technician in compounding TPU field is known.Can during forming TPU, add additive in reaction, but in the second compounding step, add usually.
TPU polymkeric substance of the present invention has about 150 ℃-Yue 220 ℃, preferred about 160 ℃-Yue 200 ℃ and more preferably from about 165 ℃-Yue 180 ℃ high-melting-point, use differential scanning calorimeter (DSC) to measure fusing point according to ASTM D-3417-99.High-melting-point is important using melt spun fibre in conjunction with other synthon in the application as polyester.Some melt application of paints also requires high-melting-point TPU with the tolerance manufacturing process, particularly requires to use those application of fluoropolymer.
TPU polymkeric substance of the present invention also has high humidity and sees through (MVT) rate.This feature is important in following application: wherein importantly transmitting moisture but also make TPU by TPU is the barrier of liquid water.The MVT that TPU polymkeric substance of the present invention is measured on 1.0 mil thick samples is greater than about 4500g/m
2It and be preferably greater than about 5500g/m
2My god.High MVT causes by the fabric of TPU coating more comfortable.Equally, in clothes from TPU preparation and with other fiber bonded melt spun fibre be more comfortable for the wearer of such clothes.High MVT also expects in using as put up a house teleblem and house wrap, needs moisture is delivered to atmosphere from building structure in the described application.
Use the Permatran-W model 100K Instrument measuring MVT numerical value of Mocan.The test sample that uses is the flat membrane sample of 1 mil thick, and this sample is produced on one inch forcing machine.Experimental film is regulated 24 hours under 50% relative humidity.Membrane sample is cut into 2 inches take advantage of 2 inches squares.After sample is put into the test tank of Permatran-W model 100K, with general test parameter input Mocan computer system.Computer starting regulating cycle and testing after finishing this cycle begins automatically.At test period with statistical test information mapping with can obtain the printed report of testing data at any time.Computer is determined the time of end of test (EOT) automatically.
TPU with high MVT forms breathable fabric, and it allows moisture to overflow provides the obstruct of liquid towards water simultaneously.The prior art breathable fabric that contains the thermoplastic layer has fine porosity or hole usually to allow moisture overflow in plastics film.TPU layer in the breathable fabric of the present invention does not have hole or hole, they be solid (solid), this causes more intact obstruct of liquid towards water infiltration to provide the comfort sense that allows moisture to overflow by the MVT performance simultaneously.
Breathable fabric contains at least one tissue layer usually, and it can be supatex fabric or Woven fabric.The fiber that is used for tissue layer can be any known natural or synthon.The example of natural fiber is cotton and wool.The example of synthon is nylon, polyester, artificial silk and Kevlar.Breathable fabric also contains one or more TPU polymer layers of the present invention.The TPU polymkeric substance is applied on the fabric by the melt coating processes, this technology comprise extrude or roll TPU fine sheet and apply the backing material to fabric.The TPU sheet material also can be extruded or be rolled, and coiling and succeeding layer are pressed onto on the fabric.Melt applies and laminated technology is well known in the art.Binder layer is generally used for obtaining the bonding of each layer in the breathable fabric.Breathable fabric also can contain fluoropolymer layer, and this fluoropolymer layer is applied usually and must heat with dry and crosslinked.
Breathable fabric can be made various clothes and be special expectation in following clothes: as sweat shirt, overcoat and the protective clothing worn by the people that work in security army and the factory.Whole clothing can be made or breathable fabric can only be used for the part of clothes from breathable fabric.
When TPU of the present invention prepares melt spun fibre, preferably use additive with slight crosslinked TPU.Preferred additives is diphenylmethanediisocyanate terminated polyether prepolymer or the end capped polyester prepolyer of diphenylmethanediisocyanate.These materials are polyethers or polyester glycol, and wherein hydroxyl changes into isocyanate groups to provide isocyanate-terminated.Crosslinking additives can be for the Hyperlast of polyether prepolymer
5130 and for the Diprane of polyester prepolyer
5128 and Diprane
5184 available from Hyperlast Limited, U.K..Preferred additives is Hyperlast
5130, it is the diphenylmethanediisocyanate terminated polyether prepolymer derived from following material: number-average molecular weight is poly-(tetramethylene ether) two pure and mild MDI of about 2000.The quantity of the crosslinking additives of using in the preferred melt spun fibre of preparation is the about 20wt% of about 5wt%-and the about 15wt% of preferably about 10wt%-of fiber.Melt spun fibre can not use crosslinking additives from TPU polymer manufacture of the present invention.Yet, found the performance that crosslinking additives can fortifying fibre.
