CN1057540C - Polyurethane products containing amido link - Google Patents
Polyurethane products containing amido link Download PDFInfo
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- CN1057540C CN1057540C CN95115663A CN95115663A CN1057540C CN 1057540 C CN1057540 C CN 1057540C CN 95115663 A CN95115663 A CN 95115663A CN 95115663 A CN95115663 A CN 95115663A CN 1057540 C CN1057540 C CN 1057540C
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- Prior art keywords
- urethane
- chain
- vulcabond
- polyvalent alcohol
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- 239000004814 polyurethane Substances 0.000 title abstract description 11
- 229920002635 polyurethane Polymers 0.000 title abstract description 11
- 125000003368 amide group Chemical group 0.000 title description 3
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 150000004985 diamines Chemical class 0.000 claims abstract description 9
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000004427 diamine group Chemical group 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229910005965 SO 2 Inorganic materials 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000003925 fat Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- SKDHHIUENRGTHK-UHFFFAOYSA-N 4-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=C(C(Cl)=O)C=C1 SKDHHIUENRGTHK-UHFFFAOYSA-N 0.000 claims 4
- NXTNASSYJUXJDV-UHFFFAOYSA-N 3-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=CC(C(Cl)=O)=C1 NXTNASSYJUXJDV-UHFFFAOYSA-N 0.000 claims 2
- 150000001875 compounds Chemical group 0.000 claims 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 229920000515 polycarbonate Polymers 0.000 claims 1
- 239000004417 polycarbonate Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- -1 tetrachlorobenzene diamines Chemical class 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229920002334 Spandex Polymers 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 239000004759 spandex Substances 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BWWHTIHDQBHTHP-UHFFFAOYSA-N 2-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=CC=C1C(Cl)=O BWWHTIHDQBHTHP-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 210000003097 mucus Anatomy 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- NYTPAANIMXKHJA-UHFFFAOYSA-N 2-methylprop-1-en-1-amine Chemical compound CC(C)=CN NYTPAANIMXKHJA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 210000004177 elastic tissue Anatomy 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229950002366 nafoxidine Drugs 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- NHDHVHZZCFYRSB-UHFFFAOYSA-N pyriproxyfen Chemical compound C=1C=CC=NC=1OC(C)COC(C=C1)=CC=C1OC1=CC=CC=C1 NHDHVHZZCFYRSB-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Polyurethanes Or Polyureas (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention relates to a polyurethane elastic product prepared in a two-stage method. In a first stage, polylol reacts with diisocyanate to form prepolymer, and then, the prepolymer reacts with diamine type chain-extending agent containing an acid amide bond to form the polyurethane elastic product.
Description
The invention relates to a kind of to contain the prepared urethane of diamines type chain extension agent of amido linkage.This urethane is applicable to the preparation polyurethane product, has the good macromolecular elastomer of high-tenacity, elasticity, degree of stretching and thermotolerance as film, fiber and elastomerics etc.
Spandex fiber (Spandex) may be defined as its urethane chain link by at least 85% weight percent of any long-chain synthetic polymer and is formed.The method for making of traditional elastic fiber is earlier by vulcabond and polyvalent alcohol (ester class or ethers) synthesizing isocyanate prepolymer, again with the chain extension agent, makes macromolecule polyurethane as diamines or glycol reaction.Formed polymer has specific link configuration: (1) tool high-melting-point and crystalline hard chain link; And (2) low-melting noncrystalline soft chain link.Hard chain link mat crystallization and intermolecular attraction and form the binding site of network structure, the low glass transition temp with the soft chain link of flexibility then makes product have elasticity.
The molecular weight that forms employed ester class of soft chain link or ethers polyvalent alcohol in the common commercial spandex fiber is about about 2000, and prepared elongate fiber rate can reach 350 to 550%.On need the special purpose than high elongation rate, it be 3500 or higher person that the molecular weight of use is also arranged.Prepared in this way spandex fiber has good elongation, but it also is low powerful and low modulus, thus its not only difficulty be applicable on the weaving purposes, have more relatively poor elasticity and thermotolerance.
