CN108559126A - 可发泡的高硬度热塑性聚氨酯 - Google Patents
可发泡的高硬度热塑性聚氨酯 Download PDFInfo
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- CN108559126A CN108559126A CN201810242375.7A CN201810242375A CN108559126A CN 108559126 A CN108559126 A CN 108559126A CN 201810242375 A CN201810242375 A CN 201810242375A CN 108559126 A CN108559126 A CN 108559126A
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- Prior art keywords
- thermoplastic polyurethane
- mol
- diisocyanate
- high rigidity
- ester
- Prior art date
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- 238000002156 mixing Methods 0.000 claims abstract description 13
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- -1 aromatic isocyanate Chemical class 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 239000012948 isocyanate Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 150000002513 isocyanates Chemical group 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 13
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- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 10
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 9
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- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011256 inorganic filler Substances 0.000 claims description 4
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- 229920000570 polyether Polymers 0.000 claims description 4
- 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 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012766 organic filler Substances 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- KAEIHZNNPOMFSS-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1CCC1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1CCC1=CC=CC=C1 KAEIHZNNPOMFSS-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
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- 239000003963 antioxidant agent Substances 0.000 claims description 2
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- 239000004305 biphenyl Substances 0.000 claims description 2
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- SXXILWLQSQDLDL-UHFFFAOYSA-N bis(8-methylnonyl) phenyl phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OC1=CC=CC=C1 SXXILWLQSQDLDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 235000010216 calcium carbonate Nutrition 0.000 claims description 2
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 claims description 2
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical class O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 claims description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 2
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 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 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 125000004957 naphthylene group Chemical group 0.000 claims description 2
- 125000005474 octanoate group Chemical group 0.000 claims description 2
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000049 pigment Substances 0.000 claims description 2
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- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims 2
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- QICVZJNIJUZAGZ-UHFFFAOYSA-N benzene;phosphorous acid Chemical compound OP(O)O.C1=CC=CC=C1 QICVZJNIJUZAGZ-UHFFFAOYSA-N 0.000 claims 1
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- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 claims 1
- 150000002009 diols Chemical class 0.000 claims 1
- 238000002845 discoloration Methods 0.000 claims 1
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 claims 1
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
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- 238000000465 moulding Methods 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
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- 238000007906 compression Methods 0.000 description 3