Prepare fiber by melt-spun and crosslinking additives blended TPU.Melt-spun is a known method, wherein with polymkeric substance fusion by extruding, enters air by spinning-nozzle, is solidified by cooling and collects by coiling fiber on collecting device.Preferred melt spun fibre under about 150 ℃-Yue 300 ℃ polymer temperature typically.
Can combine or weave with other fiber and be used for clothes clothes (clothing apparel) from the melt spun fibre of TPU of the present invention preparation.The melt-spun TPU fiber of prior art combines with cotton fibre usually, but does not combine with trevira.TPU of the present invention also can close with cotton knot, but does not resemble the TPU of prior art, because the high-melting-point of TPU, it also can combine with polyester.
TPU of the present invention also shows electrostatic dissipative properties.The surface resistivity of measuring according to ASTM D-257 of TPU is less than 1.0 * 10
11Ohm-sq.Preferably, surface resistivity is less than 3.0 * 10
10Ohm-sq.Electrostatic dissipative properties is important in several application for TPU of the present invention.Melt spun fibre processibility with electrostatic dissipative properties is better, attracts less powder dust particle because show less static charge and the fiber in their final application in weaving.This feature allows clothes to keep more cleaning.
To better understand the present invention with reference to following embodiment, this embodiment is used to illustrate, but does not limit the scope of the invention.
Embodiment
At embodiment 1,2 and 3, and the TPU of preparation in Comparative Examples 1 and 2, wherein prepare by the identical operations method.The working method of using comprises the blend of polyether intermediate and chainextender and vulcabond separately is heated to about 150 ℃ and mix these compositions then.Reaction be heat release in about 1-5 minute, be elevated to about 200 ℃-250 ℃ with temperature, in this time durations generation polymerization, prove as increase by viscosity.The physicals of the TPU that measurement forms and its are listed in table 1 and 2.Table 1 shows MVT numerical value and surface resistivity, and table 2 shows second-order transition temperature, fusing point, hardness, modulus, ultimate elongation, and modulus in flexure.
Embodiment 4 shows from the melt spun fibre of the TPU preparation of being produced by embodiment 2.Table 3 display fibers processing conditions.
Embodiment 1
Be 1450 polyoxyethylene glycol (PEG) with 0.17 mole of (241.61 gram) molecular weight 90 ℃ down with two (2-hydroxyethyl) ether (HQEE) the chainextender blend of 0.29 mole of (58.39 gram) Resorcinol.This blend or physical mixture are then by reacting as above-mentioned standard high temperature random melt polymerization method and 0.460 mole of (115 gram) methylene-bis diphenyl diisocyanate (MDI), to obtain being appointed as the TPU polymkeric substance of embodiment 1.
Embodiment 2
Be 1450 polyoxyethylene glycol (PEG) with 0.173 mole of (250.67 gram) molecular weight 90 ℃ down with two (2-hydroxyethyl) ether (HQEE) the chainextender blend of 0.257 mole of (50.83 gram) Resorcinol.This blend or physical mixture are then by reacting as above-mentioned standard high temperature random melt polymerization method and 0.427 mole of (106.78 gram) methylene-bis diphenyl diisocyanate (MDI), to obtain being appointed as the TPU polymkeric substance of embodiment 2.
Embodiment 3
Be 1450 polyoxyethylene glycol (PEG) with 0.176 mole of (255.72 gram) molecular weight 90 ℃ down with two (2-hydroxyethyl) ether (HQEE) the chainextender blend of 0.224 mole of (44.28 gram) Resorcinol.This blend or physical mixture are then by reacting as above-mentioned standard high temperature random melt polymerization method and 0.399 mole of (99.65 gram) methylene-bis diphenyl diisocyanate (MDI), to obtain being appointed as the TPU polymkeric substance of embodiment 3.
