CN114148000A - Method for preparing polyurethane pultrusion composite material - Google Patents
Method for preparing polyurethane pultrusion composite material Download PDFInfo
- Publication number
- CN114148000A CN114148000A CN202010938117.XA CN202010938117A CN114148000A CN 114148000 A CN114148000 A CN 114148000A CN 202010938117 A CN202010938117 A CN 202010938117A CN 114148000 A CN114148000 A CN 114148000A
- Authority
- CN
- China
- Prior art keywords
- glue injection
- polyurethane
- infiltration
- release
- fiber
- 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.)
- Pending
Links
- 239000004814 polyurethane Substances 0.000 title claims abstract description 126
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 126
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 58
- 238000002347 injection Methods 0.000 claims description 147
- 239000007924 injection Substances 0.000 claims description 147
- 239000003292 glue Substances 0.000 claims description 142
- 230000008595 infiltration Effects 0.000 claims description 96
- 238000001764 infiltration Methods 0.000 claims description 96
- 239000004744 fabric Substances 0.000 claims description 74
- 239000000835 fiber Substances 0.000 claims description 60
- 239000000203 mixture Substances 0.000 claims description 56
- 229920005862 polyol Polymers 0.000 claims description 48
- 150000003077 polyols Chemical class 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 38
- 230000002787 reinforcement Effects 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000005056 polyisocyanate Substances 0.000 claims description 12
- 229920001228 polyisocyanate Polymers 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- WTQHNWLXESYFAM-UHFFFAOYSA-N 3,5-dimethylidenecyclohexene Chemical compound C=C1CC=CC(=C)C1 WTQHNWLXESYFAM-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- XURVRZSODRHRNK-UHFFFAOYSA-N o-quinodimethane Chemical compound C=C1C=CC=CC1=C XURVRZSODRHRNK-UHFFFAOYSA-N 0.000 claims description 4
- NRNFFDZCBYOZJY-UHFFFAOYSA-N p-quinodimethane Chemical compound C=C1C=CC(=C)C=C1 NRNFFDZCBYOZJY-UHFFFAOYSA-N 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 2
- 238000009408 flooring Methods 0.000 claims description 2
- 230000004313 glare Effects 0.000 claims description 2
- 239000012212 insulator Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- -1 whiskers Substances 0.000 description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 14
- 239000012948 isocyanate Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 238000002791 soaking Methods 0.000 description 13
- 239000004721 Polyphenylene oxide Substances 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 150000002513 isocyanates Chemical class 0.000 description 12
- 229920000570 polyether Polymers 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000003365 glass fiber Substances 0.000 description 10
- 235000015112 vegetable and seed oil Nutrition 0.000 description 10
- 239000008158 vegetable oil Substances 0.000 description 10
- 229920000049 Carbon (fiber) Polymers 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 239000004917 carbon fiber Substances 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- 238000012644 addition polymerization Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 229920005906 polyester polyol Polymers 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 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
- 150000001412 amines Chemical class 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 238000007348 radical reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- 229940035437 1,3-propanediol Drugs 0.000 description 3
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- 239000007806 chemical reaction intermediate Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 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 3
- 150000002431 hydrogen Chemical group 0.000 description 3
- 239000006082 mold release agent Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 3
- 229960004063 propylene glycol Drugs 0.000 description 3
- 235000013772 propylene glycol Nutrition 0.000 description 3
- 239000000243 solution Substances 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
- 238000009736 wetting Methods 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 2
- 229940043375 1,5-pentanediol Drugs 0.000 description 2
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 2
- 229920002748 Basalt fiber Polymers 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- 235000019483 Peanut oil Nutrition 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 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
- 239000002671 adjuvant Substances 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 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
- 150000002596 lactones Chemical class 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 239000000312 peanut oil Substances 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
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000002683 reaction inhibitor Substances 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 230000003068 static effect Effects 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
- 238000010998 test method Methods 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 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
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- 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
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-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
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
- BOZRCGLDOHDZBP-UHFFFAOYSA-N 2-ethylhexanoic acid;tin Chemical compound [Sn].CCCCC(CC)C(O)=O BOZRCGLDOHDZBP-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
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- 239000004604 Blowing Agent Substances 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
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- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- CQQXCSFSYHAZOO-UHFFFAOYSA-L [acetyloxy(dioctyl)stannyl] acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)(OC(C)=O)CCCCCCCC CQQXCSFSYHAZOO-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
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- 238000010924 continuous production Methods 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
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- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical compound [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 description 1
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- 239000003085 diluting agent Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 229940113120 dipropylene glycol Drugs 0.000 description 1
- BRWZYZWZBMGMMG-UHFFFAOYSA-J dodecanoate tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BRWZYZWZBMGMMG-UHFFFAOYSA-J 0.000 description 1
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- 230000005611 electricity Effects 0.000 description 1
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- 229940093476 ethylene glycol Drugs 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
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- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
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- 150000004053 quinones Chemical class 0.000 description 1
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- 229940037312 stearamide Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
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- 239000000080 wetting agent Substances 0.000 description 1
- 239000011276 wood tar Substances 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
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
- B29C70/521—Pultrusion, i.e. forming and compressing by continuously pulling through a die and impregnating the reinforcement before the die
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
- B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
- B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
- B29B15/14—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length of filaments or wires
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
Abstract
The invention relates to a method and equipment for preparing a polyurethane pultrusion composite material by using a polyurethane pultrusion process, the polyurethane pultrusion composite material prepared by the method and application thereof.
Description
Technical Field
The invention belongs to the field of a polyurethane pultrusion process. In particular, the present invention relates to a method and apparatus for preparing a polyurethane pultruded composite using a polyurethane pultrusion process, the polyurethane pultruded composite prepared by the method, and uses thereof.
Background
The pultrusion composite material has the characteristics of high fiber content, uniform quality and the like, and is deeply concerned by the industry. The pultrusion process is simple and efficient, can realize continuous production, and is widely adopted. The general specific operation mode of the pultrusion process is as follows: continuously leading the fiber yarn or the fiber fabric out of a creel, carrying out resin infiltration through an open impregnation tank or a closed infiltration box, putting the fiber after resin infiltration into a mold with a certain cross section shape for heating and curing, continuously pulling out the mold by a traction device, and finally cutting the fiber yarn or the fiber fabric into required length on line, thereby preparing the corresponding composite material.
The traditional pultrusion process mainly adopts an open impregnation mode, namely, fibers, fabrics or felts pass through an impregnation tank with a compression roller or a compression bar, and the fibers with resin are gradually extruded by a preformed plate and then enter a heated die to be cured. The traditional open type gum dipping method has a series of problems such as high VOC (volatile organic compounds) volatilization, higher resin waste rate, high porosity content of finished products and the like. Moreover, the time required for shutdown and product specification replacement is relatively long and the cost is relatively high.
In addition, the surface of the existing polyurethane pultrusion composite material is generally smooth and cannot meet the requirement of a polyurethane product which needs a certain roughness surface and can be further processed or spliced.
CN111169045A discloses a wind-powered electricity generation blade girder sheet pultrusion gumming device, mould, equipment and method, and the pultrusion gumming device includes: the glue dipping mold comprises a closed first mold cavity and a first heating device arranged outside the first mold cavity; the first die cavity is provided with a feed inlet and a discharge outlet, and the first die cavity is also provided with a glue injection port penetrating into the first die cavity; and the glue outlets of the glue injection devices are connected with the glue injection port and are suitable for injecting glue solution into the first mold cavity. The dipping device, the die, the equipment and the method for pultrusion of the main beam sheet of the wind power blade can avoid the influence of environmental factors on the performance of the glue solution, the glue solution is mixed and used at present, the concentration uniformity is high, the positioning trend of the fiber is accurate and controllable, the length and the temperature of each segment in the die are further controlled, the content of the fiber material is controlled, the dipping effect and the curing effect are ensured, and the performance of the prepared product is better.