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- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
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- 239000004425 Makrolon Substances 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
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- 230000005587 bubbling Effects 0.000 description 1
- NIHJEJFQQFQLTK-UHFFFAOYSA-N butanedioic acid;hexanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCCCC(O)=O NIHJEJFQQFQLTK-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 238000006471 dimerization reaction Methods 0.000 description 1
- 125000002474 dimethylaminoethoxy group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])C([H])([H])O* 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/08—Polyurethanes from polyethers
Abstract
可发泡的高硬度热塑性聚氨酯,通过于热塑性聚氨酯材料的软段相中引入二种及以上的聚合多元醇的混合组分,使得热塑性聚氨酯材料在肖氏硬度A85~A98的高硬度下,具有较低的结晶度。该技术方案使得热塑性聚氨酯材料具备较高的发泡剂穿透效率与较低的发泡温度,同时发泡材料具备较高的肖氏硬度和形状稳定性。
Description
技术领域
本发明涉及IPC分类C08L75/04中热塑性聚氨酯制备技术,尤其是可发泡的高硬度热塑性聚氨酯。
背景技术
热塑性聚氨酯(TPU)是热塑性弹性体中的半结晶材料,基本结构由软段相和硬段相组成。软段相通常由摩尔质量为600g/mol~8000g/mol的聚合多元醇构成,硬段相通常由二异氰酸酯与短链的二元醇和/或二元胺链接单元构成。通过调整软段相和硬段相的分子结构与质量比,可以对TPU材料的物理和化学性能进行调控。由于TPU材料具有良好的物理机械、磨耗、抗撕裂传播和耐化学品等性能,同时生产过程绿色环保,人们进一步拓展了其在发泡制品中的应用。TPU发泡材料具有密度低、收缩率小、表面质地均匀,同时还具有TPU树脂特有的性能,可广泛地应用于减震材料、包装材料、儿童玩具、体育用品、航空模型、保温隔热材料以及汽车内饰材料等领域。
本发明涉及可发泡的高硬度TPU及其制备方法,即用于制备发泡TPU材料的原材料树脂的制备技术。
相关专利文献公开较少。例如:
中国专利申请01822392.3提供一种有均一发泡构造、达到被研磨面的平滑性和平滑化效率的改善、使用期比先有技术的延长、且适合用来作为研磨垫料的聚氨酯泡沫体。这个目的是由一种聚氨酯泡沫体达到的,该泡沫体用一种通过使一种聚合物多元醇、一种有机二异氰酸酯和一种链增长剂反应产生的、以约6wt%或以上的数量含有源于异氰酸酯的氮原子、显示出5×109dyn/cm2或以上的50℃动态粘弹性(E′50)的TPU制成,其密度为0.5~1.0g/cm3、泡孔尺寸为5~200μm、硬度(JIS-C硬度)为90或以上。
相关国家、国际组织公开的专利文献有限。例如:
DE 4015714 A1发明了一种利用玻璃纤维增强的TPU而制备发泡TPU板的方法,利用玻璃纤维对于TPU材料软段相的通道作用提升可发泡性能,实施例中所用TPU材料基于单一多元醇组分。该TPU板无法进行模塑加工,因此在实际应用中面临加工与塑形上的困难。
WO 94/20568发明了一种可模塑的TPU泡沫,实施例中TPU材料基于单一多元醇组分。其缺点在于发泡过程中的高能耗,所需发泡温度为145~165℃。
