CN117866170A - Water-based polyurethane with high mechanical strength and high elongation at break and preparation method thereof - Google Patents
Water-based polyurethane with high mechanical strength and high elongation at break and preparation method thereof Download PDFInfo
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- CN117866170A CN117866170A CN202410004003.6A CN202410004003A CN117866170A CN 117866170 A CN117866170 A CN 117866170A CN 202410004003 A CN202410004003 A CN 202410004003A CN 117866170 A CN117866170 A CN 117866170A
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- epoxy resin
- chain extender
- diisocyanate
- reaction
- polysiloxane
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 87
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 24
- 239000003822 epoxy resin Substances 0.000 claims abstract description 53
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 53
- -1 polysiloxane Polymers 0.000 claims abstract description 47
- 239000004970 Chain extender Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 27
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 19
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 5
- 238000004945 emulsification Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 27
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 22
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 20
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 20
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 20
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 16
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 10
- 150000002009 diols Chemical class 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- QILXPCHTWXAUHE-UHFFFAOYSA-N [Na].NCCN Chemical compound [Na].NCCN QILXPCHTWXAUHE-UHFFFAOYSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- FCVCFERLLIDEQL-UHFFFAOYSA-N diphenyl carbonate;hexane-1,6-diol Chemical compound OCCCCCCO.C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 FCVCFERLLIDEQL-UHFFFAOYSA-N 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 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 claims description 2
- 239000004971 Cross linker Substances 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 8
- 238000004132 cross linking Methods 0.000 abstract description 7
- 238000002390 rotary evaporation Methods 0.000 abstract description 5
- 239000012948 isocyanate Substances 0.000 abstract description 4
- 150000002513 isocyanates Chemical class 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 70
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 45
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 37
- 229910052757 nitrogen Inorganic materials 0.000 description 35
- 238000001816 cooling Methods 0.000 description 20
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 17
- 239000012975 dibutyltin dilaurate Substances 0.000 description 17
- 238000010521 absorption reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 230000001804 emulsifying effect Effects 0.000 description 13
- 239000000839 emulsion Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000011049 filling Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000010907 mechanical stirring Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229920001558 organosilicon polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- NIEHEMAZEULEKB-UHFFFAOYSA-N ortho-ethylanisole Natural products CCC1=CC=CC=C1OC NIEHEMAZEULEKB-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to aqueous polyurethane with high mechanical strength and high elongation at break and a preparation method thereof. The method comprises the following steps: the diisocyanate, the dihydric alcohol, the polysiloxane and the catalyst are stirred and mixed uniformly, the temperature is raised for reaction for 150-200 min, then the epoxy resin and the chain extender A are added for reaction for 100-150 min, then the chain extender B and the cross-linking agent are continuously added for reaction for 80-100 min, then the temperature is reduced, the neutralizing agent is continuously added for reaction for 20-40 min, meanwhile, the organic solvent is added in the reaction process, and finally the aqueous polyurethane with high mechanical strength and high elongation at break is obtained after emulsification and rotary evaporation. According to the invention, epoxy resin is grafted into a main chain of waterborne polyurethane through reaction of polyhydroxy crosslinking sites and isocyanate, polysiloxane is blocked into the main chain of waterborne polyurethane through terminal hydroxyl, and a chain extender B, a crosslinking agent and the like are added for reaction, so that the tensile stress of the prepared modified waterborne polyurethane material reaches 43.5MPa, and the elongation at break reaches 1276%.
Description
Technical Field
The invention belongs to the technical field of high-molecular waterborne polyurethane, and particularly relates to waterborne polyurethane with high mechanical strength and high elongation at break and a preparation method thereof.
Background
Polyurethanes are a generic term for polymers containing a large number of urethane groups in the main chain of the high molecular structure, generally consisting of hard segments of isocyanate and soft segments of polyol. The traditional solvent-based polyurethane can cause certain pollution to the environment due to the fact that a large amount of solvent volatilizes during film forming and curing, so that along with the limitation of an organic solvent, the solvent-based polyurethane is gradually replaced by the aqueous polyurethane, and the aqueous polyurethane has the advantages of being nontoxic, pollution-free, easy to store, convenient to use and the like.
