CN1059478C - Method for production of polyurethane elastic fibre - Google Patents
Method for production of polyurethane elastic fibre Download PDFInfo
- Publication number
- CN1059478C CN1059478C CN94110109A CN94110109A CN1059478C CN 1059478 C CN1059478 C CN 1059478C CN 94110109 A CN94110109 A CN 94110109A CN 94110109 A CN94110109 A CN 94110109A CN 1059478 C CN1059478 C CN 1059478C
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- Prior art keywords
- screw rod
- vulcabond
- production
- elastomeric fiber
- polyalcohol
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- Legal status (The legal status 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 status listed.)
- Expired - Fee Related
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- 239000000835 fiber Substances 0.000 title claims abstract description 36
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 26
- 239000004814 polyurethane Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000004970 Chain extender Substances 0.000 claims abstract description 8
- 238000013329 compounding Methods 0.000 claims description 10
- 239000004615 ingredient Substances 0.000 claims description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 229920005749 polyurethane resin Polymers 0.000 claims 2
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 claims 1
- 238000007500 overflow downdraw method Methods 0.000 claims 1
- 150000004989 p-phenylenediamines Chemical class 0.000 claims 1
- 229920002334 Spandex Polymers 0.000 abstract description 8
- 229920003225 polyurethane elastomer Polymers 0.000 abstract description 8
- 239000004759 spandex Substances 0.000 abstract description 8
- 239000012948 isocyanate Substances 0.000 abstract description 7
- 150000002513 isocyanates Chemical class 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 2
- 210000004177 elastic tissue Anatomy 0.000 abstract 2
- 230000000694 effects Effects 0.000 abstract 1
- 238000009987 spinning Methods 0.000 description 13
- 229920001971 elastomer Polymers 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000000806 elastomer Substances 0.000 description 9
- 229920000728 polyester Polymers 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- -1 isocyanide ester Chemical class 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- 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 description 1
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- JANFCFFNYNICBG-UHFFFAOYSA-N 4-n-naphthalen-1-ylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC2=CC=CC=C12 JANFCFFNYNICBG-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical class CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 241001112258 Moca Species 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 101000879635 Streptomyces albogriseolus Subtilisin inhibitor Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Abstract
The present invention provides a method for producing polyurethane elastic fiber by polyatomic alcohol and isocyanate, which is characterized in that the polyatomic alcohol and the isocyanate are synthesized into a linearity polyurethane elastomer by one step in a double-screw extruder by chain extender; the polyurethane elastomer is spun into elastic fiber. When the method provided by the present invention, the production process of spandex fiber can be greatly simplified, the investment for devices is reduced, production cost is reduced, and the labour condition and the production environment of workers can be improved. Great social benefit and economic effect can be generated by applying the method provided by the present invention.
Description
The invention belongs to the technical field of production of chemical fibre method, the method for a kind of production of linear polyurethane elastomer and polyurethane elastomeric fiber promptly is provided.
Polyurethane elastomeric fiber China names and is spandex fibre, and it is divided into polyester-type and polyether-type two big classes usually.From molecular structure, it is to be formed by amorphism low melting point polymer (soft segment) and high crystalline high-melting-point polymer (rigid chain segment) block polymerization, and its soft segment system is by molecular weight 500～5, and 000 polyester or polyethers are formed; " rigidity " segment of high crystalline then is made up of urethane bonds, amido link, urea key etc.United States Patent (USP) 3009762 discloses the method for american rubber company manufacturing PAUR elastomer, it is characterized in that earlier making molecular weight with the polyol condensating reaction is about 1900 polyester, with excessive isocyanate reaction generation performed polymer, add appropriate solvent and make polyurethane elastomeric fiber again with chemical spinning.United States Patent (USP) 2726219 and 3094374 discloses the method for du pont company production EU elastomer, it is characterized in that: make raw material with polyether polyol and the acid of isocyanide ester, make linear polyester elastomer through prepolymerization reaction, chain extending reaction and three processes of cessation reaction, adopt solwution method to be spun into polyurethane elastomeric fiber again with ether structure and carbamate and urea structure.Above-mentioned two kinds of prepolymer methods are produced the method for polyurethane elastomer, because its complex process, equipment investment are big, thereby the production cost height.And they spin polyurethane elastomeric fiber with chemical spinning and solwution method, because employed solvent (as dimethyl formamide) toxicity is bigger, can will seriously jeopardize the healthy of direct labor, environment is also had bigger pollution, these factors have all limited the development of polyurethane elastomeric fiber
The objective of the invention is to seek comparatively easy, the economic and nontoxic production of linear polyurethane elastomer and the method for polyurethane elastomeric fiber, reduce production costs, improve direct labor's working condition, to open up the new way of development China polyurethane elastomeric fiber.
