CN111183166B - 聚氨酯复合材料 - Google Patents
聚氨酯复合材料 Download PDFInfo
- Publication number
- CN111183166B CN111183166B CN201880061079.5A CN201880061079A CN111183166B CN 111183166 B CN111183166 B CN 111183166B CN 201880061079 A CN201880061079 A CN 201880061079A CN 111183166 B CN111183166 B CN 111183166B
- Authority
- CN
- China
- Prior art keywords
- diphenylmethane diisocyanate
- polyurethane composition
- polyurethane
- range
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000004814 polyurethane Substances 0.000 title claims abstract description 80
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 44
- 239000012948 isocyanate Substances 0.000 claims abstract description 21
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012779 reinforcing material Substances 0.000 claims abstract description 11
- 239000000835 fiber Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 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 6
- 229920005862 polyol Polymers 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 230000002787 reinforcement Effects 0.000 claims 2
- 239000011152 fibreglass Substances 0.000 claims 1
- 238000009730 filament winding Methods 0.000 claims 1
- 238000009787 hand lay-up Methods 0.000 claims 1
- 238000001802 infusion Methods 0.000 claims 1
- 238000001746 injection moulding Methods 0.000 claims 1
- 229920005906 polyester polyol Polymers 0.000 claims 1
- 238000001721 transfer moulding Methods 0.000 claims 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000006082 mold release agent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000002657 fibrous material Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- -1 polyoxypropylene Polymers 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229920002748 Basalt fiber Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical class [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000001408 fungistatic effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- FBPFZTCFMRRESA-UHFFFAOYSA-N hexane-1,2,3,4,5,6-hexol Chemical class OCC(O)C(O)C(O)C(O)CO FBPFZTCFMRRESA-UHFFFAOYSA-N 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical class CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