US 2010/0222442 A1发明了一种可模塑的TPU泡沫,通过在TPU材料中引入合适的发泡剂,克服了发泡过程中的高能耗,实施例中TPU材料基于单一多元醇组分。其缺点在于仅适用于较低硬度的TPU材料,即肖氏硬度A84及以下。
相比于较低硬度的TPU材料,肖氏硬度A85及以上的TPU材料具有更高的机械强度、尺寸稳定性、耐热性以及耐化学品等性能。然而,高硬度的TPU材料通常具有较高的结晶度与较强的抗微区变形能力,前者不利于发泡剂的浸渍与穿透,后者使得硬段相区的塑化能力下降,导致发泡效率低下与生产成本的增加。
发明内容
本发明的目的是提供可发泡的高硬度TPU,具备较高的发泡剂穿透效率、泡沫硬度和泡沫形稳性,而且,发泡能耗较低。
本发明的目的将通过以下技术措施来实现:
包括原料组分与制备方法,其中组分至少包含(a)和(b),或(c)、(d)和(e);其中:
(a)为异氰酸酯,是脂肪族、脂肪环族、芳香族异氰酸酯中的一种或二种以上的混合物。
(b)为软段相中对(a)异氰酸酯呈反应性的多羟基组分化合物,包括聚酯醇、聚醚醇、聚碳酸酯醇中的一种单一聚合醇或它们的混合物,该单一聚合醇具有的摩尔质量为600g/mol~8000g/mol。
(c)为扩链剂,包括摩尔质量为50g/mol~499g/mol的脂肪族、脂环族或芳香族化合物。
(d)为促进二异氰酸酯(a)的NCO基团与原料组分(b)和(c)的OH基团间反应的催化剂,包括三乙胺、二甲基环己胺、N-甲基吗啉、N,N’-二甲基哌嗪、2-(二甲基氨基乙氧基)乙醇、二氮杂二环[2.2.2]辛烷以及有机金属化合物中的一种。
(e)为助剂或添加剂,将助剂或添加剂(e)分别添加至组分(a)~(d)中。助剂或添加剂(e)包括防粘剂、表面活性剂、阻燃剂、抗氧化剂、内/外润滑剂、脱模剂、染料或颜料以及稳定剂、有机/无机填料、增塑剂以及增强剂。
生产方法为:将(a)异氰酸酯与(b)摩尔质量为600g/mol~8000g/mol的聚合多元醇,或(c)扩链剂摩尔质量为50g/mol~499g/mol,或者,在(d)催化剂或(e)助剂或添加剂的存在下一起反应生产。
制备过程通过一步法或预聚体法在皮带系统上或反应挤出机中连续合成;或者,通过预聚体法分批次合成,在这些方法中,组分(a)和组分(b),或者,组分(c)、(d)、(e)依次或同时混合,混合后反应随机发生。将所有组分依次或同时混合、引入挤出机/带式机上,在100~260℃下,并将反应得到的TPU挤出、冷却和造粒。丸粒的平均直径优选0.2~12mm,在进一步加工之前,制得TPU丸粒在80~120℃下,熟化1~24h,其中,TPU是通过流变仪以5K/分钟的加热速率测量的,起始流动温度低于200℃,并且TPU的熔融指数小于135g/10min,其根据ASTM D1238,在205℃下,施加5kg的重量测量。
制备过程中,原料组分(b)和(c)的摩尔比为10:1~1:10。
制备过程反应在指数下进行,该指数为65~115,其中,指数的定义为,原料组分(a)中异氰酸酯基的摩尔数与在原料组分(b)和(c)中对异氰酸酯呈反应性的基团的摩尔总数的比值,即对组分(b)和组分(c)中活泼氢摩尔总数的比值。
作为上述合成方法的替换,TPU也可通过于双螺杆挤出机中熔融、共混两种及以上TPU而制备。在该方法中,先于挤出机混合斗中调匀二种及以上基于单一或多种聚合多元醇的TPU的珠粒,随后引入挤出机中,在150~260℃下,熔融共混,将得到的TPU经挤出、冷却和造粒。
本发明的优点和效果:通过于TPU材料的软段相中引入二种及以上的聚合多元醇的混合组分,使得TPU材料在肖氏硬度A85~A98的高硬度下,具有较低的结晶度。该技术方案使得TPU材料具备较高的发泡剂穿透效率与较低的发泡温度,同时发泡材料具备较高的肖氏硬度和形状稳定性。适用于如鞋底、汽车内饰、家具和其它对于尺寸要求严苛的注塑件中。
具体实施方式
本发明TPU材料的肖氏硬度优选A85~A95,具有较高的肖氏硬度和较好的尺寸稳定性,其中特别优选A86~A90。
本发明包括原料组分与制备方法,其中组分至少包含(a)和(b),或(c)、(d)和(e):其中:
(a)异氰酸酯组分。优选二异氰酸酯,包括三~八亚甲基二异氰酸酯、2-乙基亚丁基-1,4-二异氰酸酯、2-甲基五亚甲基-1,5-二异氰酸酯、环己烷-1,4-二异氰酸酯、1-甲基环己烷-2,4-或2,6-二异氰酸酯、1,4或1,3-二(异氰酸甲酯基)环己烷(HXDI)、二环己基甲烷-4,4’-或2,4’-或2,2’-二异氰酸酯、1-异氰酸酯-3,3,5-三甲基-5-异氰酸甲酯基环己烷即异佛尔酮二异氰酸酯(IPDI)、甲苯-2,4-或2,6-二异氰酸酯(TDI)、二苯甲烷-2,2’-或2,4’或4,4’-二异氰酸酯(MDI)、亚萘基-1,5-二异氰酸酯(NDI)、3,3’-二甲基联苯二异氰酸酯、1,2-二苯乙烷二异氰酸酯中的一种或二种以上的混合物。