The invention provides a kind of new method of producing polyurethane elastomeric fiber, it makes main raw material with polyester or polyether polyol and isocyanates, it is characterized in that: (1) adopts chain extender to make a polyalcohol and isocyanates step synthesizing linear polyurethane elastomer in double screw extruder; (2) adopt melt method that the linear polyester elastomer is spun into polyurethane elastomeric fiber.
The chain extender that adopts among the present invention can be 1, and 4-butanediol (being called for short BDO) also can be a trimethylolpropane (TMP); Can also be 3,3 '-two chloro-4,4 '-diphenyl methane diamines (MOCA) or other diamine compounds.Its optimum range of the addition of chain extender is calculated as by the mole proportioning: polyalcohol: chain extender: isocyanates=1: (1～3): (2～4).
The double screw extruder that is adopted among the present invention must be fit to special technical requirement of the present invention.Its measuring pump precision must reach 0.5～1.0%, the draw ratio of screw rod (32～42): 1.Temperature Distribution along screw axial must be controlled in segmentation, is divided into 4～5 sections usually, and temperature range is 100～230 ℃, and control accuracy is ± 1 ℃.The screw rod revolution is 5～200 rev/mins, and head pressure is 10～200 kilograms/square centimeter.
The method of production polyurethane elastomeric fiber provided by the present invention can also add-compounding ingredient of determined number when adding chain extender.The adding of compounding ingredient can increase the heat endurance and the photostability of linear polyester elastomer and polyurethane elastomeric fiber effectively, play age inhibiting effect, the compounding ingredient that is added can be that phenol antiager is the multifunctional derivative such as the 2.6-di-tert-butyl-4-methylphenol of hindered phenol and phenol in the present invention; 2,2 '-methylene-two-(4-methyl-6-t-butyl phenol) or three (3,5-di-tert-butyl-4 acrinyl) isocyanuric acid ester, compounding ingredient also can be the derivative such as the N of p-phenylenediamine (PPD), N '-diphenyl-para-phenylene diamine; N, N '-two-β naphthyl p-phenylenediamine and N-phenyl-N '-isopropyl p-phenylenediamine (PPD).Said compounding ingredient can also be benzophenone and benzotriazole derivatives as 2-hydroxyl-4-methoxy benzophenone; 2-(2 '-hydroxyl-5_ aminomethyl phenyl) benzotriazole and 2-(3 ', 5 '-di-tert-butyl-2 '-hydroxy phenyl) 5 chlorobenzotriazoles.The optimal addn of compounding ingredient is 0.05～1% by the total weight (percentage by weight) of reactant.
Because the present invention adopts chain extender and with one step of double screw extruder synthesizing linear polyurethane elastomer, production technology is greatly simplified, and has reduced equipment investment, has reduced production cost; And owing to adopt the melt method spinning, promptly directly heating makes the linear polyester elastomer be in the melting state to carry out spinning, do not need to use any solvent, this can make the direct labor need not to contact harmful substance such as dimethyl formamide again, and the environment of factory and workman's working condition all can improve; And no longer containing residual toxic solvent in the polyurethane elastomeric fiber of being produced, this also is useful for wearing and using the people's of these elastomers health.