CN107405842B discloses a pultrusion device. The apparatus comprises a section (3) for receiving the fibres, a section (4) for injecting resin into the fibres, a section for injecting resin into the fibres, and a section for shaping the impregnated fibres, wherein the fibres converge in the resin injection section after they have passed the receiving section to receive the resin, the resin flowing outwardly after the resin has been injected as the fibres travel from the injection section through the impregnation section.
US2005221085 a1 discloses the preparation of polymer-coated, coated fiber composites, hybrid composites and methods and apparatus for making the same. This document provides for maximum spraying and coating of the roving of coated fibers with a stream of molten polymer without physical contact with the solid medium, thereby simultaneously protecting the fiber surface from damage and peeling off the coating. When a product made of the composite material of the application is used, the electromagnetic shielding performance is improved. The method and apparatus of this document uses a nozzle sprayer assembly having a plurality of orifices to enable the thermoplastic or thermoset polymer to more effectively penetrate into the fiber bundles, thereby providing more uniform partial coverage of all of the fibers. The hybrid composite may be composed of two or more reinforcements and one or more matrix polymers.
Despite the above disclosures, there is still a need in the art for an improved process and apparatus suitable for the process, so as to improve the quality and surface condition of the polyurethane pultrusion composite material with the release fabric, improve the production efficiency, and meet the requirements of energy conservation, emission reduction and environmental friendliness.
Disclosure of Invention
In one aspect of the present invention, there is provided a method of preparing a pultruded polyurethane composite comprising:
placing at least one release fabric (2) and at least one fibre-reinforced material (1) in a infiltration tank (5) comprising an inlet (5a) and an outlet (5 b); wherein the release cloth partially covers the fiber reinforcement material (1);
partially impregnating a polyurethane composition with a fiber-reinforced material (1) that is not covered with a release fabric, the fiber-reinforced material (1);
and (3) drawing the soaked fiber reinforced material (1) and the demolding cloth (2) through a mold (6), and curing and molding to obtain the polyurethane pultrusion composite material.
The release fabric does not cover the fibrous reinforcement entirely, but only partially. The polyurethane composition contacts the fiber reinforcement material through the portion not covered with the release fabric and wets the fiber reinforcement material.
Preferably, the at least one piece of release fabric (2) is two pieces of release fabric (2a, 2b), the two pieces of release fabric (2a, 2b) are respectively arranged at two opposite inner sides (5i, 5j) of the infiltration box (5), the fiber reinforced material (1) is arranged between the two pieces of release fabric (2a, 2b), the glue injection device (4) comprises at least two glue injection ports (4a, 4b), and the two glue injection ports (4a, 4b) are arranged at two opposite side faces (5m, 5n) of the infiltration box (5) where the release fabric is not arranged.
The method for preparing the polyurethane pultrusion composite material uses a continuous pultrusion process, the demolding cloth and the fiber reinforced material are drawn to pass through the infiltration box at a certain speed, the polyurethane composition is injected into the infiltration box through the glue injection device to infiltrate the fiber reinforced material, and preferably, the polyurethane composition is partially injected into the fiber reinforced material (1) which is not covered by the demolding cloth and infiltrates the fiber reinforced material (1). The speed at which the infiltrated fiber reinforcement and release cloth are drawn through the mold is 0.2-2m/min, preferably 0.2-1.5 m/min. The polyurethane composition is injected at a rate of 30 g/min to 2000g/min, preferably 40 g/min to 1500g/min, more preferably 60 g/min to 1200 g/min. Surprisingly, the method of the present invention, including the features of the release fabric, the proper glue injection location, the infiltration method, the pulling speed, and the speed of injecting the polyurethane composition, not only provides a high quality polyurethane pultruded composite having a satisfactory surface, but also improves production efficiency and saves costs.
Preferably, the vertical distance between the glue injection device (4) and the infiltration box inlet (5a) in the pultrusion direction is 20-250mm, preferably 30-200mm, and more preferably 50-190 mm. As shown in fig. 2, X represents the vertical distance between the glue injection device (4) and the infiltration box inlet (5a) in the pultrusion direction.
Preferably, the cross-sectional area ratio of the inlet (5a) to the outlet (5b) of the infiltration box (5) is 2: 1-10: 1, more preferably 3: 1-8: 1. The inlet (5a) is the opening through which the fibre reinforcement and the release cloth are introduced into the infiltration tank in the pultrusion direction, and the infiltration tank outlet (5b) is the opening through which the fibre reinforcement and the release cloth are pulled out.
Preferably, the gram weight of the release cloth (2a, 2b) is 40-160g/m2Preferably 50 to 150g/m2Preferably 70g/m2-120g/m2。
Preferably, the glue injection device (4) further comprises at least one glue injection runner (4i), and the glue injection runner (4i) is communicated with the two glue injection ports (4a, 4 b).
Preferably, the shape of the glue injection flow channel (4i) is selected from the group consisting of circular, oval, rectangular, drop-shaped, triangular, trapezoidal, streamlined, fan-shaped, dam-shaped and any combination thereof, preferably circular, oval or fan-shaped.
Preferably, the length of the glue injection flow channel (4i) is larger than or equal to the width of the infiltration box (4), and the width of the glue injection flow channel is 6-30mm, preferably 8-20 mm. As shown in fig. 4, Y represents the width of the glue injection flow channel.
Preferably, the glue injection flow channel (4i) is provided with at least two flow channel holes (4ia, 4ib) and/or at least one gap (4ic), and the diameter of the flow channel holes is 0.5-5mm, preferably 1-4mm, and more preferably 1.5-3 mm.
Preferably, the center distance between the two farthest runner holes (4ia, 4ib) in the runner holes is 5% -90%, preferably 10% -80%, and more preferably 15% -70% of the length of the glue injection runner.
Preferably, the width of the gap is 0.5-4mm, preferably 1-3mm, and the length of the gap (4ic) is 5% -90%, preferably 10% -80%, more preferably 15% -70% of the length of the glue injection flow channel (4 i).
Preferably, the method further comprises mixing the polyurethane composition using an automatic metering mixing device.
Preferably, the polyurethane composition comprises the following components:
component A comprising one or more organic polyisocyanates;
component B, comprising:
B1) one or more organic polyols in an amount of 21-60 wt.%, preferably 21-40 wt.%, based on the total weight of the polyurethane composition in 100 wt.%;
B2) one or more compounds having the structure of formula (I) in an amount of 0 to 35 wt.%, preferably 4.6 to 35 wt.%, based on 100 wt.% of the total weight of the polyurethane composition
Wherein R1 is selected from hydrogen, methyl or ethyl; r2 is selected from alkylene having 2 to 6 carbon atoms, 2-bis (4-phenylene) -propane, 1, 4-bis (methylene) benzene, 1, 3-bis (methylene) benzene, 1, 2-bis (methylene) benzene; n is an integer selected from 1 to 6; and
component C, a radical initiator.
Preferably, the organic polyol has a functionality of from 1.7 to 6, preferably from 1.9 to 4.5, and a hydroxyl number of from 150-.