Comparative Examples 1
Be 1450 polyoxyethylene glycol (PEG) with 0.178 mole of (257.95 gram) molecular weight 60 ℃ down with 0.467 mole of (42.05 gram) 1, the blend of 4-butyleneglycol (BDO) chainextender.This blend or physical mixture are then by reacting as above-mentioned standard high temperature random melt polymerization method and 0.666 mole of (166.41 gram) methylene-bis diphenyl diisocyanate (MDI), to obtain being appointed as the TPU polymkeric substance of Comparative Examples 1.
Comparative Examples 2
Be 1000 polyoxyethylene glycol (PEG) with 0.246 mole of (245.62 gram) molecular weight 60 ℃ down with 0.604 mole of (54.38 gram) 1, the blend of 4-butyleneglycol (BDO) chainextender.This blend or physical mixture are then by reacting as above-mentioned standard high temperature random melt polymerization method and 0.850 mole of (212.46 gram) methylene-bis diphenyl diisocyanate (MDI), to obtain being appointed as the TPU polymkeric substance of Comparative Examples 2.
Embodiment 4
With the pellet of the TPU polymkeric substance produced among the embodiment 2 80 ℃ down dry 6 hours to reduce moisture content to less than 0.03wt%.Fiber is expressed into the spinning nozzle that orifice diameter is 0.5mm by single screw extrusion machine.The fiber of under the speed of 200 meters per minutes, reeling.Be displayed in Table 3 the condition that is used to spin antistatic/permeable fiber.
| Table 1 | ||
| ?MVT(g/m 2My god) | Surface resistivity (ohm-sq) | |
| Test method | The Permatran W model 100K of Mocon | ?ASTM?D-257 |
| Embodiment 1 | ?5892 | ?2.5×10 10 |
| Embodiment 2 | ?6679 | ?2.3×10 10 |
| Embodiment 3 | ?11330 | ?1.6×10 10 |
| Comparative Examples 1 | ?4459 | ?1.7×10 10 |
| Comparative Examples 2 | ?2128 | ?7.9×10 10 |
| Table 2 | ||||||
| Test method | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 2 | |
| Second-order transition temperature (℃) | ASTM?D-3417-99 | ?-30 | ?-26 | ?-34 | ?-8.5 | |
| Fusing point (℃) | ASTM?D-3417-99 | ?177 | ?170 | ?154 | ?160 | |
| Hardness (Shao Shi A) | ASTM?D-2240 | ?86A | ?83A | ?79A | ?80A | ?86A |
| Modulus (psi)@50% percentage elongation@100% percentage elongation@200% percentage elongation@300% percentage elongation@400% percentage elongation@500% percentage elongation | ? ? ? ASTM?D-412/D-638 ? ? ? | ? ?864 ?1010 ?1240 ?1580 ?1950 ?2280 | ? ?741 ?900 ?1160 ?1520 ?1960 ?2370 | ? ?580 ?706 ?855 ?1020 ?1230 ?1420 | ? ?607 ?731 ?942 ?1370 ?2170 ?3430 | ? ? ?990 ? ?1840 ? ? |
| Elongation limit (%) | ASTM?D-412/D-638 | ?714 | ?760 | ?963 | ?631 | ?590 |
| Ultimate tensile strength (psi) | ASTM?D-412/D-638 ? | ?2910 ? | ?4120 ? | ?2130 ? | ?5990 ? | ?5100 ? |
| Modulus in flexure (psi) | ASTM?D-790 | ?5510 | ?4320 | ?3200 | ?2530 | |
| Table 3. fiber process condition | ||
| Embodiment 2 | ||
| Dry | Time (h) | 6 |
| Temperature (℃) | 80 | |
| Forcing machine | Zone 1 (℃) | 180 |
| Zone 2 (℃) | 190 | |
| Zone 3 (℃) | 195 | |
| Zone 4 (℃) | 197 | |
| Back pressure (psi) | 1000 | |
| Spinning nozzle (℃) | 197 | |
| The coiling condition | Speed (m/min) | 200 |
Melt spun fibre shows high elongation rate, well processed, the excellent properties of ventilation property and high temperature tolerance.