In addition, the growth of hard chain link molecular chain length but can cause the minimizing of elongation at break and the lifting of fiber strength, but also can cause unsettled high viscosity polymer solution and the unfavorable spinning processing that continues simultaneously.
Purpose of the present invention promptly be to provide a kind of polyurethane elastomer its be suitable for preparing tool high-tenacity, elasticity, elongation and stable on heating polyurethane product.
Above-mentioned purpose is to reach by the chain extension agent that use contains amido linkage.
Chain extension agent of the present invention has following array structure:
NH
2R
1-CONH-R-NHOC-R
2-NH
2(A) wherein R is the straight chain or the branched chain C of a replacement or non-replacement
2-C
12Alkylene (alkylene), replace or non-replacement C
3-C
12Cyclic alkylene, or the aromatic group of representing with following general formula I-IV:
Wherein, Y represents C
nH
2n(n represents 1 or 2), O, S, SO
2Perhaps do not have; R
3And R
4Represent halogen, CH respectively
3, CH
3O, C
2H
5O or H, it can be identical or different;
R wherein
5, R
6, R
7And R
8Represent halogen, C respectively
1-C
6Alkyl or hydrogen can be identical or different; R
1And R
2Then be respectively the aromatic group that following general formula V-VI represents:
R wherein
9Represent halogen, C
1-C
6Alkyl or hydrogen.
Below be the present invention to be done illustrate further with embodiment.
Fig. 1 is the stress strain relationship figure of embodiment 7 formed fibers.
According to the present invention, polyurethane prepares with one or two stage processing procedure. In the phase I, vulcabond and polyalcohol in organic atent solvent (such as N, N '-dimethylacetylamide and N-methyl nafoxidine ketone) carry out prepolymerization. The mol ratio of NCO and OH is 2: 1 to 4.5: 1, and preferably 2.15: 1 to 4.2: 1, the best was 2.1: 1 to 4: 1. Can in system, add catalyst to promote prepolymerization. The amount of catalyst is controlled at the scope of 0.005 to 0.1 percentage by weight. In second stage, synthetic pre-polymerization is fit to prolong the agent solution hybrid reaction to form high viscosity solution with diamine chain. Made high viscosity solution can be processed into the leather and fur products of polyurethane film or the multiple layer of polyurethane, or is spun into elastomer by dry type or wet type spinning method. High viscosity solution also can premix with the thermoplastic polyurethane of at least 10% percentage by weight, make elastomer by melt-spun processing again.
In order to obtain have high elongation rate and elastomeric polyurethane product of the present invention, polyalcohol comprises various polyester, PPG and Merlon or its copolymer. Should be noted that polyalcohol of the present invention does not comprise the urethano key unit, cause the polyurethane product percentage elongation and the elasticity that are produced to reduce to avoid soft chain link rigidity to increase. In addition, if use copolymer, in order to obtain desired characteristic, the chain length of the carboxyl chain link in copolymer be for
M is preferably between 1 to 8, and x and n be at 1 to 40, preferably 1 to 20. Applicable polyalcohol is PPG and copolymer thereof. Molecular weight needs greater than 500, and is preferably large 1000, and take large 2000 for the best.