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Abstract
本发明涉及聚氨酯组合物,其包含:(1)异氰酸酯;和(2)异氰酸酯反应性化合物;其中异氰酸酯包括2,2'‑二苯基甲烷二异氰酸酯和2,4'‑二苯基甲烷二异氰酸酯,并且2,2'‑二苯基甲烷二异氰酸酯的量在10‑100重量%的范围内,基于2,2'‑二苯基甲烷二异氰酸酯和2,4'‑二苯基甲烷二异氰酸酯的总重量。本发明还涉及包含所述聚氨酯组合物和增强材料的聚氨酯复合材料,以及由所述聚氨酯复合材料制备的制品。
Description
技术领域
本发明涉及聚氨酯组合物,包含所述聚氨酯组合物和增强材料的聚氨酯复合材料,以及由所述聚氨酯复合材料生产的制品。
背景技术
聚氨酯(PU)复合材料由于其广泛的性能而现在用于许多应用中。特别地,与传统结构材料如混凝土、钢、铝和常规热固性树脂相比,聚氨酯复合材料在拉挤成型工艺中显示出优异的性能和独特的优点。
拉挤成型工艺是一种用于制造纤维增强型材的连续工艺,其中,在敞开的浴槽中或在封闭的注射箱中用聚氨酯组合物浸渍纤维,然后使其成型和硬化。尽管聚氨酯具有各种优点,但其相对短的加工时间使得通过拉挤成型工艺生产大尺寸部件具有挑战性,例如桥梁构件、大型人造木材、大型柱结构、复杂的窗型材、冷藏集装箱等。
CN104045806A公开了一种用于制备聚氨酯复合材料的聚氨酯组合物,包括:a)多异氰酸酯组分,其中所述多异氰酸酯组分包含2,2'-二苯基甲烷二异氰酸酯和2,4'-二苯基甲烷二异氰酸酯;和b)异氰酸酯反应性组分。
US2013/0309924A1公开了一种增强的拉挤聚氨酯,其可通过使A)聚醚多元醇,B)环氧化物与C)有机多异氰酸酯反应获得。
US8,663,414B2公开了一种拉挤树脂体系,包括a)二异氰酸酯或多异氰酸酯,b)具有至少两个对异氰酸酯呈反应性的基团的化合物,c)催化剂,d)官能度大于或等于2的多元酸,和任选地,e)其它助剂或添加剂,其中在标准压力下,所述多元酸的沸点为至少200℃,和所述多元酸可溶于具有至少两个对异氰酸酯呈反应性的基团的化合物中。
然而,仍然需要找到具有相对长的加工时间以允许生产较大尺寸的部件的聚氨酯组合物。
发明概述
因此,本发明提供了一种聚氨酯组合物,其包含:
(1)异氰酸酯;以及
(2)异氰酸酯反应性化合物;
其中异氰酸酯包括2,2'-二苯基甲烷二异氰酸酯(2,2'-MDI)和2,4'-二苯基甲烷二异氰酸酯(2,4'-MDI),并且2,2'-二苯基甲烷二异氰酸酯的量在基于2,2'-二苯基甲烷二异氰酸酯和2,4'-二苯基甲烷二异氰酸酯的总重量的10-100重量%的范围内。
本发明提供一种聚氨酯复合材料,其包含:
(1)上述聚氨酯组合物;以及
(2)增强材料。
本发明还提供由上述聚氨酯复合材料生产的制品。
本发明的聚氨酯组合物具有延长的胶凝时间,使得聚氨酯组合物特别适合于生产大尺寸部件,例如桥梁构件、大型人造木材、大型柱结构、复杂的窗型材、冷藏集装箱等。
实施方案
在本发明的一个实施方案中,提供了聚氨酯组合物,其中所述聚氨酯组合物包含:(1)异氰酸酯;和(2)异氰酸酯反应性化合物;其中异氰酸酯包括2,2'-二苯基甲烷二异氰酸酯和2,4'-二苯基甲烷二异氰酸酯,并且2,2'-二苯基甲烷二异氰酸酯的量在10-100重量%,优选15-70重量%,更优选20-50重量%,还更优选20-30重量%的范围内,基于2,2'-二苯基甲烷二异氰酸酯和2,4'-二苯基甲烷二异氰酸酯的总重量。
在聚氨酯组合物中,2,2'-二苯基甲烷二异氰酸酯和2,4'-二苯基甲烷二异氰酸酯的总量为50-100重量%,优选60-90重量%,更优选60-80重量%,基于异氰酸酯的总重量。
聚氨酯组合物可以是致密的或泡沫体。在本发明的一个实施方案中,聚氨酯组合物具有30g/l-900g/l的自由起发密度(rise density)。