Preferably, the B2) component is selected from: hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or combinations thereof.
Preferably, the polyurethane composition has a gel time at 25 ℃ of from 10 to 40 minutes, preferably from 15 to 30 minutes, more preferably from 16 to 28 minutes.
Preferably, the fibrous reinforcement (1) is selected from glass fibers, carbon fibers, polyester fibers, natural fibers, aramid fibers, nylon fibers, basalt fibers, boron fibers, silicon carbide fibers, asbestos fibers, metal fibers or combinations thereof.
Preferably, the thickness of the fibrous reinforcement (1) is greater than or equal to 2mm, preferably greater than or equal to 3mm, more preferably between 2 and 8 mm.
Preferably, the infiltration tank (5) is closed, and the pressure in the infiltration tank (5) is preferably 0.1-15 bar.
Preferably, the infiltration box (5) is provided with an observation window.
Preferably, a yarn guide plate (3') is arranged in front of the infiltration box (5) or behind the infiltration box (5).
Preferably, a preformed plate (3) is arranged in front of the infiltration box (5) or behind the infiltration box (5).
Preferably, the polyurethane pultruded composite has a cure time of 15 to 90 seconds, preferably 18 to 80 seconds, at 150-220 ℃.
Through repeated experiments, the method for preparing the polyurethane pultrusion composite material can simply and efficiently prepare the polyurethane pultrusion composite material with a satisfactory quality and a non-smooth or rough surface meeting the requirement.
Particularly for fiber reinforced materials with certain thickness, the method of the invention can realize good infiltration and simultaneously can prepare the polyurethane pultrusion composite material with satisfactory surface property.
In another aspect of the invention, an apparatus (10) for the method for preparing a polyurethane pultrusion composite material comprises a glue injection device (4) and an infiltration box (5), wherein the glue injection device (4) comprises at least two glue injection ports (4a, 4b), and the glue injection ports (4a, 4b) are positioned on two opposite sides (5m, 5n, or, 5i, 5j) of the infiltration box (5).
In the process of the invention, the polyurethane composition is injected directly into the fibrous reinforcement. The glue injection opening according to the invention should be close to the fiber reinforcement not covered by the release cloth, but not close to the fiber reinforcement covered by the release cloth, to ensure that the polyurethane composition is injected directly into the fiber reinforcement without being impregnated into the fiber reinforcement through the release cloth.
Preferably, the infiltration box (5) is a cuboid, and the glue injection ports (4a, 4b) are located on two sides (5m, 5n) of the infiltration box in the direction perpendicular to the horizontal plane.
Preferably, the glue injection device (4) further comprises at least two glue injection pipes (4k, 4g), and the glue injection pipes (4k, 4g) are arranged in the infiltration box (5) through the glue injection ports (4a, 4 b).
Preferably, the glue injection device (4) further comprises at least one glue injection runner (4i), and the glue injection runner (4i) is communicated with the glue injection ports (4a, 4 b).
Preferably, the shape of the glue injection flow channel (4i) is selected from the group consisting of circular, oval, rectangular, drop-shaped, triangular, trapezoidal, streamlined, fan-shaped, dam-shaped and any combination thereof, preferably circular, oval or fan-shaped.
Preferably, the length of the glue injection flow channel (4i) is larger than or equal to the width of the infiltration box, and the width of the glue injection flow channel is 6-30mm, preferably 8-20 mm.
Preferably, the glue injection flow channel (4i) is provided with at least two flow channel holes (4ia, 4ib) and/or at least one gap (4ic), and the diameter of the flow channel holes is 0.5-5mm, preferably 1-4mm, and more preferably 1.5-3 mm;
preferably, the center distance between the two farthest runner holes (4ia, 4ib) in the runner holes is 5% -90%, preferably 10% -80%, and more preferably 15% -70% of the length of the glue injection runner;
preferably, the width of the gap is 0.5-4mm, preferably 1-3mm, and the length of the gap (4ic) is 5% -90%, preferably 10% -80%, more preferably 15% -70% of the length of the glue injection flow channel (4 i).
Preferably, the vertical distance between the glue injection device (4) and the inlet of the infiltration box (5) is 20-250mm, preferably 30-200mm, and more preferably 50-190 mm.
Preferably, the cross-sectional area ratio of the inlet (5a) to the outlet (5b) of the infiltration box is 2: 1-10: 1, preferably 3: 1-8: 1.
Preferably, the shape of the glue injection flow channel (4i) is selected from a circle, an ellipse, a rectangle, a water drop shape, a triangle, a trapezoid, a streamline shape, a fan shape, a dam shape and any combination thereof, the length of the glue injection flow channel (4i) is more than or equal to the width of the infiltration box (5), and the width of the glue injection flow channel (4i) is 6-30mm, preferably 8-20 mm.
The equipment comprising the glue injection device and the infiltration box can still well infiltrate the fiber reinforced material under the condition of using the demoulding cloth, thereby preparing the high-quality polyurethane pultrusion composite material with uniform resin distribution and good curing. Particularly unexpectedly, the glue injection device and the infiltration box with special structures (such as a glue injection opening and a glue injection runner) and the corresponding positions, connection and/or methods thereof greatly improve the infiltration efficiency and effect, can prepare the polyurethane pultrusion composite material with the required surface condition, and can also improve the production efficiency and save raw materials and cost.
In still another aspect of the present invention, there is provided a pultruded polyurethane composite produced by the method of the present invention for producing a pultruded polyurethane composite.
In a further aspect of the present invention, there is provided a polyurethane product comprising a polyurethane composite obtained by the method for preparing a pultruded polyurethane composite according to the present invention as described above.
Preferably, the polyurethane product is selected from: cable trays, door and window curtain wall frames, ladder frames, tent poles or tubes, glare shields, flooring, sucker rods, utility poles and crossarms, guard rails, grilles, construction profiles, container profiles and sheets, bicycle frames, fishing poles, cable cores, insulator mandrels, antenna covers, single or sandwich continuous sheets, or sheets for making turbine fan blade girders.
Through repeated experiments, we unexpectedly find that the method for preparing the polyurethane pultrusion composite material, which comprises the demoulding cloth, the fiber reinforced material, the glue injection device, the infiltration box and the like, the mutual position relation of the demoulding cloth, the fiber reinforced material, the glue injection device, the infiltration box and the like, the area ratio of the inlet and the outlet of the infiltration box and the like, can simply and efficiently prepare the polyurethane pultrusion composite material with satisfactory quality and required non-smooth or rough surface. The equipment comprising the glue injection device and the infiltration box can well infiltrate the fiber reinforced material under the condition of using the demoulding cloth, thereby preparing the high-quality polyurethane pultrusion composite material with uniform resin distribution and good curing.
The method for preparing the polyurethane composite material by the polyurethane pultrusion process adopts the polyurethane composition, skillfully designs the glue injection device and the infiltration box which are adapted to the polyurethane composition, and improves the surface condition of the polyurethane pultrusion composite material, improves the production efficiency and saves the cost by using a proper method.
In addition, the polyurethane composition has longer gel time, and can realize better polyurethane pultrusion. The polyurethane composite material has excellent physical properties and high glass fiber content.
In addition, the polyurethane composition has shorter curing time and longer gel time, and can be better and more flexibly (for example, the polyurethane composition can be soaked and molded for a longer time) suitable for preparing a polyurethane pultrusion composite material, in particular a large polyurethane pultrusion composite material, such as a profile for preparing a main beam of a fan blade. In particular, the fibrous reinforcement material can be wetted and shaped for a longer period of time at normal temperatures, for example before entering the mould, and can be cured more quickly at high temperatures, for example after entering the mould.