According to the present invention, vulcabond can be the mixture of symmetry classes aromatic diisocyanate, fats vulcabond, cycloaliphatic class vulcabond or its different mixing proportion. Wherein, symmetrical aromatics vulcabond, such as 4,4 '-methine two (4-phenyl isocyanate), and cycloaliphatic vulcabond are best such as Isosorbide-5-Nitrae-cyclohexyl diisocyanate. One of the vulcabond that mixes example is by 4 of at least 85% percentage by weight, and 4 '-methine two (4-phenyl isocyanate) and 1,6-hexane diisocyanate are mixed and formed. Another preferred example is by 4 of 90wt% at least, and 4 '-methine (mix and form by two (4-phenyl isocyanate) and Isosorbide-5-Nitrae-cyclohexyl diisocyanate. The chain elongation agent that the present invention was suitable for is to be represented by formula (A). The agent of this kind chain elongation is to carry out stoichiometric reaction by the diamines that will select and replacement or non-substituted contraposition or a position nitrobenzoyl chloride, carries out hydrogenation again and forms. The embodiment of these diamines comprises 4; 4 '-methine diphenylamines, 4; 4 '-ether diphenylamines, 4; 4 '-sulfonyldianiline, 3,3 '-two chloro-4,4 '-methine diphenylamines, 3; 3 '-dimethyl-4; 4 '-benzidine, 4,4 '-benzidine, 3,3 '-two chloro-4; 4 '-benzidine, tetrachlorobenzene diamines, 3; 3 '-dimethoxy-4,4 '-benzidine, phenylenediamine, 3,4 '-sulfonic group diphenylamines, 3; 3 '-diacetoxy-4; 4 '-biphenyl, one amine, Isosorbide-5-Nitrae '-secondary dimethyl phenylene diamine and 3,4 '-ether diphenylamines etc. Wherein to contain SO2-key or to contain the diamines of chlorine substituent derivative best. Should be noted that the mixture that also can use contraposition or a position nitrobenzoyl chloride. (R is inferior hydrocarbon or cyclic alkylene) chain elongation agent is to make with interfacial reaction method in a solvent that is fit to, this solvent comprises chlorine alkanes, chlorine alkene class, oxolane, benzene class, benzene alkanes (such as dimethylbenzene etc.), alkanes (such as n-hexane etc.), propane oxide, cycloalkanones, naphthenic and cyclenes class etc., preferably alkanes, naphthenic or benzene alkanes. And when R was aromatic series or substituting group derivative, then the chain elongation agent was adopted the cryogenic fluid synthetic method and is prepared, and reaction temperature is to be lower than 30 ℃ as good, and is best below 20 ℃, with 0 to 10 ℃ of the best.
To be described further with embodiment below the present invention.
Embodiment 1
Diamine chain prolongs the preparation of agent
1 mole hexanediamine is dissolved in the potassium hydroxide aqueous solution that contains 2 moles, and the xylene solution with 2.05 moles of right-nitrobenzoyl chlorides mixes again.Under 20 ℃, react about 40 minutes with the 2000rpm stirring velocity after, filter it.Fully cleaning filtration final vacuum drying through water and ether.The fusing point of prepared product A is 136～138 ℃, output 96% (395g).
With the dimethyl vinyl-amine solution of 0.5 product of moles A, add 10%Pd/C (0.2g) at 75～80 ℃, carry out hydrogenation under 50～60psi hydrogen-pressure.After being cooled to room temperature, filtered earlier and impouring water in its precipitation is separated out.Then fully clean the back and collect drying with tetrahydrofuran (THF) and alcohol.The fusing point of its final diamines product B is 152～154 ℃, output 89% (154g).
The preparation of urethane
With 4 of metering 78.1g, 4 '-methyne hexichol isocyanic ester and 300cc N,N-DIMETHYLACETAMIDE add in the polyether glycol [molecular weight: 2000g/mole (OH:56meq/mole)] of 250g the mol ratio of NCO/OH=2.5: 1.Treat to rise to 65 ℃ of reactions 130 minutes after the stirring and dissolving, up to-NCO terminal group content is 2.3%.
Then the diamines product B 66g that preparation is finished is dissolved in the 700cc dimethylacetamide solution, again in the impouring prepolymerization precursor reactant system, and control reaction temperature continues down to stir till homogeneous mucus generates at 80 ℃, and the solid content in this mucus is about 29wt%.Intrinsic viscosity (the η of viscous fluid
Inh) and other characteristics be shown in table 1.
Embodiment 2-6
Repeat the identical step of embodiment 1, but the preparation diamine chain prolongs the starting materials and the OH of agent: NCO: NH
2The ratio difference.The chain extension agent OH of preparation embodiment 2-6: NCO: NH
2The urethane characteristic that mole is when produced is shown in table 1.