异氰酸酯可以包括单体二苯基甲烷二异氰酸酯和具有较大数目的环的二苯基甲烷二异氰酸酯同系物的混合物(聚合MDI),甲苯二异氰酸酯(TDI),例如甲苯二异氰酸酯异构体如甲苯2,4-或2,6-二异氰酸酯,或这些的混合物,萘二异氰酸酯(NDI),或它们的混合物,优选2,2'-二苯基甲烷二异氰酸酯、2,4'-二苯基甲烷二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯(4,4'-MDI)、聚合MDI,或它们的组合。
异氰酸酯反应性化合物,对于本发明也称为“多元醇”,可以包括具有至少两个对异氰酸酯呈反应性的基团的任何化合物,所述基团的实例是OH、SH、NH2、-COON和CH-酸性基团。
异氰酸酯反应性化合物是本领域技术人员已知的,并描述于例如“Kunststoffhandbuch,7,Polyurethane”[Plastics Handbook,7,Polyurethanes]CarlHanser-Verlag,第3版,1993,第3.1章中。异氰酸酯反应性化合物的实例是聚醚醇或聚酯醇。异氰酸酯反应性化合物可以是包含仲OH基团的聚醚醇或聚酯醇,实例是聚氧化丙烯。这些聚醚醇或聚酯醇的官能度优选为2-4,特别优选2-3。
通常使用具有2-8个对异氰酸酯呈反应性的氢原子的聚醚醇和/或聚酯醇,和使用低分子量多元醇,例如甘油、二丙二醇和/或三丙二醇。这些化合物的OH值通常为30-2000mgKOH/g,优选40-1000mg KOH/g。这里使用的所有具有至少两个对异氰酸酯呈反应性的基团的异氰酸酯反应性化合物的平均OH值为100-1000mg KOH/g,优选300-900mg KOH/g。
聚醚醇通过已知方法获得,例如通过在催化剂存在下,添加至少一种包含2-8个,优选2-6个,特别优选2-4个反应性氢原子的起始分子,通过氧化烯的阴离子聚合获得。所用的催化剂可以包括碱金属氢氧化物,例如氢氧化钠或氢氧化钾,或碱金属醇盐,例如甲醇钠、乙醇钠、乙醇钾或异丙醇钾,或在阳离子聚合的情况下,路易斯酸,例如五氯化锑、三氟化硼乙醚合物或漂白土。可以使用的其它催化剂是双金属氰化物化合物,称为DMC催化剂。
所用的氧化烯优选包括一种或多种在亚烷基结构部分具有2-4个碳原子的化合物,例如四氢呋喃、氧化乙烯、1,2-氧化丙烯、1,2-氧化丁烯或2,3-氧化丁烯,在每种情况下单独或以混合物形式,优选1,2-氧化丙烯和/或氧化乙烯,特别是1,2-氧化丙烯。
可使用的起始分子的实例是乙二醇、二甘醇、甘油、三羟甲基丙烷、季戊四醇、糖衍生物如蔗糖、己糖醇衍生物如山梨醇、甲胺、乙胺、异丙胺、丁胺、苄胺、苯胺、甲苯胺、甲苯二胺、萘胺、乙二胺、二亚乙基三胺、4,4'-亚甲基二苯胺、1,3-丙二胺、1,6-己二胺、乙醇胺、二乙醇胺、三乙醇胺、以及其它二-或多元醇、或二-或多元胺。
所用的聚酯醇主要通过具有2-12个碳原子的多元醇,例如乙二醇、二甘醇、丁二醇、三羟甲基丙烷、甘油或季戊四醇与具有2-12个碳原子的多元羧酸,例如琥珀酸、戊二酸、己二酸、辛二酸、壬二酸、癸二酸、癸烷二羧酸、马来酸、富马酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸和萘二羧酸的异构体或它们的酸酐的缩合来生产。
也可同时用于制备聚酯的其它原料是疏水性物质。疏水性物质是不溶于水的物质,其包含非极性有机结构部分,并且其还具有至少一个选自羟基、羧酸、羧酸酯或其混合物的反应性基团。疏水性材料的当量优选为130-1000g/mol。可以使用的材料的实例是脂肪酸,例如硬脂酸、油酸、棕榈酸、月桂酸或亚油酸,以及脂肪和油,例如蓖麻油、玉米油、向日葵油、大豆油、椰子油、橄榄油或妥尔油。如果聚酯包含疏水性物质,则疏水性物质的比例基于聚酯醇的总单体含量优选为1至30摩尔%,特别优选4至15摩尔%。
所用聚酯醇的官能度优选为1.5-5,特别优选1.8-3.5。
在一个特别优选的实施方案中,异氰酸酯反应性化合物包括聚醚醇,尤其仅聚醚醇。聚醚醇的实际平均官能度优选为2-4,特别优选2.5-3.5,尤其是2.8-3.2,它们的OH值优选为300-900mg KOH/g,它们的仲OH基团含量优选为至少50%,优选至少60%,特别优选至少70%,尤其是至少80%。这里使用的聚醚醇优选包括基于作为起始剂的甘油和基于1,2-氧化丙烯的聚醚醇。