Adopt the method for production polyurethane elastomeric fiber provided by the present invention, its performance indications of the spandex fibre of being produced can compare favourably with " Lycra " fiber (EU elastomer) that " dimension the is thought bacterium " fiber (PAUR elastomer) and the du pont company of the production of american rubber company are produced, and build the production line of identical scale, equipment investment required for the present invention is less than 1/10th of above-mentioned two companies.Because polyurethane elastomeric fiber application prospect in textile industry is very considerable, so after the present invention applies, will have a tremendous social and economic benefits.
Further set forth feature of the present invention and claimed claim below in conjunction with embodiments of the invention.
Embodiment 1.
It with molecular weight 1000 oxolane polyethers (PTMG), 1,4-butanediol, diphenyl methane-4,4_ vulcabond (MDI) injects double screw extruder by the measuring pump metering through mixing head by mole proportioning 1: 1: 2, the screw axial temperature of extruder is divided into 5 sections to be controlled, and 5 sections temperature is respectively: 150 ℃, 160 ℃, 170 ℃, 180 ℃, 200 ℃, the screw rod revolution is 30～50 rev/mins, make polyurethane section resin through underwater cutpellet, its shore hardness is 75A.Above-mentioned polyurethane section resin 210 ℃ of meltings, is carried out spinning with the VC401 spinning machine.Through its main performance standard of spandex fibre that spinning machine is spun into be: at the 1.04 gram/dawn of fibre strength, breaking elongation reaches 702.7%.
Embodiment 2.
With molecular weight is 2000 oxolane polyethers, 1,4-butanediol, diphenyl methane-4,4 '-vulcabond is by mole proportioning 1: 2: 3, adds an amount of compounding ingredient simultaneously, injects double screw extruder by measuring pump.The screw rod longitudinal temperature is divided into 4 sections controls, and each section temperature is 150 ℃-180 ℃-190 ℃-200 ℃, and the screw rod revolution is 150 rev/mins, makes polyurethane section resin through underwater cutpellet, and its shore hardness is 80A.Carry out the melting spinning with the VC404 weaving loom down at 215 ℃, its main performance index of the spandex fibre that is spun into is: at the 0.76 gram/dawn of fibre strength, breaking elongation reaches 786.2%.
Embodiment 3.
It with molecular weight 2000 polyethylene glycol adipate, 1,4-butanediol, diphenyl methane-4,4 '-vulcabond and 80/20 toluene di-isocyanate(TDI) (TDI-80) be by mole proportioning 1: 1: 1.8: 0.2, add an amount of compounding ingredient simultaneously, inject double screw extruder by measuring pump.The screw axial Temperature Distribution is 150 ℃-170 ℃-180 ℃-190 ℃, and the screw rod revolution is 100 rev/mins, and draw ratio is 38: 1.Make polyurethane section resin through underwater cutpellet.Its shore hardness is 85A.Produce SSI type melting spinning machine with Germany down at 220 ℃ and carry out the melting spinning.Its main performance index of made spandex fibre is: 0.6～0.7 gram/dawn of fibre strength; Breaking elongation 450～500%; 100% extends rebound degree 95.3% surely; 300% decides percentage elongation 92.7%.
Can also list more embodiment, common trait between them is to spin polyurethane elastomeric fiber with one-step method synthesizing linear polyurethane elastomer with melt method, and this method of the present invention is just compared the principal character that possesses patentability with the method for american rubber company, du pont company.In addition, the spinning system of polyurethane elastomeric fiber of the prior art adopts solwution method or chemical spinning, though the fiber that is spun into passes through certain post-processing, but still contain the residual organic solvent of some, as harmful substances such as dimethyl formamide, carbon tetrachloride.And the present invention adopts the melt method spinning, and it does not contact above-mentioned organic solvent, so there is not harmful substance on the fiber.This also is a notable feature of the present invention, utilizes this feature to judge whether that the behavior of invading this patent power takes place by spandex fibre being carried out micro-analysis.