Detailed Description
The following describes specific embodiments for carrying out the present invention.
The method for preparing the polyurethane pultrusion composite material comprises the following steps:
placing at least one release fabric (2) and at least one fibre-reinforced material (1) in a infiltration tank (5) comprising an inlet (5a) and an outlet (5 b); wherein the release cloth partially covers the fiber reinforcement material (1);
partially impregnating a polyurethane composition with a fiber-reinforced material (1) that is not covered with a release fabric, the fiber-reinforced material (1);
and (3) drawing the soaked fiber reinforced material (1) and the demolding cloth (2) through a mold (6), and curing and molding to obtain the polyurethane pultrusion composite material.
Preferably, the at least one piece of release fabric (2) is two layers of release fabrics (2a, 2b), the two layers of release fabrics (2a, 2b) are respectively arranged on two opposite inner sides (5i, 5j) of the infiltration box (5), the fiber reinforced material (1) is arranged between the two layers of release fabrics (2a, 2b), the glue injection device (4) comprises at least two glue injection ports (4a, 4b), and the two glue injection ports (4a, 4b) are arranged on two opposite side faces (5m, 5n) of the infiltration box (5) where no release fabric is arranged.
Preferably, the glue injection openings (4a, 4b) are located on the side of the infiltration box where the release cloth (2) is not placed, i.e. away from or not close to the release cloth (2). The infiltration box is placed or close to the side face of the demoulding cloth without an injection opening.
Preferably, the polyurethane composition comprises the following components:
component A comprising one or more organic polyisocyanates;
component B, comprising:
B1) one or more organic polyols in an amount of 21-60 wt.%, preferably 21-40 wt.%, based on the total weight of the polyurethane composition in 100 wt.%;
B2) one or more compounds having the structure of formula (I) in an amount of 0 to 35 wt.%, preferably 4.6 to 35 wt.%, based on 100 wt.% of the total weight of the polyurethane composition
Wherein R1 is selected from hydrogen, methyl or ethyl; r2 is selected from alkylene having 2 to 6 carbon atoms, 2-bis (4-phenylene) -propane, 1, 4-bis (methylene) benzene, 1, 3-bis (methylene) benzene, 1, 2-bis (methylene) benzene; n is an integer selected from 1 to 6; and
component C, a radical initiator.
When used in the present invention, the fibrous reinforcement is not required in shape and size, and may be, for example, continuous fibers, a web formed by bonding, or a fabric.
In some embodiments of the invention, the fibrous reinforcement material is selected from: glass fibers, carbon fibers, polyester fibers, natural fibers, aramid fibers, nylon fibers, basalt fibers, boron fibers, silicon carbide fibers, asbestos fibers, whiskers, metal fibers, or combinations thereof.
Optionally, the organic polyisocyanate may be any aliphatic, cycloaliphatic or aromatic isocyanate known for use in the preparation of polyurethanes. Examples include, but are not limited to: toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate (pMDI), 1, 5-Naphthalene Diisocyanate (NDI), Hexamethylene Diisocyanate (HDI), methylcyclohexyl diisocyanate (TDI), 4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), p-phenylene diisocyanate (PPDI), p-phenylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), and polymers thereof or combinations thereof. The isocyanates which can be used according to the invention preferably have a functionality of from 2.0 to 3.5, particularly preferably from 2.1 to 2.9. The isocyanate viscosity is preferably from 5 to 700 mPas, particularly preferably from 10 to 300 mPas, determined at 25 ℃ in accordance with DIN 53019-1-3.
When used in the present invention, the organic polyisocyanate includes an isocyanate dimer, trimer, tetramer, pentamer or a combination thereof.
In a preferred embodiment of the present invention, the isocyanate component a is selected from the group consisting of diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate (pMDI), and polymers, prepolymers or combinations thereof.
Blocked isocyanates may also be used as isocyanate component a, which may be prepared by reacting an excess of an organic polyisocyanate or mixtures thereof with a polyol compound. These compounds and their preparation are well known to those of ordinary skill in the art.
The polyurethane composition of the present invention comprises one or more organic polyols B1). The organic polyol is present in an amount of 21 to 60 wt.%, based on the total weight of the polyurethane composition in 100 wt.%. The organic polyol may be an organic polyol commonly used in the art for making polyurethanes, including but not limited to: polyether polyols, polyether carbonate polyols, polyester polyols, polycarbonate diols, polymer polyols, vegetable oil based polyols, or combinations thereof.
The polyether polyols may be prepared by known processes, for example by reacting an olefin oxide with an initiator in the presence of a catalyst. The catalyst is preferably, but not limited to, alkali hydroxide, alkali alkoxide, antimony pentachloride, boron fluoride etherate, or a mixture thereof. The alkylene oxide is preferably, but not limited to, tetrahydrofuran, ethylene oxide, propylene oxide, 1, 2-butylene oxide, 2, 3-butylene oxide, styrene oxide, or a mixture thereof, and ethylene oxide and/or propylene oxide is particularly preferred. The initiator is preferably, but not limited to, a polyol, preferably, but not limited to, water, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, diethylene glycol, trimethylolpropane, glycerol, bisphenol a, bisphenol S, or mixtures thereof, or a polyamine, preferably, but not limited to, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, tolylenediamine, or mixtures thereof.
The polyether carbonate polyols, which can be prepared by addition of carbon dioxide and alkylene oxides onto starters containing active hydrogen using double metal cyanide catalysts, can also be used in the present invention.
The polyester polyol is prepared by reacting dicarboxylic acid or dicarboxylic anhydride with polyhydric alcohol. The dicarboxylic acid is preferably, but not limited to, an aliphatic carboxylic acid having 2 to 12 carbon atoms, and the aliphatic carboxylic acid having 2 to 12 carbon atoms is preferably, but not limited to, succinic acid, malonic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecane carboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, or a mixture thereof. The dicarboxylic acid anhydride is preferably, but not limited to, phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, or a mixture thereof. The polyhydric alcohol reacted with the dicarboxylic acid or dicarboxylic acid anhydride is preferably, but not limited to, ethylene glycol, diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, dipropylene glycol, 1, 3-methylpropanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 1, 10-decanediol, glycerol, trimethylolpropane, or a mixture thereof. The polyester polyol also comprises polyester polyol prepared from lactone. The polyester polyol prepared from lactone is preferably, but not limited to, epsilon-caprolactone. Preferably, the polyester polyol has a molecular weight of 200-3000 and a functionality of 2-6, preferably 2-5, more preferably 2-4.
The polycarbonate diol can be prepared by reacting dihydric alcohol with dialkyl carbonate or diaryl carbonate or phosgene. The diol is preferably, but not limited to, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, diethylene glycol, trioxymethylene glycol, or a mixture thereof. The dialkyl carbonate or diaryl carbonate is preferably, but not limited to, diphenyl carbonate.