At present, the water-based polyurethane (WPU) is taken as a high-performance green environment-friendly material, has excellent comprehensive performance and strong molecular structure designability, and is superior to other water-based polymer materials in the aspects of film formation, aging resistance, friction resistance, strength and the like along with the continuous improvement of the preparation technology. However, the existing self-emulsifying aqueous polyurethane mainly achieves the aim of dispersing in water through the introduction of hydrophilic groups, and the introduction of the hydrophilic groups can lead the aqueous polyurethane to be inferior to the traditional solvent-type polyurethane in the aspects of water resistance, high temperature resistance and mechanical properties of a coating film, and has the problem that the high mechanical properties and the high elongation at break cannot be achieved.
To remedy these drawbacks, research hotspots on polyurethanes have shifted to modification of aqueous polyurethanes. The organic silicon polymer takes Si-O-Si as a main chain, and the hybrid polymer material with the organic group directly connected with silicon atoms has the advantages of low surface energy, good thermal stability and strong hydrophobicity. Therefore, a great deal of research on modification of aqueous polyurethane is to introduce organosilicon polymers into polyurethane to jointly exert the synergistic effect of organosilicon and aqueous polyurethane. However, the existing modified waterborne polyurethane has the defects of unfriendly reagents, unbalanced use amount of raw materials, incorrect modification method, low elongation at break, poor mechanical strength, insufficient water resistance, poor flexibility and the like, and cannot meet the actual application requirements.
Therefore, in order to solve the above technical problems, how to obtain an aqueous polyurethane resin of an aqueous polyurethane having high mechanical strength, high elongation at break and excellent water resistance is an urgent technical problem to be solved in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the waterborne polyurethane with high mechanical strength and high elongation at break and the preparation method thereof. The invention grafts the epoxy resin onto the main chain of the waterborne polyurethane through a plurality of crosslinking sites, and the epoxy group opens a ring to further carry out crosslinking reaction with the main chain of the polyurethane; the polysiloxane is embedded into the water-based polyurethane chain segment through the terminal hydroxyl, and the prepared modified water-based polyurethane emulsion has good mechanical property, excellent water resistance and water absorption, good temperature resistance, salt spray resistance and excellent elongation at break, and greatly meets the industrial requirements.
The technical scheme of the invention is as follows:
the preparation method of the aqueous polyurethane with high mechanical strength and high elongation at break comprises the following steps:
the diisocyanate, the dihydric alcohol, the polysiloxane and the catalyst are stirred and mixed uniformly, the temperature is raised to 80-90 ℃, the reaction is carried out for 150-200 min under the protection of inert gas, then the temperature is lowered to 60-80 ℃, the epoxy resin and the chain extender A are added, the stirring and the mixing are carried out uniformly, the reaction is carried out for 100-150 min under 80-90 ℃, then the temperature is lowered to 60-80 ℃, the chain extender B and the cross-linking agent are continuously added, the stirring and the mixing are carried out uniformly, the reaction is carried out for 80-100 min under 80-90 ℃, then the temperature is lowered to 30-50 ℃, the neutralizing agent is continuously added, the stirring and the mixing are carried out uniformly, the reaction is carried out for 20-40 min under 30-50 ℃, meanwhile, the organic solvent is added in the reaction process, and finally the aqueous polyurethane with high mechanical strength and high breaking elongation is obtained after emulsification and spin evaporation.
According to the invention, the molar ratio of diisocyanate, diol, polysiloxane, catalyst, chain extender A, chain extender B and crosslinking agent is 1: (0.15-0.35): (0.01-0.04): (0.0005-0.001): (0.2-0.4): (0.1-0.2): (0.05-0.15).
Further preferably, the molar ratio of diisocyanate, diol, polysiloxane, catalyst, chain extender a, chain extender B and crosslinking agent is 1:0.19:0.015:0.0008:0.27:0.11:0.076.
according to the invention, the molar ratio of isocyanate groups in the diisocyanate to the total active hydroxyl groups of diol, polysiloxane, chain extender A, chain extender B and crosslinking agent is 1: (0.5-1).
According to the invention, the diisocyanate is preferably one or more of toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
Further preferably, the diisocyanate is isophorone diisocyanate.