Table 1
*R in the chain extension agent
1: R
2=1: 1 (mol ratio)
*η
Inh(intrinsic viscosity) value: be the dimethylacetamide solution of measuring 0.5g/dL, insert
| Example | Chain extension agent * R R 1 R 2 | OH∶NCO∶NH 2(mol ratio) | η inh * | |
| 1 | Hexanediamine | To bit-by-bit | 1∶2.5∶1.5 | 0.80 |
| 2 | Hexanediamine | To the interdigit position | 1∶2.5∶1.5 | 0.71 |
| 3 | 2 methyl pentamethylenediamine [1,5] | To bit-by-bit | 1∶2.5∶1.5 | 0.59 |
| 4 | 4,4 '-alkylsulfonyl pentanoic | To bit-by-bit | 1∶3.2∶2.05 | 0.78 |
| 5 | 4,4 '-alkylsulfonyl pentanoic | To bit-by-bit | 1∶2.5∶1.5 | 0.65 |
| 6 | 4,4 '-alkylsulfonyl pentanoic | Between bit-by-bit | 1∶2.5∶1.35 | 0.63 |
Measured in 30 ± 0.1 ℃ of thermostatic baths.
Embodiment 7
The high thick liquid of embodiment 5 gained is with the spinning solution (dop) of the sticking scheduling of N,N-DIMETHYLACETAMIDE dilution becoming 500-530 pool (poise), and the fiber development is carried out in mat wet type spinning (φ 0.12mm capillary hole, single hole).The characteristic of resulting fiber is shown in table 2.The stress strain relationship of gained fiber is illustrated in Fig. 1.
Table 2: spandex fiber characteristic of the present invention
| Spinning temperature (℃) | Coagulation bath composition | Coagulation bath temperature (℃) | Brute force (1) (g/den) | Elongation at break (%) | Elasticity is returned (2) multiple rate (%) | Remnants stretch (3) long amounts (%) | Brute force value (g/den) under 100% extension |
| 60 | 80/20 (v/v) water/DMAC | 15 | 0.75 | 654 | 95 | 11 | 0.04 |
(1) mensuration of fiber strength value is according to DIN 53815 standards.
(2) elastic recovery rate is the moment response rate under the stretching 300%.
(3) residual elongation amount is each measured after 60 seconds continuously elongated 300% 5 time at interval.
Demonstrate good brute force, elongation and elasticity by the prepared fiber of urethane of the present invention as shown in Table 2.
Though the present invention discloses as above with preferred embodiment; right its is not in order to limit the present invention; anyly have the knack of this skill person; without departing from the spirit and scope of the present invention; when can doing a little change and retouching, so protection scope of the present invention attached claim person of defining after looking is as the criterion.
Claims (15)
1. a urethane is made up of the diamine chain prolongation agent of vulcabond, polyvalent alcohol and amide-containing;
Wherein the diamine chain of amide-containing prolongation agent has following array structure:
NH
2-R
1-CONH-R-NHOC-R
2-NH
2Wherein R is the straight chain or the branch chain C of a replacement or non-replacement
2-C
12Alkylene, replacement or non-replacement C
3-C
12Encircle inferior hydroxyl, or the fragrant chain link of representing with following general formula I-VI:
Wherein, Y represents C
nH
2n(n represents 1 or 2), O, S, SO
2Perhaps do not have; R
3And R
4Represent halogen, CH respectively
3, CH
3O, C
2H
5O or H, it can be identical or different;
R wherein
5, R
6, R
7And R
8Represent halogen, C respectively
1-C
6Alkyl or hydrogen can be identical or different; R
1And R
2Then be respectively the aromatic group of representing by following general formula V-VI:
R wherein
9Represent halogen, C
1-C
6Alkyl or hydrogen.
2. urethane as claimed in claim 1, wherein diamine chain prolongation agent is prepared by hexanediamine and paranitrobenzoyl chloride.
3. urethane as claimed in claim 1, wherein diamine chain prolongation agent is by diamines, paranitrobenzoyl chloride and m-nitrobenzoyl chloride are prepared.
4. urethane as claimed in claim 1, wherein diamine chain prolongation agent is by 4,4-sulfonic group pentanoic and paranitrobenzoyl chloride are prepared.
5. urethane as claimed in claim 1, wherein diamine chain prolongation agent is by 4,4-sulfonic group pentanoic, paranitrobenzoyl chloride and m-nitrobenzoyl chloride are prepared.