From the data of table 1, use the MVT of the TPU of the present invention of aromatic chain extender (HQEE) to compare the TPU that in the Comparative Examples of using aliphatic chainextender (BDO), prepares much bigger (2-3 doubly) as can be seen.Usually, because PEG contains oxygen groups, this oxygen groups combines with moisture and transmits moisture by TPU, so be polyether intermediate (PEG) control MVT.Very unpredictable is use by aromatic chain extender (HQEE), and the TPU that contains same polyether intermediate (PEG) in an embodiment can show that so significant MVT improves.The appearance of believing this result is that PEG is higher in the lip-deep concentration of TPU because PEG is more soluble and therefore in HQEE than in BDO.The higher surface concn of PEG has explained that it can combine with more moistures and with its transmission from the teeth outwards.The data of table 1 show that also TPU of the present invention has low surface resistivity, therefore make it have electrostatic dissipative properties.
The fusing point of data presentation TPU of the present invention in the table 2 is than the high 10-20 of Comparative Examples ℃.The meaningful part that this fusing point increases is that it allows the TPU melt spun fibre to weave with the synthon such as the polyester of the temperature of having relatively high expectations in the clothes manufacturing process.High melt point also allows fabric to be applied by TPU, and wherein fabric also has fluoropolymer coating, and this coating stands higher temperatures with dry and crosslinked this fluoropolymer.This for breathable garment as sweat shirt and winter overcoat be particularly important.High MVT also causes such clothes more comfortable for the wearer.
Although according to patent law, best mode and embodiment preferred have been described, scope of the present invention is not limited to them, but by appended claim scope restriction.
Claims (41)
1. thermoplastic polyurethane polymer, it comprises:
Polyether-polyurethane derived from following material: with at least a aromatic diisocyanate of at least a hydroxy-end capped aromatic glycol chain extender and at least a hydroxy-end capped polyether intermediate reaction, this intermediate comprises the alkylene oxide with following general formula:
Wherein x be 2 and y be the integer of 11-115, the mol ratio of wherein said vulcabond is the total mole number of described polyether intermediate of 0.98-1.03 moles/mole and described aromatic chain extender.
2. the thermoplastic polyurethane polymer of claim 1, wherein said hydroxy-end capped polyether intermediate is a polyoxyethylene glycol.
3. the thermoplastic polyurethane polymer of claim 2, the number-average molecular weight of wherein said polyoxyethylene glycol is 1,000-2,000.
4. the thermoplastic polyurethane polymer of claim 1, wherein said hydroxy-end capped aromatic diol is two (2-hydroxyethyl) ethers of Resorcinol.
5. the thermoplastic polyurethane polymer of claim 1, wherein said vulcabond is the methylene-bis diphenyl diisocyanate.
6. the thermoplastic polyurethane polymer of claim 1, wherein y is the integer of 28-38.
7. the thermoplastic polyurethane polymer of claim 1, wherein this polymkeric substance has the moisture transmission numerical value measured for greater than 4500g/m on 25.4 microns (1.0 mil) thick samples
2My god.
8. the thermoplastic polyurethane polymer of claim 7, wherein this polymkeric substance has the moisture transmission numerical value measured for greater than 5500g/m on 25.4 microns (1.0 mil) thick samples
2My god.
9. the thermoplastic polyurethane polymer of claim 1, wherein this polymkeric substance has the surface resistivity measured according to ASTM D-257 for less than 1.0 * 10
11Ohm-sq.
10. the thermoplastic polyurethane polymer of claim 9, wherein this polymkeric substance has the surface resistivity measured according to ASTM D-257 for less than 3.0 * 10
10Ohm-sq.
11. the thermoplastic polyurethane polymer of claim 1, the number-average molecular weight of wherein said hydroxy-end capped polyether intermediate is 350-10,000.
12. the thermoplastic polyurethane polymer of claim 11, the number-average molecular weight of wherein said hydroxy-end capped polyether intermediate is 1,000-2,000.
13. the thermoplastic polyurethane polymer of claim 1, wherein to have the fusing point of measuring according to ASTM D-3417-99 be 150 ℃-220 ℃ to this polymkeric substance.
14. the thermoplastic polyurethane polymer of claim 13, wherein to have the fusing point of measuring according to ASTM D-3417-99 be 165 ℃-180 ℃ to this polymkeric substance.
15. the thermoplastic polyurethane polymer of claim 1, the quantity of wherein said aromatic glycol chain extender is the described hydroxy-end capped polyether intermediate of 1.0-2.0 moles/mole.