聚氨酯组合物可进一步包含添加剂。所述添加剂可以包括任何已知用于生产聚氨酯的助剂和添加剂。可提及的实例是表面活性剂、脱模剂、偶联剂、填料、染料、颜料、阻燃剂、水解稳定剂、降粘剂、水清除剂、消泡剂,以及具有抑真菌和抑菌作用的物质。这类物质是已知的,例如描述在“Kunststoffhandbuch,Band 7,Polyurethane”[PlasticsHandbook,第7卷,Polyurethanes]Carl Hanser Verlag,1993年第3版,第3.4.4章和3.4.6-3.4.11章中。
可以使用的降粘剂的实例是γ-丁内酯、碳酸亚丙酯,以及反应性稀释剂,例如二丙二醇、二甘醇和三丙二醇。
可以使用的偶联剂包括硅烷,例如异氰酸酯硅烷、环氧硅烷或氨基硅烷。这类物质例如描述在E.P.Plueddemann的硅烷偶联剂,第2版,Plenum Press,纽约,1991和K.L.Mittal编辑,硅烷和其它偶联剂,VSP,Utrecht,1992中。
可以使用的脱模剂是任何用于生产聚氨酯的常规脱模剂,实例是长链羧酸,特别是脂肪酸,如硬脂酸,长链羧酸的胺,例如硬脂酰胺,脂肪酸酯,长链羧酸的金属盐,例如硬脂酸锌,或硅氧烷。特别合适的材料是可特别用于拉挤成型工艺的内部脱模剂,例如来自于Axel Plastics或Technick Products。Technick产品的内部脱模剂可能包含磷酸和脂肪酸。来自硬塑料的内部脱模剂可能包括脂肪酸。
在本发明的一个实施方案中,异氰酸酯反应性化合物与异氰酸酯的摩尔比为1:0.5至1:2。
还提供了聚氨酯复合材料,其中所述聚氨酯复合材料包含:
(1)上述聚氨酯组合物;以及
(2)增强材料。
优选地,增强材料是纤维材料。所用的纤维材料可以包括任何类型的连续长丝纤维。这里,连续长丝纤维是指长度至少为几米的纤维材料。这些材料例如从辊上展开。这里使用的纤维材料可以包括单独的纤维,已知为纤维粗纱、编织纤维、纤维垫、纤维稀松布和织造纤维。特别是在纤维复合材料的情况下,例如编织纤维、加捻纤维、纤维稀松布或织造纤维,也可以存在包含在所述纤维结构内包含的单根纤维内包含的较短单根纤维。优选的是,纤维材料包括玻璃纤维、玻璃毡、碳纤维、聚酯纤维、天然纤维、芳族聚酰胺纤维、玄武岩纤维或尼龙纤维,或者由这些纤维构成,并且特别优选的是使用碳纤维或玻璃纤维。
在本发明的一个实施方案中,聚氨酯组合物与增强材料的重量比为10:90-70:30,优选15:85-50:50,更优选18:82-30:70。
通常,通过混合聚氨酯组合物的组分以得到聚氨酯反应混合物,然后用所得反应混合物浸渍增强材料来制备聚氨酯复合材料。
本发明还提供了一种通过拉挤成型由上述聚氨酯复合材料制备的制品。
在本发明的一个实施方案中,所述制品是桥梁构件、大型人造木材、大型柱结构、复杂的窗型材、冷藏集装箱。
实施例
现在参考以下实施例进一步说明本发明,然而,这些实施例是用于解释的目的,而不是要限制本发明的范围。
实施例中使用的所有材料都可以从市场上购得,其用量列于表1中。
比较例1
使用得自FlackTek公司的SpeedMixer在25℃下将组分A和组分B混合1分钟。然后,通过购自SHYODU INSTRUMENT COMPANY的胶凝计时器测量胶凝时间。
另外,通过使用Speedmixer在25℃下将组分A和组分B混合1分钟,并在70℃下抽真空7分钟和在70℃下放置8分钟,然后在150℃下固化1小时,制备PU面板样品。
比较例2
比较例2是通过与比较例1相同的程序进行,不同之处在于2,2'-MDI及2,4'-MDI的量及其比例是变化的。
实施例1-5
根据表1中列出的组分和量,通过与对比例1相同的程序进行实施例1-5。
比较例1、实施例1-3的纯PU树脂的机械性能列于表2中。PU面板样品的制备可参见对比例1。
此外,使用玻璃纤维和实施例1的样品的混合物通过拉挤成型工艺制备玻璃纤维增强的PU复合材料,其中玻璃纤维的含量为基于PU复合材料重量的80重量%。测定结果示于表3。
表1显示,实施例1-3的胶凝时间明显大于比较例1和比较例2的胶凝时间,甚至是比较例1和比较例2的胶凝时间的约2倍或以上,这表明,基于所用的2,2'-MDI和2,4'-MDI的总量,2'-MDI的适当用量对于延长加工时间是重要的。此外,延长胶凝时间不会损害其固化速度。实施例1、实施例4和实施例5表明,即使2,2'-MDI和2,4'-MDI的总量大致相同,随着2,2'-MDI/2,4'-MDI的比例增加,胶凝时间也会变长。
如表2所示测量由聚氨酯组合物制备的PU面板样品的物理性能。
表2:PU面板样品的物理性能
在表2中,实施例1-3的PU面板样品的物理性能与对比例1相当,这表明胶凝时间的延长不会损害其物理性能。
表3:通过拉挤成型制备的PU复合材料样品的物理性能
性能 | 测试方法 | 实施例1 |