6. urethane as claimed in claim 1, wherein polyvalent alcohol is to be selected from the person of compound group who is made up of polyester, polyether glycol, polycarbonate and multipolymer thereof.
7. urethane as claimed in claim 6, wherein this polyvalent alcohol does not contain ammonia ester chain link.
8. urethane as claimed in claim 6, wherein this polyvalent alcohol is a multipolymer, wherein the chain length of this carboxyl chain link be by
Expression, wherein the m value is between 1 and 8, x and n value are between 1 and 40.
9. urethane as claimed in claim 6, wherein the molecular weight of polyvalent alcohol is greater than 1000.
10. urethane as claimed in claim 9, wherein the molecular weight of polyvalent alcohol is between 1000 and 4800.
11. urethane as claimed in claim 1, wherein vulcabond is to be selected from the person of compound group who is made up of aromatics vulcabond, fats vulcabond, cycloaliphatic vulcabond and composition thereof.
12. as the urethane of claim 11, wherein vulcabond is 4,4 '-methyne two (4-phenyl isocyanate) and 1, the mixture of 6-hexane diisocyanate.
13. as the urethane of claim 12, wherein 4,4 '-methyne two (4-phenyl isocyanate) accounts for this mixture more than at least 85%.
14. as the urethane of claim 11, wherein vulcabond is 4,4 '-methyne two (4-phenyl isocyanate) and 1, the mixture of 4-cyclohexyl diisocyanate.
15. as the urethane of claim 14, wherein 4,4 '-methyne two (4-phenyl isocyanate) accounts for this mixture more than at least 90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95115663A CN1057540C (en) | 1995-09-26 | 1995-09-26 | Polyurethane products containing amido link |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95115663A CN1057540C (en) | 1995-09-26 | 1995-09-26 | Polyurethane products containing amido link |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1146463A CN1146463A (en) | 1997-04-02 |
| CN1057540C true CN1057540C (en) | 2000-10-18 |
Family
ID=5080602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95115663A Expired - Fee Related CN1057540C (en) | 1995-09-26 | 1995-09-26 | Polyurethane products containing amido link |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1057540C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2628210T3 (en) * | 2013-11-14 | 2017-08-02 | Pfm Medical Titanium Gmbh | Polyurethane that has an antithrombogenic coating |
| KR102267448B1 (en) * | 2019-02-28 | 2021-06-21 | 주식회사 엘지화학 | Diamine compound, and polyimide precursor and polyimide film prepared by using the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3663511A (en) * | 1968-06-06 | 1972-05-16 | Inter Polymer Res Corp | Polyurethanes chain-extended with a hydroxyl containing amide chain extender |
| US4174455A (en) * | 1977-12-09 | 1979-11-13 | Ciba-Geigy Corporation | Anthranilates of oxyalkylated carboxamides |
| US4194070A (en) * | 1978-10-10 | 1980-03-18 | Texaco Development Corporation | Isatoic anhydride derivatives and use as chain-extenders |
| US4487912A (en) * | 1984-02-13 | 1984-12-11 | Texaco Inc. | Reaction injection molded elastomers containing acid amides |
| JPS6191269A (en) * | 1984-10-11 | 1986-05-09 | Sakata Shokai Ltd | Coating resin composition |
-
1995
- 1995-09-26 CN CN95115663A patent/CN1057540C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3663511A (en) * | 1968-06-06 | 1972-05-16 | Inter Polymer Res Corp | Polyurethanes chain-extended with a hydroxyl containing amide chain extender |
| US4174455A (en) * | 1977-12-09 | 1979-11-13 | Ciba-Geigy Corporation | Anthranilates of oxyalkylated carboxamides |
| US4194070A (en) * | 1978-10-10 | 1980-03-18 | Texaco Development Corporation | Isatoic anhydride derivatives and use as chain-extenders |
| US4487912A (en) * | 1984-02-13 | 1984-12-11 | Texaco Inc. | Reaction injection molded elastomers containing acid amides |
| JPS6191269A (en) * | 1984-10-11 | 1986-05-09 | Sakata Shokai Ltd | Coating resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1146463A (en) | 1997-04-02 |
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