16. the thermoplastic polyurethane polymer of claim 15, the quantity of wherein said aromatic glycol chain extender is the described hydroxy-end capped polyether intermediate of 1.2-1.8 moles/mole.
17. the thermoplastic polyurethane polymer of claim 1, wherein said hydroxy-end capped polyether intermediate is that number-average molecular weight is 1,000-2,000 polyoxyethylene glycol, described vulcabond is the methylene-bis diphenyl diisocyanate, described aromatic glycol chain extender be two (2-hydroxyethyl) ethers of Resorcinol and wherein this polyether polyols with reduced unsaturation have the moisture transmission on 25.4 microns (1.0 mil) thick samples, measured for greater than 5500g/m
2It and the fusing point of measuring according to ASTM D-3417-99 are 165 ℃-180 ℃.
18. a method of producing the thermoplastic polyurethane polymer, it comprises the steps:
With at least a aromatic diisocyanate, at least a hydroxy-end capped aromatic glycol chain extender and at least a hydroxy-end capped polyether intermediate are mixed and reaction, and wherein this polyether intermediate comprises the alkylene oxide with following general formula:
Wherein x be 2 and y be the integer of 11-115, the mol ratio of wherein said vulcabond is the total mole number of described polyether intermediate of 0.98-1.03 moles/mole and described aromatic chain extender.
19. the method for claim 18, wherein said chainextender is 1.0-2.0 mole chainextender/this polyether intermediate of mole to the mol ratio of described polyether intermediate.
20. the method for claim 19, wherein said hydroxy-end capped polyether intermediate is a polyoxyethylene glycol.
21. the method for claim 19, wherein said aromatic glycol chain extender are Resorcinol pair (2-hydroxyethyl) ethers.
22. the method for claim 21, wherein said vulcabond are the methylene-bis diphenyl diisocyanates.
23. the method for claim 18, wherein y is the integer of 20-80.
24. the method for claim 23, wherein y is the integer of 28-38.
25. the method for claim 18, the number-average molecular weight of wherein said hydroxy-end capped polyether intermediate is 350-10,000.
26. the method for claim 25, the number-average molecular weight of wherein said hydroxy-end capped polyether intermediate is 1,000-2,000.
27. the method for claim 18 wherein saidly is reflected at the reaction times of carrying out in the forcing machine 2 minutes-10 minutes under 100 ℃-220 ℃ temperature.
28. the method for claim 27 wherein saidly is reflected at the reaction times of carrying out in the forcing machine 3 minutes-5 minutes under 100 ℃-220 ℃ temperature.
29. ventilative goods, it comprises: (a) at least one tissue layer and (b) at least one thermoplastic polyurethane polymer's layer, wherein this polyether polyols with reduced unsaturation is the polyether-polyurethane derived from following material: with at least a aromatic diisocyanate of at least a hydroxy-end capped aromatic glycol chain extender and at least a hydroxy-end capped polyether intermediate reaction, this intermediate comprises the alkylene oxide with following general formula:
Wherein x be 2 and y be the integer of 11-115, the mol ratio of wherein said vulcabond is the total mole number of described polyether intermediate of 0.98-1.03 moles/mole and described aromatic chain extender.
30. the goods of claim 29, wherein said at least one tissue layer comprises supatex fabric.
31. the goods of claim 29, wherein said at least one tissue layer comprises Woven fabric.
32. the goods of claim 29, wherein except that described at least one tissue layer and at least one thermoplastic polyurethane polymer's layer, these goods comprise at least one fluoropolymer layer.
33. the goods of claim 32, wherein these goods are clothes, house wrap or the teleblem goods of putting up a house.
34. the goods of claim 29, wherein said hydroxy-end capped polyether intermediate is that number-average molecular weight is 1,000-2,000 polyoxyethylene glycol, described vulcabond is the methylene-bis diphenyl diisocyanate, described aromatic glycol chain extender be two (2-hydroxyethyl) ethers of Resorcinol and wherein this polyether polyols with reduced unsaturation have the moisture transmission on 25.4 microns (1.0 mil) thick samples, measured greater than being 5500g/m
2It and the fusing point of measuring according to ASTM D-3417-99 are 165 ℃-180 ℃.