The polymer polyol may be a polymer modified polyether polyol, preferably a graft polyether polyol, polyether polyol dispersion. The graft polyether polyol, preferably based on styrene and/or acrylonitrile; the styrene and/or acrylonitrile can be prepared by in-situ polymerization of styrene, acrylonitrile and a mixture of styrene and acrylonitrile; in the mixture of styrene and acrylonitrile, the ratio of styrene to acrylonitrile is 90: 10 to 10: 90, preferably 70: 30 to 30: 70. The polymer polyol can also be bio-based polyol such as castor oil, wood tar and the like. The polymer polyether polyol dispersion comprises a disperse phase, for example, a free-radical filler, a polyurea, a polyhydrazide, a polyurethane containing tertiary amino groups in bonded form and/or melamine. The amount of the dispersed phase is 1 to 50 wt.%, preferably 1 to 45 wt.%, based on 100 wt.% of the weight of the polymeric polyether polyol. Preferably the polymer polyether polyol has a polymer solids content of from 20% to 45% and a hydroxyl number of from 20 to 50mg KOH/g, based on 100% weight of the polymer polyether.
When used in the present invention, the vegetable oil-based polyol includes vegetable oil, vegetable oil polyol or a modified product thereof. Vegetable oils are compounds prepared from unsaturated fatty acids and glycerol or oils extracted from fruits, seeds, germs of plants, preferably but not limited to peanut oil, soybean oil, linseed oil, castor oil, rapeseed oil, palm oil. The vegetable oil polyol is a polyol initiated by one or more vegetable oils. Synthetic vegetable oil polyol starters include, but are not limited to, soybean oil, palm oil, peanut oil, canola oil, and castor oil. The vegetable oil polyol starter may be used to introduce hydroxyl groups by cleavage, oxidation, or transesterification, and the corresponding vegetable oil polyol may be prepared by processes well known to those skilled in the art for preparing organic polyols.
Methods for measuring hydroxyl number are well known to the person skilled in the art, for example in Houben Weyl, Methoden der Organischen Chemie, vol.XIV/2 Makromolekulare Stoffe, p.17, Georg Thieme Verlag; stuttgart 1963. The entire contents of this document are incorporated herein by reference.
When used in the present invention, unless otherwise indicated, the functionality, hydroxyl number of the organic polyol all refer to the average functionality and average hydroxyl number.
Optionally, the polyurethane composition of the invention also comprises one or more compounds B2 having the structure of formula (I)
Wherein R is1Selected from hydrogen, methyl or ethyl; r2Selected from alkylene groups having 2 to 6 carbon atoms; n is an integer selected from 1 to 6.
In a preferred embodiment of the invention, R2Selected from the group consisting of ethylene, propylene, butylene, pentylene, 1-methyl-1, 2-ethylene, 2-methyl-1, 2-ethylene, 1-ethyl-1, 2-ethylene, 2-ethyl-1, 2-ethylene, 1-methyl-1, 3-propylene, 2-methyl-1, 3-propylene, 3-methyl-1, 3-propylene, 1-ethyl-1, 3-propylene, 2-ethyl-1, 3-propylene, 3-ethyl-1, 3-propylene, 1-methyl-1, 4-butylene, 2-methyl-1, 4-butylene, 3-methyl-1, 4-butylene and 4-methyl-1, 4-butylene, 2-bis (4-phenylene) -propane, 1, 4-dimethylene-benzene, 1, 3-dimethylene-benzene, 1, 2-dimethylene-benzene.
Preferably, the B1) is selected from organic polyols, wherein the organic polyols are selected from polyols having a functionality of from 1.7 to 6, preferably from 1.9 to 4.5, and a hydroxyl number of 150-.
In a preferred embodiment of the invention, said B2) component is selected from: hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or combinations thereof.
The compounds of formula (I) can be prepared by methods customary in the art, for example by (meth) acrylic anhydride or (meth) acrylic acid, (meth) acryloyl halide compounds with HO- (R)2O)n-H is prepared by esterification, the preparation process is well known to the person skilled in the art, for example, as described in handbook of polyurethane raw materials and auxiliaries (Liu Yi Jun, published 4/1/2005) third chapter, and polyurethane Elastomers (Liu Thick Jun, published 8/2012) second chapter, which will be described inThe entire contents of the documents are incorporated herein by reference.
Preferably, the polyurethane composition of the present invention further comprises a C radical reaction initiator. The free radical initiator used in the present invention may be added to either the polyol component or the isocyanate component or both components. These initiators include, but are not limited to, peroxides, persulfides, peroxycarbonates, peroxyboric acids, azo compounds, or other suitable free radical initiators that can initiate curing of double bond containing compounds, examples of which include t-butyl peroxyisopropylcarbonate, t-butyl peroxy-3, 5, 5-trimethylhexanoate, methyl ethyl ketone peroxide, cumene hydroperoxide. Preferably, the free radical reaction initiator of the present invention is present in an amount of 0.1 to 8 wt.%, based on 100 wt.% of the total weight of the polyurethane composition of the present invention. In addition, an accelerator, such as a cobalt compound or an amine compound, may be present.
Optionally, the polyurethane composition may further comprise a catalyst for catalyzing the reaction of isocyanate groups (NCO) with hydroxyl groups (OH). Suitable catalysts for the polyurethane reaction are preferably, but not limited to, amine catalysts, organometallic catalysts, or mixtures thereof. The amine catalyst is preferably, but not limited to, triethylamine, tributylamine, triethylenediamine, N-ethylmorpholine, N, N, N ', N' -tetramethyl-ethylenediamine, pentamethyldiethylenetriamine, N-methylaniline, N, N-dimethylaniline, or a mixture thereof. The organometallic catalyst is preferably, but not limited to, organotin compounds, such as: tin (II) acetate, tin (II) octoate, tin ethylhexanoate, tin laurate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin maleate, dioctyltin diacetate, or mixtures thereof. Preferably, the catalyst is used in an amount of 0.001 to 10 wt.%, based on 100 wt.% of the total weight of the polyurethane composition of the present invention.
In the addition polymerization reaction of isocyanate groups with hydroxyl groups in the embodiments of the present invention, the isocyanate groups may be contained in the isocyanate groups in the organic polyisocyanate (component a), may also be contained in the reaction intermediate product of the organic polyisocyanate (component a) with the organic polyol (B1) component) or B2) component, and the hydroxyl groups may be contained in the reaction intermediate product of the organic polyol (B1) component) or B2) component, or may be contained in the reaction intermediate product of the organic polyisocyanate (component a) with the organic polyol (B1) component) or B2) component.
In the embodiment of the present invention, the radical polymerization is an addition polymerization of the olefinic bond, wherein the olefinic bond may be the olefinic bond contained in the B2) component, or the olefinic bond contained in the intermediate product of the reaction of the B2) component with the organic polyisocyanate.
In the present example, the polyurethane addition polymerization (i.e., the addition polymerization of isocyanate groups and hydroxyl groups) was carried out simultaneously with the radical polymerization. As known to those skilled in the art, suitable reaction conditions can be selected so that the polyurethane addition polymerization reaction and the free radical polymerization reaction are carried out in sequence, but the polyurethane matrix prepared in the way is different from the polyurethane resin matrix prepared by simultaneously carrying out the polyurethane addition polymerization reaction and the free radical polymerization reaction, so that the mechanical properties and the manufacturability of the prepared polyurethane composite material are different.
Optionally, the polyurethane composition described above may also contain adjuvants or additives, including but not limited to: fillers, internal mold release agents, flame retardants, smoke suppressants, dyes, pigments, antistatic agents, antioxidants, UV stabilizers, diluents, defoamers, coupling agents, surface wetting agents, leveling agents, water scavengers, catalysts, molecular sieves, thixotropic agents, plasticizers, blowing agents, foam stabilizers, foam homogenizers, free radical reaction inhibitors or combinations thereof, which components may optionally be comprised in the isocyanate component a) and/or the polyurethane composition B) of the invention. These components can also be stored separately as component D) and, when used for the preparation of polyurethane composites, are mixed with the isocyanate component A) and/or the polyurethane composition B) according to the invention before the preparation.