Claims (1)
- A kind of method of producing polyurethane elastomeric fiber with polyalcohol and vulcabond may further comprise the steps successively:A, adopt chain extender 1,4-butanediol and compounding ingredient make a polyalcohol and vulcabond step synthesizing linear elastic polyurethane resin in double screw rod extruder, wherein this compounding ingredient is the multifunctional derivative of hindered phenol and phenol, p-phenylene diamine derivative or benzophenone or benzotriazole derivatives, addition is 0.05～1% of a reactant gross weight, polyalcohol: 1, the 4-butanediol: the mol ratio of vulcabond is 1: 1～2: 2～3, the measuring pump precision of described double screw rod extruder is 0.5～1.0%, the draw ratio of screw rod is 32～42: 1,4～5 sections controls of Temperature Distribution along screw axial, temperature range is 150～230 ℃, control accuracy is ± 1 ℃, the screw rod revolution is 5～200 rev/mins, and head pressure is 10～200 kilograms/square centimeter.B, employing fusion method are made polyurethane elastomeric fiber with this elastic polyurethane resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110109A CN1059478C (en) | 1994-03-12 | 1994-03-12 | Method for production of polyurethane elastic fibre |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110109A CN1059478C (en) | 1994-03-12 | 1994-03-12 | Method for production of polyurethane elastic fibre |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1108705A CN1108705A (en) | 1995-09-20 |
| CN1059478C true CN1059478C (en) | 2000-12-13 |
Family
ID=5034097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94110109A Expired - Fee Related CN1059478C (en) | 1994-03-12 | 1994-03-12 | Method for production of polyurethane elastic fibre |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1059478C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19504671C1 (en) * | 1995-02-13 | 1996-06-05 | Fischer Karl Ind Gmbh | Method and apparatus for melt-spinning polyurethane and / or polyurethaneurea and threads obtained thereafter |
| CN100537859C (en) * | 2003-07-16 | 2009-09-09 | 李绍光 | A kind of melt spinning method of making polyurethane elastomeric fiber |
| CN1303122C (en) * | 2003-08-28 | 2007-03-07 | 冯鹰 | Production equipment of polyurethane fibre chip and application method of said polyurethane fibre chip |
| CN103554423B (en) * | 2013-10-28 | 2016-05-25 | 南通润力机械制造有限公司 | A kind of preparation method who is suitable for ocean flexible joint modified polyurethane rubber |
| CN108560076B (en) * | 2018-05-15 | 2020-09-25 | 浙江华峰氨纶股份有限公司 | Medical polyurethane elastomer with biocompatibility and preparation method thereof |
| CN109853071A (en) * | 2018-12-27 | 2019-06-07 | 无锡金通高纤股份有限公司 | A kind of preparation method of thermoplastic polyurethane monofilament |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0367445A2 (en) * | 1988-10-28 | 1990-05-09 | Minnesota Mining And Manufacturing Company | Extruder polymerization of polyurethanes |
| WO1991000304A1 (en) * | 1989-06-27 | 1991-01-10 | The Dow Chemical Company | Melt polymerization process for making polyurethanes |
| CN1068341A (en) * | 1991-07-03 | 1993-01-27 | 钟纺株式会社 | Polyurethane Thermoplastic Elastomer, its manufacture method and manufacturing installation and by its spandex fiber of making |
-
1994
- 1994-03-12 CN CN94110109A patent/CN1059478C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0367445A2 (en) * | 1988-10-28 | 1990-05-09 | Minnesota Mining And Manufacturing Company | Extruder polymerization of polyurethanes |
| WO1991000304A1 (en) * | 1989-06-27 | 1991-01-10 | The Dow Chemical Company | Melt polymerization process for making polyurethanes |
| CN1068341A (en) * | 1991-07-03 | 1993-01-27 | 钟纺株式会社 | Polyurethane Thermoplastic Elastomer, its manufacture method and manufacturing installation and by its spandex fiber of making |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1108705A (en) | 1995-09-20 |
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