35. melt spun fibre that comprises the thermoplastic polyurethane polymer, wherein said polyether polyols with reduced unsaturation is the polyether-polyurethane derived from following material: with at least a aromatic diisocyanate of at least a hydroxy-end capped aromatic glycol chain extender and at least a hydroxy-end capped polyether intermediate reaction, this intermediate comprises the alkylene oxide with following general formula:
Wherein x be 2 and y be the integer of 11-115, the mol ratio of wherein said vulcabond is the total mole number of described polyether intermediate of 0.98-1.03 moles/mole and described aromatic chain extender.
36. the melt spun fibre of claim 35, it comprises the additive that is used for crosslinked described polyether polyols with reduced unsaturation.
37. the melt spun fibre of claim 36, the described additive that wherein is used for crosslinked described polyether polyols with reduced unsaturation is a diphenylmethanediisocyanate terminated polyether prepolymer, wherein this prepolymer derived from poly-(tetramethylene ether) glycol of methylene-bis diphenyl diisocyanate reaction.
38. the melt spun fibre of claim 37, the usage quantity of wherein said additive is the 5wt%-20wt% of this fiber.
39. clothes clothes that comprise melt spun fibre, this fiber is the thermoplastic polyurethane polymer's fiber derived from following material: with at least a aromatic diisocyanate of at least a hydroxy-end capped aromatic glycol chain extender and at least a hydroxy-end capped polyether intermediate reaction, this intermediate contains the alkylene oxide with following general formula:
Wherein x be 2 and y be the integer of 11-115, the mol ratio of wherein said vulcabond is the total mole number of described polyether intermediate of 0.98-1.03 moles/mole and described aromatic chain extender.
40. the clothes clothes of claim 39, it comprises with the woven trevira of described melt-spun thermoplastic polyurethane polymer fiber.
41. the clothes clothes of claim 40, wherein said hydroxy-end capped polyether intermediate is a polyoxyethylene glycol, described vulcabond is the methylene-bis diphenyl diisocyanate, described aromatic glycol chain extender is that two (2-hydroxyethyl) ethers of Resorcinol and wherein said polyether polyols with reduced unsaturation have the moisture transmission measured for greater than 5500g/m on 25.4 microns (1.0 mil) thick samples
2It and the fusing point of measuring according to ASTM D-3417-99 are 165 ℃-180 ℃.
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| US42488402P | 2002-11-08 | 2002-11-08 | |
| US60/424,884 | 2002-11-08 | ||
| US10/694,558 | 2003-10-27 |
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| CN102713040A (en) * | 2010-01-25 | 2012-10-03 | 路博润高级材料公司 | High strength non-woven elastic fabrics |
| WO2013041471A2 (en) * | 2011-09-20 | 2013-03-28 | Bayer Intellectual Property Gmbh | Thermoplastic polyurethane for producing hydrophilic fibers |
| CN111253544B (en) * | 2020-01-14 | 2022-04-19 | 湖南盛天新材料有限公司 | Environment-friendly chain extender and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3901852A (en) * | 1974-07-29 | 1975-08-26 | Upjohn Co | Thermoplastic polyurethanes prepared from 4,4'-methylenebis (phenyl isocyanate) |
| US4532316A (en) * | 1984-05-29 | 1985-07-30 | W. L. Gore & Assoc., Inc. | Phase separating polyurethane prepolymers and elastomers prepared by reacting a polyol having a molecular weight of 600-3500 and isocyanate and a low molecular weight chain extender in which the ratios of reactants have a limited range |
| US5840233A (en) * | 1997-09-16 | 1998-11-24 | Optimer, Inc. | Process of making melt-spun elastomeric fibers |
-
2003
- 2003-10-28 CN CNB2003801027887A patent/CN100341914C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3901852A (en) * | 1974-07-29 | 1975-08-26 | Upjohn Co | Thermoplastic polyurethanes prepared from 4,4'-methylenebis (phenyl isocyanate) |
| US4532316A (en) * | 1984-05-29 | 1985-07-30 | W. L. Gore & Assoc., Inc. | Phase separating polyurethane prepolymers and elastomers prepared by reacting a polyol having a molecular weight of 600-3500 and isocyanate and a low molecular weight chain extender in which the ratios of reactants have a limited range |
| US5840233A (en) * | 1997-09-16 | 1998-11-24 | Optimer, Inc. | Process of making melt-spun elastomeric fibers |
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