The internal mold release agent which can be used in the present invention includes any conventional mold release agent used for producing polyurethane, and examples thereof include long-chain carboxylic acids, particularly fatty acids such as stearic acid, amines of long-chain carboxylic acids such as stearamide, fatty acid esters, metal salts of long-chain carboxylic acids such as zinc stearate, or polysiloxanes.
Examples of flame retardants that can be used in the present invention include triaryl phosphate, trialkyl phosphate, triaryl or trialkyl phosphate with halogen, melamine resins, halogenated paraffins, red phosphorus, or combinations thereof.
Other adjuvants useful in the present invention include water scavengers such as molecular sieves; defoamers, such as polydimethylsiloxane; coupling agents, such as monoepoxyethane or organic amine functional trialkoxysilane or combinations thereof. Coupling agents are particularly preferred for improving the adhesion of the resin matrix to the fibrous reinforcement. Finely particulate fillers, such as clays and fumed silicas, are commonly used as thixotropic agents.
The radical reaction inhibitor which can be used in the present invention includes polymerization inhibitors and retarders and the like, such as some phenols, quinone compounds or hindered amine compounds, examples of which include methylhydroquinone, p-methoxyphenol, benzoquinone, polymethine pyridine derivatives, low valent copper ions and the like.
Generally, the term "gel time" refers to the time until the reaction system A-and B-components begin to mix until the viscosity reaches a certain value (e.g., about 10000 mPa.s). The gel time mentioned in the examples of the present invention is a time measured by using a gel tester.
Through repeated experiments, we unexpectedly found that the method for preparing the polyurethane pultrusion composite material can simply and efficiently prepare the polyurethane pultrusion composite material with the required rough surface with satisfactory quality. The method is suitable for the method, and the glue injection device and the infiltration box which are specially designed can better infiltrate the fiber reinforced material, particularly the fiber infiltration material with certain thickness in shorter time.
In addition, the polyurethane composition has shorter curing time and longer gel time, can be better and more flexibly (for example, can be soaked and molded for a longer time) and is suitable for preparing a polyurethane pultrusion composite material, in particular a large polyurethane pultrusion composite material. In particular, the fibrous reinforcement material can be wetted and shaped for a longer period of time at normal temperatures, for example before entering the mould, and can be cured more quickly at high temperatures, for example after entering the mould.
The equipment (10) used for the method for preparing the polyurethane pultrusion composite material comprises a glue injection device (4) and a soaking box (5), wherein the glue injection device (4) comprises at least two glue injection openings (4a, 4b), and the glue injection openings (4a, 4b) are positioned on two opposite sides (5m, 5n or 5i, 5j) of the soaking box (5).
Preferably, the infiltration box (5) is a cuboid, and the glue injection ports (4a, 4b) are located on two sides (5m, 5n) of the infiltration box in the direction perpendicular to the horizontal plane.
Surprisingly, we have found that when the glue injection opening is located on the side of the infiltration box close to the release fabric (for example, 5i, 5j shown in fig. 3), the polyurethane composition contacts the release fabric first during glue injection, and then contacts the fiber reinforcement material through the release fabric, the infiltration effect is poor, and when the glue injection opening is located on the side of the infiltration box not provided with the release fabric, close to or far from the release fabric (for example, 5m, 5n shown in fig. 2), the better infiltration effect can be achieved. The infiltration box is arranged at or close to the side of the demoulding cloth, and a glue injection opening is not needed. Preferably, the two surfaces of the infiltration box parallel to the horizontal plane have larger areas, and the four surfaces perpendicular to the horizontal plane have smaller areas. The inlet and the outlet are not suitable to be provided with glue injection ports because the fiber reinforced material and the demoulding cloth need to be pulled to pass through. Therefore, preferably, at least two glue injection ports are respectively arranged on two sides of the infiltration box, which are perpendicular to the horizontal plane and also perpendicular to the plane where the inlet and the outlet of the infiltration box are located.
Preferably, the glue injection device (4) further comprises at least two glue injection pipes (4k, 4g), and the glue injection pipes (4k, 4g) are arranged in the infiltration box (5) through the glue injection ports (4a, 4 b).
Preferably, the glue injection device (4) further comprises at least one glue injection runner (4i), and the glue injection runner (4i) is communicated with the glue injection ports (4a, 4 b).
Preferably, the shape of the glue injection flow channel (4i) is selected from the group consisting of circular, oval, rectangular, drop-shaped, triangular, trapezoidal, streamlined, fan-shaped, dam-shaped and any combination thereof, preferably circular, oval or fan-shaped.
Preferably, the length of the glue injection flow channel (4i) is larger than or equal to the width of the infiltration box (5), and the width of the glue injection flow channel (4i) is 6-30mm, preferably 8-20 mm.
Preferably, the glue injection flow channel (4i) is provided with at least two flow channel holes (4ia, 4ib) or at least one gap (4ic), and the diameter of the flow channel hole is 0.5-5mm, preferably 1-4mm, and more preferably 1.5-3 mm. The size and number of the runner holes on the glue injection runner can be adjusted according to the size of the prepared polyurethane pultrusion composite material or the infiltration box, and can be more than 2, preferably 2-5. Similarly, the size and number of the gaps on the glue injection runner can be adjusted according to the size of the polyurethane pultrusion composite material or the infiltration box to be prepared, and can be more than one, preferably 2-4.
Preferably, the center-to-center distance between the two farthest runner holes (4ia, 4ib) is 5% -90%, preferably 10% -80%, more preferably 15% -70% of the length of the glue injection runner (4 i).
Preferably, the width of the gap (4ic) is 0.5-4mm, preferably 1-3mm, and the length of the gap (4ic) is 5% -90%, preferably 10% -80%, and more preferably 15% -70% of the length of the glue injection runner (4 i).
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the event that a definition of a term in this specification conflicts with a meaning commonly understood by those skilled in the art to which the invention pertains, the definition set forth herein shall govern.
The present invention is illustrated by the following examples, but it should be understood that the scope of the present invention is not limited to these examples.
Drawings
The invention is illustrated below with reference to the accompanying drawings:
FIG. 1 shows a schematic view of the die and process flow shown in the method of producing a polyurethane pultruded composite according to a preferred embodiment of the present invention, wherein: 1 represents a fiber reinforcement, and 2 represents a release fabric; 3 denotes a preform sheet; 4 denotes a glue injection device; 5 denotes a infiltration box; 6 denotes a die, 7 denotes a profile/polyurethane pultrusion composite, and 8 denotes a clamping device.
Fig. 2 is a relative position diagram of the preferred infiltration box and glue injection device/and demolding cloth of the invention, wherein: 2a and 2b represent release fabrics (in order to avoid the figure being too complicated, the fiber reinforced material which should be arranged between the two release fabrics is not drawn), 4 represents a glue injection device, 4a and 4b represent a glue injection opening, 5 represents a soaking box, 5a represents a soaking box inlet, 5b represents a soaking box outlet, 5m and 5n represent two opposite sides of the soaking box (5), 4i represents a glue injection flow channel, and X represents the vertical distance between the glue injection device (4) and the soaking box inlet (5a) in the pultrusion direction.
FIG. 3 shows a front view of a preferred infiltration cassette of the present invention, wherein 5i and 5j respectively show the top and bottom opposite sides of the infiltration cassette.