According to the present invention, the diol is preferably one or more of polyether diol having a molecular weight of 500 to 4000, polyester diol having a molecular weight of 500 to 4000, or polyolefin diol having a molecular weight of 500 to 4000.
Further preferably, the glycol is 1, 6-hexanediol diphenyl carbonate glycol having a molecular weight of 2000.
According to the invention, the polysiloxane is preferably hydroxyl-terminated polydimethylsiloxane having a molecular weight of 500 to 5000.
Further preferably, the polysiloxane is a hydroxyl-terminated polydimethylsiloxane having a molecular weight of 500, 1000, 2000.
According to the invention, the catalyst is preferably one or more of di-n-octyl tin dilaurate, monobutyl tin oxide, dibutyl tin maleate and dibutyl tin dilaurate.
Further preferably, the catalyst is dibutyltin dilaurate.
According to the invention, the epoxy resin is preferably one or more of bisphenol A type epoxy resin E-51, bisphenol A type epoxy resin E-20, bisphenol A type epoxy resin E-44, phenolic type epoxy resin F-48 or phenolic type epoxy resin F-44.
Further preferably, the epoxy resin is bisphenol A type epoxy resin E-44.
According to the invention, the mass ratio of polysiloxane to epoxy resin is preferably 1: (0.5-3); the epoxy resin accounts for 2-8% of the total mass of the preparation raw materials.
Further preferably, the mass ratio of the polysiloxane to the epoxy resin is 1:1.5; the epoxy resin accounts for 6% of the total preparation raw material mass.
According to the invention, the chain extender A is one or more of dimethylolpropionic acid, dimethylolbutyric acid and ethylenediamine sodium sulfonate.
Further preferably, the chain extender a is dimethylolpropionic acid.
According to the invention, the chain extender B is one or more of 1,4 butanediol, glycerol, pentaerythritol and isovaleryltetraol.
Further preferably, the chain extender B is 1,4 butanediol.
According to the invention, the cross-linking agent is preferably one or more of diethanolamine, trimethylolpropane, pentaerythritol and diethylenetriamine.
Further preferably, the crosslinking agent is trimethylolpropane.
According to a preferred embodiment of the present invention, the neutralizing agent is one or more of triethylamine, dimethylethanolamine, diethylethanolamine or 2-amino-2-methylpropanol.
Further preferably, the neutralizing agent is triethylamine.
According to the invention, the organic solvent is preferably one or more of acetone, butanone, dimethyl sulfoxide, tetrahydrofuran, ethyl formate and anisole.
Further preferably, the organic solvent is acetone.
The aqueous polyurethane with high mechanical strength and high elongation at break prepared by the method.
Application of waterborne polyurethane in preparation of paint and adhesive
The invention has the technical characteristics and beneficial effects that:
1. according to the invention, polysiloxane and epoxy resin are used as main modifiers, and the epoxy resin and the polysiloxane are connected into the waterborne polyurethane, so that the waterborne polyurethane with the polysiloxane and the epoxy resin synergistically modified is prepared. The synthesis steps of the aqueous polyurethane are simple, and the used raw materials are low in cost and easy to obtain, and are environment-friendly.
2. According to the invention, epoxy resin is grafted into a waterborne polyurethane main chain through the reaction of polyhydroxy crosslinking sites and isocyanate, polysiloxane is blocked into the waterborne polyurethane main chain through hydroxyl end blocks, and the proportions of diisocyanate, dihydric alcohol, polysiloxane, catalyst, chain extender A, chain extender B, crosslinking agent, polysiloxane and epoxy resin are strictly limited, so that the prepared modified waterborne polyurethane material has good hydrophobicity, excellent salt fog resistance and excellent mechanical property, the tensile stress reaches 43.5MPa, and the elongation at break reaches 1276%.
3. According to the preparation method, the epoxy resin is grafted into the main chain of the waterborne polyurethane after the polyhydroxy crosslinking site reacts with isocyanate, and the epoxy group is subjected to ring opening in subsequent reaction to further carry out crosslinking reaction with the main chain of the polyurethane, so that an additional strengthening agent is not needed, and the cost of the modified waterborne polyurethane material is reduced.