(b)对(a)的异氰酸酯呈反应性的多羟基组分化合物。软段相中含有二种及以上的摩尔质量为600g/mol~2500g/mol的聚醚多元醇的混合物,优选聚四亚甲基醚多元醇的混合物,特别优选聚四亚甲基醚二元醇的混合物;并且优选的平均官能度为1.8~2.2,特别优选2.0。优选基于己二酸和1,4-丁二醇、具有摩尔质量为600g/mol~3500g/mol的聚酯二元醇的混合物。
(c)为扩链剂。优选二官能度的化合物,包括亚烷基中具有2~10个碳原子的直链二醇/二胺,特别优选其中偶数个碳原子的二醇/二胺或其混合物。
(d)为催化剂。优选三乙胺、二甲基环己胺、N-甲基吗啉、N,N’-二甲基哌嗪、2-(二甲基氨基乙氧基)乙醇、二氮杂二环[2.2.2]辛烷以及有机金属化合物中的一种。特别优选有机金属化合物,包括钛酸酯、二乙酸亚锡、二辛酸亚锡、二月桂酸亚锡、二乙酸二丁基锡、二月桂酸二丁基锡、乙酰丙酮铁(III)等。实际操作中,催化剂在多羟基组分化合物(b)中的质量比通常为1ppm~500ppm。
(e)为助剂或添加剂。如果合适的话,还可以将助剂或添加剂(e)添加至组分(a)~(d)中。在一个优选的实施方案中,TPU可包含磷化合物。合适的磷化合物是三价磷的有机化合物,包括亚磷酸酯,优选为亚磷酸三苯酯、亚磷酸三(壬基苯基)酯、亚磷酸三(十八烷基)酯、亚磷酸三月桂基酯、亚磷酸三(2,4-二叔丁基苯基)酯、亚磷酸三异癸基酯、亚磷酸苯基二烷基酯、二亚磷酸二异癸基季戊四醇酯、二亚磷酸二(2,4-二叔丁基苯基)季戊四醇酯、二亚磷酸二硬脂基季戊四醇酯、亚磷酸异癸基二苯基酯、亚磷酸二异癸基苯基酯、亚磷酸二聚丙二醇苯基酯或它们的混合物。其中,填料优选有机/无机粉末或其混合物。特别优选的是无机粉末,包括高岭土、滑石、碳酸钙、石英、氧化铝、硅酸铝、硅石或它们的混合物。填料平均粒径优选在0.1~100μm范围内,特别优选1~30μm范围内。实际操作中,该部分无机填料在TPU中的质量比通常为0.01~10%,优选0.1~8%。包含特别优选质量比1~5%的有机和/或无机填料,该含量基于TPU的总重。
本发明制备过程中为了调节TPU材料的硬度,原料组分(b)和(c)的摩尔比可以连续且广泛地进行变化。原料组分(b)和(c)的摩尔比优选10:1~1:10,特别优选1:1~1:6,此时,TPU的硬度随着组分(c)含量的增加而升高。
本发明制备过程反应在常规指数下进行,优选指数为65~115,特别优选指数为85~110。其中,指数的定义为,原料组分(a)中异氰酸酯基的摩尔数与在原料组分(b)和(c)中对异氰酸酯呈反应性的基团的摩尔总数的比值,即对组分(b)和组分(c)中活泼氢摩尔总数的比值。例如,反应指数是100时,组分(a)中的每一个异氰酸酯基团,在组分(b)或(c)中都有一个对应的活泼氢原子。如果指数大于100,则表明异氰酸酯基团数目大于活泼氢原子总数目。
本发明通过一步法或预聚体法在皮带系统上或反应挤出机中连续合成;或者,通过预聚体法分批次合成。在这些方法中,组分(a)和组分(b),或者,组分(c)、(d)、(e)依次或同时混合,混合后反应随机发生。
本发明在挤出机或带式机合成TPU的方法中,将所有组分依次或同时混合、引入挤出机/带式机上,在100~260℃下,优选130~240℃下反应,并将反应得到的TPU挤出、冷却和造粒。丸粒的平均直径优选0.2~12mm,特别优选0.6~6mm。如果合适的话,在进一步加工之前,制得TPU丸粒在80~120℃下,优选100~110℃下,熟化1~24h。其中,TPU是通过流变仪以5K/分钟的加热速率测量的,起始流动温度低于200℃,更优选始流动温度低于190℃;并且TPU的熔融指数最多具有135g/10min,尤其是小于100g/10min,其根据ASTM D1238,在205℃下,施加5kg的重量测量。
本发明中优选的TPU还可以通过于挤出机中熔融共混两种及以上、基于单一或多种聚合多元醇的TPU的共混物而制备。例如,先于混合斗中混合调匀二种及以上基于单一或多种聚合多元醇的TPU的珠粒,随后引入挤出机中,在150~260℃下,优选180~240℃下,熔融共混,并将得到的TPU经挤出、冷却和造粒。
下面结合实施例对本发明作进一步说明。
为便于本领域专业技术人员能够迅速理解本发明,将实施例1、2和3对比列表如下:
具体的实施例包括:
实施例1:软段相中,聚合多元醇聚四亚甲基醚平均摩尔质量1333g/mol,软段相1质量份中TPU组成,1,4-丁二醇0.11份,4,4'-MDI 0.50份;TPU性能包括,检测标准ASTMD2240,肖氏硬度A86;检测标准ASTM D792,密度1.09g/cm3;检测标准CFT-500D流变仪,软化点159.3℃,初始流动温度179.3℃;检测标准ASTM D412,100%定伸强度6.49Mpa,300%定伸强度12.71Mpa,拉伸强度35.13Mpa,断裂伸长率633.32%;检测标准ASTM D624,撕裂强度52.37kN/m;检测标准Tape法,磨耗43.3g;检测标准23℃,72h,永久压缩形变22%;发泡参数包括,发泡剂为超临界二氧化碳,发泡温度113℃,发泡时间100s;泡沫性能包括,检测标准ASTM D792,泡沫丸粒密度0.20g/cm3,检测标准ASTMD2240,泡沫肖氏硬度C43,检测标准HG/T 2874,成型热收缩<1%。
实施例2:软段相中,聚合多元醇聚四亚甲基醚平均摩尔质量1333g/mol,软段相1质量份中TPU组成,1,4-丁二醇0.15份,4,4'-MDI 0.60份;TPU性能包括,检测标准ASTMD2240,肖氏硬度A90;检测标准ASTM D792,密度1.12g/cm3;检测标准CFT-500D流变仪,软化点165℃,初始流动温度189℃;检测标准ASTM D412,100%定伸强度9.10Mpa,300%定伸强度17.21Mpa,拉伸强度40.30Mpa,断裂伸长率537.20%;检测标准ASTM D624,撕裂强度96.65kN/m;检测标准Tape法,磨耗35.4g;检测标准23℃,72h,永久压缩形变15%;发泡参数包括,发泡剂为超临界二氧化碳,发泡温度118℃,发泡时间150s;泡沫性能包括,检测标准ASTM D792,泡沫丸粒密度0.21g/cm3,检测标准ASTM D2240,泡沫肖氏硬度C54,检测标准HG/T 2874,成型热收缩<1%。
实施例3:软段相中,聚合多元醇为聚己二酸丁二醇酯和聚己二酸乙二醇丁二醇酯,平均摩尔质量1500g/mol,软段相1质量份中TPU组成,1,4-丁二醇0.12份,4,4'-MDI0.51份;TPU性能包括,检测标准ASTM D2240,肖氏硬度A87;检测标准ASTM D792,密度1.20g/cm3;检测标准CFT-500D流变仪,软化点169.5℃,初始流动温度206.2℃;检测标准ASTM D412,100%定伸强度8.97Mpa,300%定伸强度20.48Mpa,拉伸强度45.11Mpa,断裂伸长率445.76%;检测标准ASTM D624,撕裂强度96.59kN/m;检测标准Tape法,磨耗33.2g;检测标准23℃,72h,永久压缩形变20%;发泡参数包括,发泡剂为超临界二氧化碳,发泡温度136℃,发泡时间150s;泡沫性能包括,检测标准ASTM D792,泡沫丸粒密度0.35g/cm3,检测标准ASTM D2240,泡沫肖氏硬度C48,检测标准HG/T 2874,成型热收缩<1%。
本发明保护范围不受以上实施例以及所列合成方法的限制。
Claims (9)
1.可发泡的高硬度热塑性聚氨酯,其特征在于,包括原料组分与制备方法,其中组分至少包含(a)和(b),或(c)、(d)和(e);其中:
(a)为异氰酸酯,是脂肪族、脂肪环族、芳香族异氰酸酯中的一种或二种以上的混合物;
(b)为软段相中对(a)异氰酸酯呈反应性的多羟基组分化合物,包括聚酯醇、聚醚醇、聚碳酸酯醇中的一种单一聚合醇或它们的混合物,该单一聚合醇具有的摩尔质量为600g/mol~8000g/mol;
(c)为扩链剂,包括摩尔质量为50g/mol~499g/mol的脂肪族、脂环族或芳香族化合物;
(d)为促进二异氰酸酯(a)的NCO基团与原料组分(b)和(c)的OH基团间反应的催化剂,包括三乙胺、二甲基环己胺、N-甲基吗啉、N,N’-二甲基哌嗪、2-(二甲基氨基乙氧基)乙醇、二氮杂二环[2.2.2]辛烷以及有机金属化合物中的一种;
(e)为助剂或添加剂,将助剂或添加剂(e)分别添加至组分(a)~(d)中。助剂或添加剂(e)包括防粘剂、表面活性剂、阻燃剂、抗氧化剂、内/外润滑剂、脱模剂、染料或颜料以及稳定剂、有机/无机填料、增塑剂以及增强剂;
生产方法为:将(a)异氰酸酯与(b)摩尔质量为600g/mol~8000g/mol的聚合多元醇,或(c)扩链剂摩尔质量为50g/mol~499g/mol,或者,在(d)催化剂或(e)助剂或添加剂的存在下一起反应生产;