FIG. 4 is a cross-sectional view of a preferred infiltration cartridge of the present invention, wherein 5 is the infiltration cartridge, 5a is the infiltration cartridge inlet, and 5b is the infiltration cartridge outlet.
Fig. 5 is a schematic diagram of a preferred glue injection device including a glue injection runner, where 4 denotes the glue injection device, 4a and 4b denote glue injection ports, 4i denotes the glue injection runner, 4ia and 4ib denote runner holes on the glue injection runner, and Y denotes a width of the glue injection runner.
Fig. 6 is a schematic diagram of another preferred glue injection device including a glue injection runner according to the present invention, in which 4 denotes the glue injection device, 4a and 4b denote glue injection ports, 4i denotes the glue injection runner, and 4ic denotes a gap on the glue injection runner.
Examples
The performance parameter test in the examples of the present application shows:
functionality, means according to the industry formula: a functionality of hydroxyl value (Mw/56100); wherein the molecular weight is determined by GPC high performance liquid chromatography;
isocyanate index, which means a value calculated by the following formula:
the NCO content, which is the NCO group content in the system, was determined by GB/T12009.4-2016.
Pultrusion rate/degree, i.e. the speed at which the migrating fibrous reinforcement passes through the die, is the length of pultruded fibrous reinforcement passing through the die per minute, i.e. the length of the product produced per minute; the specific test method comprises the following steps: the length of the pultruded fibre reinforcement material measured using a speed sensor or stopwatch plus a ruler divided by the time used is the length of passage through the die per unit time, i.e. the rate/degree of pultrusion.
The curing time refers to the time from the beginning of mixing of the A component and the B component of the reaction system to curing.
The gel time is a time until the reaction system A-and B-components begin to be mixed until the viscosity reaches a certain value (for example, about 10000mPa. s). The gel time of the present invention is measured using a gel tester. The specific test method comprises the steps of uniformly mixing the component A and the component B, placing the mixture in a gel tester, and recording the time from pressing a start button to stopping the gel tester as the gel time.
Raw material sources and descriptions
TABLE 1 raw materials List
Example 1:
the production process of glass fiber reinforced polyurethane pultruded section/sheet with demolding cloth is exemplified by the production of 3mm x 100mm flat plate. In addition, in the embodiment, the cross-sectional area ratio of the inlet and the outlet of the infiltration box is 1: 7; the vertical distance between the glue injection device (4) and the inlet (5a) of the infiltration box in the pultrusion direction is 50 mm; the width of the glue injection runner is 10mm, the diameter of the runner hole is 2mm, the length of the runner hole is 200mm, and the length of the gap is 50 mm.
Firstly, the glue injection device (4), the infiltration box (5), the mould (6) and the like are assembled and fixed on a pultrusion platform. The method comprises the following steps of leading 220 bundles of glass fibers (1) out of a creel, leading two pieces of demolding cloth (2a, 2b) out of the creel, sequentially passing through a yarn guide plate/pre-forming plate (3), a wetting box (5) and a mold (6) together with the glass fibers (1), and then leading the glass fibers to be completely pulled down by a traction device, wherein the demolding cloth 2a is close to the upper side (5i) of the wetting box (5), and the demolding cloth 2b is close to the lower side (5j) of the wetting box. And (3) opening a heating device of the mold (6), and sequentially controlling the mold temperature from an inlet to an outlet as follows: 80C/180/190C, starting the glue injection machine after the temperature is stable, continuously pumping the isocyanate component and the polyol component B (100 parts of polyol component 1: 4 parts of polyol component 2) to a static mixing head according to the weight ratio of 100: 130, injecting resin into the glue injection flow channel from glue injection ports (4a, 4B) on two sides (5m, 5n) of the infiltration box (5) after the resin is mixed by the mixing head, enabling the resin to flow to the upper multiple flow channel holes through the resin and be uniformly injected into the infiltration box and be fully injected (the average glue injection speed is 110g/min), fully soaking the glass fiber (1) and the demolding cloth (2), and controlling the glue injection pressure in the infiltration box (5) to be 0.1-15 bar. The glass fiber (1) and the demoulding cloth (2a, 2b) soaked by the soaking box (5) are continuously pulled through the mould (6) by a traction device (8) at the speed of 0.5m/min, the plate is smooth and has no dry yarn after being taken out of the mould, and when the polyurethane pultrusion composite material/section bar is prepared by knocking metal at the position 1 m away from the mould, the sound is crisp, and the soaking and curing are good.
Before the prepared polyurethane pultrusion composite material/profile is further processed and used, the demolding cloth is removed, and the polyurethane pultrusion composite material/profile with the surface condition with the composite requirement can be obtained.
Example 2:
a production process of carbon fiber polyurethane pultruded sheet with release cloth is provided to produce a 3mm x 100mm flat plate. In addition, in the embodiment, the cross-sectional area ratio of the inlet and the outlet of the infiltration box is 1: 7; the vertical distance between the glue injection device (4) and the inlet (5a) of the infiltration box in the pultrusion direction is 50 mm; the width of the glue injection runner is 10mm, the diameter of the runner hole is 2mm, the length of the runner hole is 200mm, and the length of the gap is 50 mm.
Firstly, the glue injection device (4), the infiltration box (5), the mould (6) and the like are assembled and fixed on a pultrusion platform. The method comprises the following steps of leading 140 bundles of carbon fibers (1) out of a creel, simultaneously leading two pieces of demolding cloth (2a, 2b) out of the creel, sequentially passing through a yarn guide plate/pre-forming plate (3), a soaking box (5) and a mold (6) together with the carbon fibers (1), and then drawing forwards by a drawing device to enable the carbon fibers to be completely drawn. A release cloth (2a) is adjacent to the upper side (5i) of the infiltration box (5) and a release cloth (2b) is adjacent to the lower side (5j) of the infiltration box. And (3) opening a heating device of the mold (6), and sequentially controlling the mold temperature from an inlet to an outlet as follows: 80C/180/190C, starting the glue injection machine after the temperature is stable, continuously pumping the isocyanate component and the polyol component B (100 parts of polyol component 1: 4 parts of polyol component 2) to a static mixing head according to the weight ratio of 100: 130, injecting resin into the glue injection flow channel from glue injection ports (4a, 4B) on two sides (5i, 5j) of the infiltration box (5) after the resin is mixed by the mixing head, enabling the resin to flow to the upper multiple flow channel holes through the resin and be uniformly injected into the infiltration box and be fully injected (the average glue injection speed is 110g/min), enabling the carbon fiber (1) and the demolding cloth (2) to be fully soaked, and controlling the glue injection pressure in the infiltration box (5) to be 0.1-15 bar. The carbon fiber (1) and the demoulding cloth (2a, 2b) soaked by the soaking box (5) are continuously pulled through the mould (6) by a traction device (8) at the speed of 0.5m/min, the plate is smooth and has no dry yarn after being taken out of the mould, and when the polyurethane pultrusion composite material/section bar is prepared by knocking metal at the position 1 m away from the mould, the sound is clear and crisp, which indicates that the soaking and the curing are good.
Before the prepared polyurethane pultrusion composite material/profile is further processed and used, the demolding cloth is removed, and the polyurethane pultrusion composite material/profile with the surface condition with the composite requirement can be obtained.