4. The preparation method of the invention also uses an internal cross-linking agent and a micromolecular chain extender, which further improve the internal cross-linking density of the modified waterborne polyurethane material, further improve the mechanical property, obviously reduce the addition amount of the epoxy resin, improve the contact angle of the modified waterborne polyurethane material and effectively enhance the water resistance and salt fog resistance of the modified waterborne polyurethane material.
Drawings
FIG. 1 is an infrared spectrum of the aqueous polyurethane with high mechanical strength and high elongation at break prepared in example 1.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
Example 1
The preparation method of the aqueous polyurethane with high mechanical strength and high elongation at break comprises the following steps:
in a four-neck flask with a thermometer probe, a snake-shaped condenser pipe, a mechanical stirring rod and a nitrogen inlet, firstly opening a nitrogen valve, introducing nitrogen for 10min, filling the four-neck flask with nitrogen, adding 16.38g isophorone diisocyanate (IPDI), 27.85g 1, 6-hexanediol diphenyl carbonate diol (PCDL, mn=2000), 0.04g dibutyl tin dilaurate (DBTDL) and 2.15g hydroxyl-terminated Polydimethylsiloxane (PDMS), stirring and mixing uniformly, heating to 85 ℃, reacting for 180min under the protection of nitrogen, then cooling to 70 ℃, adding 2.7g dimethylolpropionic acid (DMPA) and 1.07g epoxy resin E-44 dissolved in acetone, stirring and mixing uniformly, reacting at 85 ℃ for 120min, cooling to 70 ℃, continuously adding 0.75g of 1, 4-Butanediol (BDO) and 0.75g of Trimethylolpropane (TMP), stirring and mixing uniformly, reacting at 85 ℃ for 90min, cooling to 40 ℃, continuously adding 2.04g of Triethylamine (TEA), reacting at 40 ℃ for 30min, simultaneously adding 30ml of acetone into the system in the reaction process, finally adding the reaction product solution into 100ml of water, emulsifying at 25 ℃ for 10min by using an emulsifying machine at 5000rpm, and removing the acetone by rotary evaporation for 60min by using a rotary evaporator at 40 ℃ to obtain the aqueous polyurethane with high mechanical strength and high elongation at break.
The infrared spectrum of the aqueous polyurethane prepared in this example is shown in fig. 1.
As can be seen from FIG. 1, at 3415cm -1 The characteristic absorption peak is N-H telescopic vibration absorption peak at 1661cm -1 The characteristic absorption peak of the left and right is NHCOO-medium-C=O stretching vibration absorption peak, which proves the synthesis of polyurethane chain segment at 805cm -1 The characteristic absorption peak of the left and right is the flexural vibration absorption peak of Si-C, which proves that the polysiloxane is introduced at 878cm -1 The characteristic absorption peak of the left and right is the characteristic absorption peak of benzene ring in the epoxy resin, which proves that the introduction of the epoxy resin E44 is carried out at 910cm -1 The absorption peak does not appear on the left and right sides, and the epoxy resin is proved to carry out ring-opening grafting reaction, namely the waterborne polyurethane material modified by polysiloxane and epoxy resin is successfully prepared.
Example 2
The preparation method of the aqueous polyurethane with high mechanical strength and high elongation at break comprises the following steps:
in a four-neck flask with a thermometer probe, a snake-shaped condenser pipe, a mechanical stirring rod and a nitrogen inlet, firstly opening a nitrogen valve, introducing nitrogen for 10min, filling the four-neck flask with nitrogen, adding 16.38g isophorone diisocyanate (IPDI), 27.85g 1, 6-hexanediol diphenyl carbonate diol (PCDL, mn=2000), 0.04g dibutyl tin dilaurate (DBTDL) and 2.15g hydroxyl-terminated Polydimethylsiloxane (PDMS), stirring and mixing uniformly, heating to 85 ℃, reacting for 180min under the protection of nitrogen, then cooling to 70 ℃, adding 2.7g dimethylolpropionic acid (DMPA) and 2.19g epoxy resin E-44 dissolved in acetone, stirring and mixing uniformly, reacting at 85 ℃ for 120min, cooling to 70 ℃, continuously adding 0.75g of 1, 4-Butanediol (BDO) and 0.75g of Trimethylolpropane (TMP), stirring and mixing uniformly, reacting at 85 ℃ for 90min, cooling to 40 ℃, continuously adding 2.04g of Triethylamine (TEA), reacting at 40 ℃ for 30min, simultaneously adding 30ml of acetone into the system in the reaction process, finally adding the reaction product solution into 100ml of water, emulsifying at 25 ℃ for 10min by using an emulsifying machine at 5000rpm, and removing the acetone by rotary evaporation for 60min by using a rotary evaporator at 40 ℃ to obtain the aqueous polyurethane with high mechanical strength and high elongation at break.