拉伸强度(MPa) | GB/T 1447 | 1120 |
E-模量(GPa) | GB/T 1447 | 51 |
弯曲强度(MPa) | GB/T 1449 | 1450 |
弯曲模量(GPa) | GB/T 1449 | 52 |
纵向剪切强度(MPa) | GB/T 1447 | 63 |
横向剪切强度(MPa) | GB/T 1447 | 16.4 |
硬度(肖氏D) | ISO 7619-1 | >85 |
热变形温度(℃) | GB 1634 | 250 |
通过用实施例1的样品浸渍玻璃纤维(Owens Corning PS4100)经由拉挤成型方法制备PU复合材料样品。PU复合材料的物理性能优异,如表3所示,其特别适合于生产大尺寸复合材料部件,例如桥梁构件、大型人造木材、大型柱结构、复杂的窗型材、冷藏集装箱。
对于本领域技术人员来说,在不背离本发明的范围或精神的情况下,可以对本发明进行各种修改和变化。因此,本发明旨在覆盖落入所附权利要求及其等同物的范围内的这些修改和变化。
Claims (20)
1.一种聚氨酯组合物,其包含:
(1)异氰酸酯;以及
(2)异氰酸酯反应性化合物;
其中异氰酸酯包括2,2'-二苯基甲烷二异氰酸酯和2,4'-二苯基甲烷二异氰酸酯,并且2,2'-二苯基甲烷二异氰酸酯的量在10-30重量%的范围内,基于2,2'-二苯基甲烷二异氰酸酯和2,4'-二苯基甲烷二异氰酸酯的总重量,
其中2,2'-二苯基甲烷二异氰酸酯和2,4'-二苯基甲烷二异氰酸酯的总量在60-100重量%的范围内,基于异氰酸酯的总重量。
2.根据权利要求1所述的聚氨酯组合物,其中2,2'-二苯基甲烷二异氰酸酯和2,4'-二苯基甲烷二异氰酸酯的总量在60-90重量%的范围内,基于异氰酸酯的总重量。
3.根据权利要求1所述的聚氨酯组合物,其中2,2'-二苯基甲烷二异氰酸酯和2,4'-二苯基甲烷二异氰酸酯的总量在60-80重量%的范围内,基于异氰酸酯的总重量。
4.根据权利要求1-3中任一项所述的聚氨酯组合物,其中所述异氰酸酯反应性化合物与所述异氰酸酯的摩尔比在1:0.5至1:2的范围内。
5.根据权利要求1-3中任一项所述的聚氨酯组合物,其中所述异氰酸酯还包含4,4'-二苯基甲烷二异氰酸酯、聚合MDI或其组合。
6.根据权利要求1-3中任一项所述的聚氨酯组合物,其中2,2'-二苯基甲烷二异氰酸酯的量在15-30重量%的范围内,基于2,2'-二苯基甲烷二异氰酸酯和2,4'-二苯基甲烷二异氰酸酯的总重量。
7.根据权利要求1-3中任一项所述的聚氨酯组合物,其中2,2'-二苯基甲烷二异氰酸酯的量在20-30重量%的范围内,基于2,2'-二苯基甲烷二异氰酸酯和2,4'-二苯基甲烷二异氰酸酯的总重量。
8.根据权利要求1-3中任一项所述的聚氨酯组合物,其中所述异氰酸酯反应性化合物选自聚醚多元醇、聚酯多元醇和它们的组合。
9.根据权利要求1-3中任一项所述的聚氨酯组合物,其中所述2,2'-二苯基甲烷二异氰酸酯和2,4'-二苯基甲烷二异氰酸酯进一步与多元醇反应以形成预聚物。
10.根据权利要求1-3中任一项所述的聚氨酯组合物,其中所述聚氨酯组合物是致密的或泡沫体。
11.根据权利要求10所述的聚氨酯组合物,其中所述聚氨酯组合物具有30g/l至900g/l的自由起发密度。
12.一种聚氨酯复合材料,其包含:
(1)根据权利要求1至11中任一项所述的聚氨酯组合物;以及
(2)增强材料。
13.根据权利要求12所述的聚氨酯复合材料,其中所述增强材料为纤维。
14.根据权利要求13所述的聚氨酯复合材料,其中所述增强材料为玻璃纤维。
15.根据权利要求12至14中任一项所述的聚氨酯复合材料,其中所述聚氨酯组合物与所述增强材料的重量比在10:90至70:30的范围内。
16.根据权利要求12至14中任一项所述的聚氨酯复合材料,其中所述聚氨酯组合物与所述增强材料的重量比在15:85至50:50的范围内。
17.根据权利要求12至14中任一项所述的聚氨酯复合材料,其中所述聚氨酯组合物与所述增强材料的重量比在18:82至30:70的范围内。
18.一种由根据权利要求12至17中任一项所述的聚氨酯复合材料生产的制品。
19.根据权利要求18所述的制品,其中所述制品通过拉挤成型、长丝缠绕、树脂传递模塑、真空辅助树脂浸渍、手工铺叠方法或树脂注射模塑来生产。
20.根据权利要求18或19所述的制品,其中所述制品是桥梁构件、大型人造木材、大型柱结构、复杂的窗型材、冷藏集装箱。
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