From the experimental results of the above examples 1 and 2, it can be seen that the method for preparing a polyurethane pultruded composite according to the present invention can prepare a polyurethane pultruded composite having good infiltration and curing. Both glass fiber and carbon fiber can produce excellent quality polyurethane pultruded composite material with satisfactory surface. In addition, the polyurethane composition of the invention has shorter curing time and longer gel time, can be better and more flexible (for example, can be soaked and molded for a longer time) and is suitable for the preparation of polyurethane products, in particular large polyurethane products.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Claims (19)
1. A method of making a polyurethane pultruded composite comprising:
placing at least one release fabric (2) and at least one fibre-reinforced material (1) in a infiltration tank (5) comprising an inlet (5a) and an outlet (5 b); wherein the release fabric (2) partially covers the fiber reinforcement (1);
partially impregnating a polyurethane composition with a fiber-reinforced material (1) that is not covered with a release fabric (2) to the fiber-reinforced material (1);
and (3) drawing the soaked fiber reinforced material (1) and the demolding cloth (2) through a mold (6), and curing and molding to obtain the polyurethane pultrusion composite material.
2. A method as claimed in claim 1, characterized in that the at least one release cloth (2) is two release cloths (2a, 2b), the two release cloths (2a, 2b) being arranged on two opposite inner sides (5i, 5j) of the infiltration tank (5), respectively, and the fibre-reinforcement material (1) being arranged between the two release cloths (2a, 2 b).
3. Method according to claim 1 or 2, characterized in that the wetted fibrous reinforcement (1) and the release fabric (2) are drawn through a mould (6) at a speed of 0.2-2m/min, preferably 0.2-1.5m/min, and the polyurethane composition is injected into the infiltration box (5) by an injection device (4) at a speed of 30-2000g/min, preferably 40-1500g/min, more preferably 60-1200 g/min.
4. The method as claimed in claim 1 or 2, characterized in that the infiltration tank (5) has a ratio of the cross-sectional areas of the inlet (5a) and the outlet (5b) of 2: 1 to 10: 1, more preferably 3: 1 to 8: 1.
5. A method as claimed in claim 3, wherein the polyurethane composition is injected into the infiltration tank by a glue injection device (4), the glue injection device (4) further comprises at least one glue injection flow channel (4i), the glue injection flow channel (4i) is communicated with the two glue injection ports (4a, 4b), and the two glue injection ports (4a, 4b) are located on two opposite sides (5m, 5n) of the infiltration tank (5) where the release fabric is not placed.
6. Method according to claim 5, characterized in that the compound injection channel (4i) is provided with at least two channel holes (4ia, 4ib) and/or at least one slit (4ic), the diameter of the channel holes (4ia, 4ib) being 0.5-5mm, preferably 1-4mm, more preferably 1.5-3 mm.
7. The method according to claim 1 or 2, characterized in that the polyurethane composition comprises the following components:
component A comprising one or more organic polyisocyanates;
component B, comprising:
B1) one or more organic polyols in an amount of 21-60 wt.%, preferably 21-40 wt.%, based on the total weight of the polyurethane composition in 100 wt.%;
B2) one or more compounds having the structure of formula (I) in an amount of 0 to 35 wt.%, preferably 4.6 to 35 wt.%, based on 100 wt.% of the total weight of the polyurethane composition
Wherein R1 is selected from hydrogen, methyl or ethyl; r2 is selected from alkylene having 2 to 6 carbon atoms, 2-bis (4-phenylene) -propane, 1, 4-bis (methylene) benzene, 1, 3-bis (methylene) benzene, 1, 2-bis (methylene) benzene; n is an integer selected from 1 to 6; and
component C, a radical initiator.
8. A method according to claim 1 or 2, characterized in that the fibrous reinforcement (1) is a layer of fibrous reinforcement material having a thickness of more than or equal to 2mm, preferably more than or equal to 3mm, more preferably between 2 and 8 mm.
9. An apparatus for use in the method of producing a pultruded polyurethane composite according to any of the claims 1 to 8, comprising a compound injection device (4) and an infiltration tank (5), said compound injection device (4) comprising at least two compound injection openings (4a, 4b), said compound injection openings (4a, 4b) being located on opposite sides (5m, 5n, or, 5i, 5j) of the infiltration tank (5).
10. The apparatus according to claim 9, wherein the infiltration tank (5) is a rectangular parallelepiped, and the glue injection openings (4a, 4b) are located on two sides (5m, 5n) of the infiltration tank perpendicular to the horizontal plane.
11. The apparatus according to claim 9 or 10, characterized in that the glue injection device (4) further comprises at least two glue injection pipes (4k, 4g), and the glue injection pipes (4k, 4g) are arranged in the infiltration box (5) through the glue injection ports (4a, 4 b).
12. The apparatus according to claim 9 or 10, wherein the glue injection device (4) further comprises at least one glue injection channel (4i), and the glue injection channel (4i) is communicated with the glue injection ports (4a, 4 b).
13. Device according to claim 9 or 10, characterized in that the compound injection channel (4i) is provided with at least two channel holes (4ia, 4ib) and/or at least one slit (4ic), the diameter of the channel holes being 0.5-5mm, preferably 1-4mm, more preferably 1.5-3 mm.
14. The apparatus according to claim 13, characterized in that the centers of the two most distant flow channel holes (4ia, 4ib) are spaced from each other by 5% to 90%, preferably 10% to 80%, more preferably 15% to 70% of the length of the glue injection flow channel.
15. Device according to claim 13 or 14, characterized in that the width of the gap is 0.5-4mm, preferably 1-3mm, and the length of the gap (4ic, 4id) is 5-90%, preferably 10-80%, more preferably 15-70% of the length of the glue injection channel (4 i).
16. The apparatus as claimed in claim 9 or 10, characterized in that the infiltration tank has an inlet (5a) to outlet (5b) cross-sectional area ratio of 2: 1 to 10: 1, preferably 3: 1 to 8: 1.
17. A polyurethane pultruded composite produced by the method of producing a polyurethane pultruded composite according to any of the claims 1 to 8.
18. A polyurethane product comprising a polyurethane composite made by the method of making a polyurethane pultruded composite according to any of claims 1 to 8.
19. The polyurethane product of claim 18, wherein the polyurethane product is selected from the group consisting of: cable trays, door and window curtain wall frames, ladder frames, tent poles or tubes, glare shields, flooring, sucker rods, utility poles and crossarms, guard rails, grilles, construction profiles, container profiles and sheets, bicycle frames, fishing poles, cable cores, insulator mandrels, antenna covers, single or sandwich continuous sheets, or sheets for making turbine fan blade girders.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010938117.XA CN114148000A (en) | 2020-09-08 | 2020-09-08 | Method for preparing polyurethane pultrusion composite material |
| PCT/EP2021/074178 WO2022053376A1 (en) | 2020-09-08 | 2021-09-01 | A method for preparing a pultruded polyurethane composite |
| CN202180054761.3A CN116096557A (en) | 2020-09-08 | 2021-09-01 | Method for preparing polyurethane pultrusion composite material |
| EP21770008.7A EP4210935A1 (en) | 2020-09-08 | 2021-09-01 | A method for preparing a pultruded polyurethane composite |
| US18/023,188 US20230356483A1 (en) | 2020-09-08 | 2021-09-01 | A method for preparing a pultruded polyurethane composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010938117.XA CN114148000A (en) | 2020-09-08 | 2020-09-08 | Method for preparing polyurethane pultrusion composite material |
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| CN114148000A true CN114148000A (en) | 2022-03-08 |
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| CN202010938117.XA Pending CN114148000A (en) | 2020-09-08 | 2020-09-08 | Method for preparing polyurethane pultrusion composite material |
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