Example 3
The preparation method of the aqueous polyurethane with high mechanical strength and high elongation at break comprises the following steps:
in a four-neck flask with a thermometer probe, a snake-shaped condenser pipe, a mechanical stirring rod and a nitrogen inlet, firstly opening a nitrogen valve, introducing nitrogen for 10min, filling the four-neck flask with nitrogen, adding 16.38g isophorone diisocyanate (IPDI), 27.85g 1, 6-hexanediol diphenyl carbonate diol (PCDL, mn=2000), 0.04g dibutyl tin dilaurate (DBTDL) and 2.15g hydroxyl-terminated Polydimethylsiloxane (PDMS), stirring and mixing uniformly, heating to 85 ℃, reacting for 180min under the protection of nitrogen, then cooling to 70 ℃, adding 2.7g dimethylolpropionic acid (DMPA) and 3.36g epoxy resin E-44 dissolved in acetone, stirring and mixing uniformly, reacting at 85 ℃ for 120min, cooling to 70 ℃, continuously adding 0.75g of 1, 4-Butanediol (BDO) and 0.75g of Trimethylolpropane (TMP), stirring and mixing uniformly, reacting at 85 ℃ for 90min, cooling to 40 ℃, continuously adding 2.04g of Triethylamine (TEA), reacting at 40 ℃ for 30min, simultaneously adding 30ml of acetone into the system in the reaction process, finally adding the reaction product solution into 100ml of water, emulsifying at 25 ℃ for 10min by using an emulsifying machine at 5000rpm, and removing the acetone by rotary evaporation for 60min by using a rotary evaporator at 40 ℃ to obtain the aqueous polyurethane with high mechanical strength and high elongation at break.
Example 4
The preparation method of the aqueous polyurethane with high mechanical strength and high elongation at break comprises the following steps:
in a four-neck flask with a thermometer probe, a snake-shaped condenser pipe, a mechanical stirring rod and a nitrogen inlet, firstly opening a nitrogen valve, introducing nitrogen for 10min, filling the four-neck flask with nitrogen, adding 16.38g isophorone diisocyanate (IPDI), 27.85g 1, 6-hexanediol diphenyl carbonate diol (PCDL, mn=2000), 0.04g dibutyl tin dilaurate (DBTDL) and 2.15g hydroxyl-terminated Polydimethylsiloxane (PDMS), stirring and mixing uniformly, heating to 85 ℃, reacting for 180min under the protection of nitrogen, then cooling to 70 ℃, adding 2.7g dimethylolpropionic acid (DMPA) and 4.58g epoxy resin E-44 dissolved in acetone, stirring and mixing uniformly, reacting at 85 ℃ for 120min, cooling to 70 ℃, continuously adding 0.75g of 1, 4-Butanediol (BDO) and 0.75g of Trimethylolpropane (TMP), stirring and mixing uniformly, reacting at 85 ℃ for 90min, cooling to 40 ℃, continuously adding 2.04g of Triethylamine (TEA), reacting at 40 ℃ for 30min, simultaneously adding 30ml of acetone into the system in the reaction process, finally adding the reaction product solution into 100ml of water, emulsifying at 25 ℃ for 10min by using an emulsifying machine at 5000rpm, and removing the acetone by rotary evaporation for 60min by using a rotary evaporator at 40 ℃ to obtain the aqueous polyurethane with high mechanical strength and high elongation at break.