制备过程通过一步法或预聚体法在皮带系统上或反应挤出机中连续合成;或者,通过预聚体法分批次合成,在这些方法中,组分(a)和组分(b),或者,组分(c)、(d)、(e)依次或同时混合,混合后反应随机发生;将所有组分依次或同时混合、引入挤出机/带式机上,在100~260℃下,并将反应得到的热塑性聚氨酯挤出、冷却和造粒;丸粒的平均直径优选0.2~12mm,在进一步加工之前,制得热塑性聚氨酯丸粒在80~120℃下,熟化1~24h,其中,热塑性聚氨酯是通过流变仪以5K/分钟的加热速率测量的,起始流动温度低于200℃,并且热塑性聚氨酯小于135g/10min,其根据ASTM D1238,在205℃下,施加5kg的重量测量;
制备过程中,原料组分(b)和(c)的摩尔比为10:1~1:10;
制备过程反应在指数下进行,该指数为65~115,其中,指数的定义为,原料组分(a)中异氰酸酯基的摩尔数与在原料组分(b)和(c)中对异氰酸酯呈反应性的基团的摩尔总数的比值,即对组分(b)和组分(c)中活泼氢摩尔总数的比值。
2.如权利要求1所述的可发泡的高硬度热塑性聚氨酯,其特征在于,(a)为二异氰酸酯,包括三~八亚甲基二异氰酸酯、2-乙基亚丁基-1,4-二异氰酸酯、2-甲基五亚甲基-1,5-二异氰酸酯、环己烷-1,4-二异氰酸酯、1-甲基环己烷-2,4-或2,6-二异氰酸酯、1,4或1,3-二(异氰酸甲酯基)环己烷(HXDI)、二环己基甲烷-4,4’-或2,4’-或2,2’-二异氰酸酯、1-异氰酸酯-3,3,5-三甲基-5-异氰酸甲酯基环己烷即异佛尔酮二异氰酸酯(IPDI)、甲苯-2,4-或2,6-二异氰酸酯(TDI)、二苯甲烷-2,2’-或2,4’或4,4’-二异氰酸酯(MDI)、亚萘基-1,5-二异氰酸酯(NDI)、3,3’-二甲基联苯二异氰酸酯、1,2-二苯乙烷二异氰酸酯中的一种或二种以上的混合物。
3.如权利要求1所述的可发泡的高硬度热塑性聚氨酯,其特征在于,(b)为软段相中含有二种及以上的摩尔质量为600g/mol~2500g/mol的聚醚多元醇的混合物,并且,平均官能度为1.8~2.2,优选2.0。
4.如权利要求1所述的可发泡的高硬度热塑性聚氨酯,其特征在于,作为聚醚多元醇混合组分的替换,也可使用具有摩尔质量为600g/mol~3500g/mol的己二酸和1,4-丁二醇的聚丁二醇己二酸酯二元醇的混合物,官能度为2.0。
5.如权利要求1所述的可发泡的高硬度热塑性聚氨酯,其特征在于,扩链剂为亚烷基中具有2、4、6、8、10个碳原子的直链二醇/二胺或其混合物。
6.如权利要求1所述的可发泡的高硬度热塑性聚氨酯,其特征在于,(d)催化剂为有机金属化合物,包括钛酸酯、二乙酸亚锡、二辛酸亚锡、二月桂酸亚锡、二乙酸二丁基锡、二月桂酸二丁基锡、乙酰丙酮铁(III)中的一种,(d)催化剂在多羟基组分化合物(b)中的质量比为1ppm~500ppm。
7.如权利要求1所述的可发泡的高硬度热塑性聚氨酯,其特征在于,助剂或添加剂(e)中稳定剂包括光/热/变色和/或水解的稳定剂;或者,助剂或添加剂(e)为三价磷的有机化合物,包括亚磷酸酯,具体包括亚磷酸三苯酯、亚磷酸三(壬基苯基)酯、亚磷酸三(十八烷基)酯、亚磷酸三月桂基酯、亚磷酸三(2,4-二叔丁基苯基)酯、亚磷酸三异癸基酯、亚磷酸苯基二烷基酯、二亚磷酸二异癸基季戊四醇酯、二亚磷酸二(2,4-二叔丁基苯基)季戊四醇酯、二亚磷酸二硬脂基季戊四醇酯、亚磷酸异癸基二苯基酯、亚磷酸二异癸基苯基酯、亚磷酸二聚丙二醇苯基酯中的一种或它们的混合物;或者,助剂或添加剂(e)为无机粉末填料,包括高岭土、滑石、碳酸钙、石英、氧化铝、硅酸铝、硅石或它们的混合物,平均粒径在1~30μm范围内,在热塑性聚氨酯中基于热塑性聚氨酯的总重的质量比为0.1~8%。
8.如权利要求1所述的可发泡的高硬度热塑性聚氨酯,其特征在于,原料组分(b)和(c)的摩尔比为1:1~1:6,此时,热塑性聚氨酯的硬度随着组分(c)含量的增加而升高。
9.如权利要求1所述的可发泡的高硬度热塑性聚氨酯,其特征在于,热塑性聚氨酯通过双螺杆挤出机中熔融、共混两种及以上热塑性聚氨酯而制备;在该方法中,先于挤出机混合斗中调匀二种及以上基于单一或多种聚合多元醇的热塑性聚氨酯的珠粒,随后引入挤出机中,在150~260℃下,熔融共混,将得到的热塑性聚氨酯经挤出、冷却和造粒。
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