Comparative example 1
The preparation method of the aqueous polyurethane comprises the following steps:
in a four-neck flask with a thermometer probe, a snake-shaped condenser pipe, a mechanical stirring rod and a nitrogen inlet, firstly opening a nitrogen valve, introducing nitrogen for 10min, filling the four-neck flask with nitrogen, adding 16.38g isophorone diisocyanate (IPDI), 30.0g 1, 6-hexanediol diphenyl carbonate diol (PCDL, mn=2000), 0.04g dibutyltin dilaurate (DBTDL), 2.15g hydroxyl-terminated Polydimethylsiloxane (PDMS), stirring and mixing uniformly, heating to 85 ℃, reacting for 180min under the protection of nitrogen, then cooling to 70 ℃, adding 2.7g dimethylolpropionic acid (DMPA), stirring and mixing uniformly, reacting for 90min at 85 ℃, then cooling to 70 ℃, continuously adding 0.75g 1,4 Butanediol (BDO) and 0.75g trimethylol propane (TMP), stirring and mixing uniformly, reacting for 90min at 85 ℃, then cooling to 40 rpm, continuously adding 2.04g triethylamine (DBTDL), reacting for 30min at 40 ℃, simultaneously, adding 30ml hydroxyl-terminated Polydimethylsiloxane (PDMS), finally, adding 2.7g dimethylolpropionic acid (DMPA), stirring and mixing uniformly at 40 ml, evaporating the aqueous solution to a water-soluble polyurethane by a rotary emulsifying machine at 25ml under the condition of water-based emulsion at 40 ℃ for 10min, and evaporating the aqueous solution to obtain the aqueous polyurethane emulsion.
In this comparative example, no epoxy resin was added as compared with the example.
Comparative example 2
The preparation method of the aqueous polyurethane comprises the following steps:
in a four-neck flask with a thermometer probe, a snake-shaped condenser pipe, a mechanical stirring rod and a nitrogen inlet, firstly opening a nitrogen valve, introducing nitrogen for 10min, filling the four-neck flask with nitrogen, adding 9.1g isophorone diisocyanate (IPDI), 25g 1, 6-hexanediol diphenyl carbonate diol (PCDL, mn=2000), 0.04g dibutyltin dilaurate (DBTDL), 1.7g hydroxyl-terminated Polydimethylsiloxane (PDMS), stirring and mixing uniformly, heating to 85 ℃, reacting for 180min under the protection of nitrogen, then cooling to 70 ℃, adding 2.2g dimethylol propionic acid (DMPA) and 2.7g epoxy resin E-44 dissolved in acetone, stirring and mixing uniformly, reacting at 85 ℃ for 120min, cooling to 40 ℃, continuously adding 1.6g Triethylamine (TEA), reacting at 40 ℃ for 30min, simultaneously adding 30ml acetone into the system in the reaction process, finally adding the reaction product solution into 100ml water, emulsifying at 25 ℃ for 10min at 5000rpm by using an emulsifying machine, evaporating at 40 ℃ for 60min, and removing the aqueous polyurethane by rotating and evaporating.
In comparison with the examples, no crosslinking agent (trimethylolpropane) and no chain extender B (1, 4-butanediol) were added in this comparative example.
Comparative example 3
The preparation method of the aqueous polyurethane comprises the following steps:
in a four-neck flask with a thermometer probe, a snake-shaped condenser pipe, a mechanical stirring rod and a nitrogen inlet, firstly opening a nitrogen valve, introducing nitrogen for 10min, filling the four-neck flask with nitrogen, adding 12.3g isophorone diisocyanate (IPDI), 26.2g 1, 6-hexanediol diphenyl carbonate diol (PCDL, mn=2000), 0.04g dibutyltin dilaurate (DBTDL), 1.8g hydroxyl-terminated Polydimethylsiloxane (PDMS), stirring and mixing uniformly, heating to 85 ℃, reacting for 180min under the protection of nitrogen, then cooling to 70 ℃, adding 2.4g dimethylolpropionic acid (DMPA) and 2.9g epoxy resin E-44 dissolved in acetone, stirring and mixing uniformly, reacting at 85 ℃ for 120min, then cooling to 70 ℃, continuously adding 0.7g 1, 4-Butanediol (BDO), stirring and mixing uniformly, reacting at 85 ℃ for 90min, further cooling to 40 ℃, continuously adding 1.81g Triethylamine (TEA), reacting at 40 ℃ for 30min, adding the reaction product into a water-soluble polyurethane, evaporating and emulsifying for 25ml under the condition of acetone at 25 rpm, evaporating for 10min, and removing the aqueous solution by a rotary emulsifying machine at 25 rpm under the condition of 40 rpm to obtain the aqueous polyurethane product.
In this comparative example, a crosslinking agent (trimethylolpropane) was not added as compared with the example.
Test examples
1. The aqueous polyurethanes of examples 1 to 4 and comparative examples 1 to 3 of the same mass were weighed respectively, and their centrifugal stability was tested, specifically: the appearance of the different examples was observed by centrifugation in a 3500r/min centrifuge for 15 min.
TABLE 1 influence of epoxy resin content on appearance and stability of modified waterborne polyurethane
As is clear from Table 1, the modified aqueous polyurethanes prepared in examples 1 to 4 and comparative examples 1 to 3 of the present invention were not layered, indicating that they were excellent in mechanical stability and could be stored for 6 months without deterioration.
2. Respectively weighing the aqueous polyurethane of examples 1-4 and the aqueous polyurethane of comparative examples 1-3 with the same mass to prepare emulsion, coating by an automatic film coating machine at a coating speed of 12mm/s, drying the aqueous polyurethane in a dry environment for 24 hours at a thickness of 120 micrometers, and testing pencil hardness and adhesive force grades thereof, wherein the adhesive force is according to national standard GB/T9286-1998 "cross-cut test of colored paint and varnish-paint film"; pencil hardness according to national standard GB/T6739-1996 pencil test method for coating hardness.
TABLE 2 influence of epoxy resin content on pencil hardness and adhesion of modified waterborne polyurethane
3. Respectively weighing the aqueous polyurethane of the examples 1-4 and the aqueous polyurethane of the comparative examples 1-3 with the same mass, preparing emulsion, dripping the emulsion on a glass slide, testing the contact angle by a sitting-drop method, and characterizing the water resistance of the aqueous polyurethane; we made films with glass petri dishes and placed in water for 24 hours to test their absorptivity.
TABLE 3 influence of epoxy resin content on contact angle and Water absorption of modified waterborne polyurethane
4. The aqueous polyurethane of examples 1-4 and the aqueous polyurethane of comparative examples 1-3 with the same mass are respectively weighed to prepare emulsion, the emulsion is added into a polytetrafluoroethylene mould, dried for 48 hours at room temperature, then put into an oven for drying for 10 hours at 60 ℃ to form a film, and the mechanical properties including tensile stress and elongation at break are tested by a universal material testing machine.
TABLE 4 influence of epoxy resin content on tensile stress and elongation at break of modified waterborne polyurethane
5. The aqueous polyurethane of examples 1-4 and the aqueous polyurethane of comparative examples 1-3 of the same mass are respectively weighed to prepare emulsion, the emulsion is coated by an automatic coating machine, the coating speed is 12mm/s, the thickness of a wet film preparation device is 120 micrometers, the wet film preparation device is put into a dry environment to be dried for 24 hours, the salt spray resistance is tested, and the test standard is QC/T484-1999 Standard automobile paint coating of the automobile industry of the people's republic of China, and the salt spray is 5wt% sodium chloride solution.
TABLE 5 influence of epoxy resin content on salt spray resistance of modified waterborne polyurethane
As is clear from tables 1 to 5, when the content of the modified waterborne polyurethane epoxy resin prepared in the embodiments 1 to 4 is 6%, the stability meets the requirement, the pencil hardness can reach 5H, the adhesive force can reach 0 level, the contact angle can reach 108.6 degrees, the water absorption is reduced to 3.2%, the tensile stress reaches 43.5MPa, the elongation at break is also up to 1276%, while in the comparative examples 2 to 3, under the condition that the chain extender B, the crosslinking agent and the crosslinking agent are not added respectively, the hardness of the coating film is obviously reduced, only H and 2H are reached, the water absorption is increased, the salt fog resistance is also poor, the elongation at break and the tensile strength are both reduced, and the key effect of the chain extender B and the crosslinking agent on the performance of the coating film can be seen.
The present invention is not limited to the above-mentioned embodiments, and any equivalent embodiments which can be changed or modified by the technical content disclosed above can be applied to other fields, but any simple modification, equivalent changes and modification made to the above-mentioned embodiments according to the technical substance of the present invention without departing from the technical content of the present invention still belong to the protection scope of the technical solution of the present invention.
Claims (8)
1. The preparation method of the aqueous polyurethane with high mechanical strength and high elongation at break is characterized by comprising the following steps:
the diisocyanate, the dihydric alcohol, the polysiloxane and the catalyst are stirred and mixed uniformly, the temperature is raised to 80-90 ℃, the reaction is carried out for 150-200 min under the protection of inert gas, then the temperature is lowered to 60-80 ℃, the epoxy resin and the chain extender A are added, the stirring and the mixing are carried out uniformly, the reaction is carried out for 100-150 min under 80-90 ℃, then the temperature is lowered to 60-80 ℃, the chain extender B and the cross-linking agent are continuously added, the stirring and the mixing are carried out uniformly, the reaction is carried out for 80-100 min under 80-90 ℃, then the temperature is lowered to 30-50 ℃, the neutralizing agent is continuously added, the stirring and the mixing are carried out uniformly, the reaction is carried out for 20-40 min under 30-50 ℃, meanwhile, the organic solvent is added in the reaction process, and finally the aqueous polyurethane with high mechanical strength and high breaking elongation is obtained after emulsification and spin evaporation.
2. The method of claim 1, wherein the diisocyanate, diol, polysiloxane, catalyst, chain extender a, chain extender B, and crosslinker are present in a molar ratio of 1: (0.15-0.35): (0.01-0.04): (0.0005-0.001): (0.2-0.4): (0.1-0.2): (0.05-0.15);
further preferably, the molar ratio of diisocyanate, diol, polysiloxane, catalyst, chain extender a, chain extender B and crosslinking agent is 1:0.19:0.015:0.0008:0.27:0.11:0.076.
3. the method of claim 1, wherein the molar ratio of isocyanate groups in the diisocyanate to the total active hydroxyl groups of diol, polysiloxane, chain extender a, chain extender B and crosslinker is 1: (0.5-1).
4. The preparation method according to claim 1, wherein the diisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate;
further preferred, the diisocyanate is isophorone diisocyanate;
the dihydric alcohol is one or more of polyether dihydric alcohol with molecular weight of 500-4000, polyester dihydric alcohol with molecular weight of 500-4000, or polyolefin dihydric alcohol with molecular weight of 500-4000;
further preferably, the glycol is 1, 6-hexanediol diphenyl carbonate glycol having a molecular weight of 2000.
5. The method according to claim 1, wherein the polysiloxane is a hydroxyl-terminated polydimethylsiloxane having a molecular weight of 500 to 5000;
further preferably, the polysiloxane is a hydroxyl-terminated polydimethylsiloxane having a molecular weight of 500, 1000, 2000.
6. The method of claim 1, wherein the epoxy resin is one or more of bisphenol a type epoxy resin E-51, bisphenol a type epoxy resin E-20, bisphenol a type epoxy resin E-44, phenolic type epoxy resin F-48, or phenolic type epoxy resin F-44;
further preferably, the epoxy resin is bisphenol A type epoxy resin E-44;
the mass ratio of the polysiloxane to the epoxy resin is 1: (0.5-3); the epoxy resin accounts for 2-8% of the total mass of the preparation raw materials;
further preferably, the mass ratio of the polysiloxane to the epoxy resin is 1:1.5; the epoxy resin accounts for 6% of the total preparation raw material mass.
7. The preparation method according to claim 1, wherein the chain extender A is one or more of dimethylolpropionic acid, dimethylolbutyric acid and sodium ethylenediamine sulfonate;
further preferably, the chain extender A is dimethylolpropionic acid;
the chain extender B is one or more of 1,4 butanediol, glycerol, pentaerythritol and isovaleryltetraol;
further preferably, the chain extender B is 1,4 butanediol;
the cross-linking agent is one or more of diethanolamine, trimethylolpropane, pentaerythritol and diethylenetriamine;
further preferably, the crosslinking agent is trimethylolpropane.
8. An aqueous polyurethane having high mechanical strength and high elongation at break, prepared by the method according to any one of claims 1 to 7.
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