WO2015144391A1 - A process for manufacturing a fiber reinforced epoxy composite article, the composite articles obtained and the use thereof - Google Patents
A process for manufacturing a fiber reinforced epoxy composite article, the composite articles obtained and the use thereof Download PDFInfo
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- WO2015144391A1 WO2015144391A1 PCT/EP2015/054266 EP2015054266W WO2015144391A1 WO 2015144391 A1 WO2015144391 A1 WO 2015144391A1 EP 2015054266 W EP2015054266 W EP 2015054266W WO 2015144391 A1 WO2015144391 A1 WO 2015144391A1
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- WIPO (PCT)
- Prior art keywords
- accelerator
- sulfonic acid
- resin composition
- resin
- process according
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 71
- 230000008569 process Effects 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000000835 fiber Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title abstract description 19
- 239000004593 Epoxy Substances 0.000 title description 6
- 229920005989 resin Polymers 0.000 claims abstract description 64
- 239000011347 resin Substances 0.000 claims abstract description 64
- 239000011342 resin composition Substances 0.000 claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 33
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000004693 imidazolium salts Chemical class 0.000 claims abstract description 20
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 17
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000003733 fiber-reinforced composite Substances 0.000 claims abstract description 7
- 238000010276 construction Methods 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 62
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 27
- 238000002347 injection Methods 0.000 claims description 19
- 239000007924 injection Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 16
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 15
- 238000001721 transfer moulding Methods 0.000 claims description 13
- WLWXEDJMZHONIG-UHFFFAOYSA-N 4-methylbenzenesulfonate;1-methyl-1h-imidazol-1-ium Chemical compound C[NH+]1C=CN=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 WLWXEDJMZHONIG-UHFFFAOYSA-N 0.000 claims description 10
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 8
- WOKQGMYCUGJNIJ-UHFFFAOYSA-M 1,3-dimethylimidazol-1-ium;methyl sulfate Chemical compound COS([O-])(=O)=O.CN1C=C[N+](C)=C1 WOKQGMYCUGJNIJ-UHFFFAOYSA-M 0.000 claims description 5
- 230000002829 reductive effect Effects 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 description 24
- 239000003822 epoxy resin Substances 0.000 description 22
- 238000002156 mixing Methods 0.000 description 21
- 239000000203 mixture Substances 0.000 description 20
- -1 hexahydro- phthalic Chemical class 0.000 description 19
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 14
- 238000011049 filling Methods 0.000 description 10
- 238000001879 gelation Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 8
- 239000002608 ionic liquid Substances 0.000 description 8
- 229920003319 Araldite® Polymers 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 238000000113 differential scanning calorimetry Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical class [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 3
- 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 3
- PAFZNILMFXTMIY-UHFFFAOYSA-N Cyclohexylamine Natural products NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002118 epoxides Chemical group 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000009745 resin transfer moulding Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 3
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 description 2
- VVHFXJOCUKBZFS-UHFFFAOYSA-N 2-(chloromethyl)-2-methyloxirane Chemical compound ClCC1(C)CO1 VVHFXJOCUKBZFS-UHFFFAOYSA-N 0.000 description 2
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical class NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-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
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 150000001912 cyanamides Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical class NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 150000002357 guanidines Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000001802 infusion Methods 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
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002989 phenols Chemical class 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
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- JCUZDQXWVYNXHD-UHFFFAOYSA-N 2,2,4-trimethylhexane-1,6-diamine Chemical compound NCCC(C)CC(C)(C)CN JCUZDQXWVYNXHD-UHFFFAOYSA-N 0.000 description 1
- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- ZRYCRPNCXLQHPN-UHFFFAOYSA-N 3-hydroxy-2-methylbenzaldehyde Chemical compound CC1=C(O)C=CC=C1C=O ZRYCRPNCXLQHPN-UHFFFAOYSA-N 0.000 description 1
- 239000011165 3D composite Substances 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 1
- WXQZLPFNTPKVJM-UHFFFAOYSA-N 4-[(4-hydroxycyclohexyl)methyl]cyclohexan-1-ol Chemical compound C1CC(O)CCC1CC1CCC(O)CC1 WXQZLPFNTPKVJM-UHFFFAOYSA-N 0.000 description 1
- HDPBBNNDDQOWPJ-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 HDPBBNNDDQOWPJ-UHFFFAOYSA-N 0.000 description 1
- OTJFTLRXGXUHEJ-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)ethenyl]phenol Chemical group C1=CC(O)=CC=C1C(=C)C1=CC=C(O)C=C1 OTJFTLRXGXUHEJ-UHFFFAOYSA-N 0.000 description 1
- BDBZTOMUANOKRT-UHFFFAOYSA-N 4-[2-(4-aminocyclohexyl)propan-2-yl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1C(C)(C)C1CCC(N)CC1 BDBZTOMUANOKRT-UHFFFAOYSA-N 0.000 description 1
- CDBAMNGURPMUTG-UHFFFAOYSA-N 4-[2-(4-hydroxycyclohexyl)propan-2-yl]cyclohexan-1-ol Chemical compound C1CC(O)CCC1C(C)(C)C1CCC(O)CC1 CDBAMNGURPMUTG-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 description 1
- SVLTVRFYVWMEQN-UHFFFAOYSA-N 5-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound CC1CC(C(O)=O)C(C(O)=O)C=C1 SVLTVRFYVWMEQN-UHFFFAOYSA-N 0.000 description 1
- RBHIUNHSNSQJNG-UHFFFAOYSA-N 6-methyl-3-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2(C)OC2CC1C1(C)CO1 RBHIUNHSNSQJNG-UHFFFAOYSA-N 0.000 description 1
- ADAHGVUHKDNLEB-UHFFFAOYSA-N Bis(2,3-epoxycyclopentyl)ether Chemical compound C1CC2OC2C1OC1CCC2OC21 ADAHGVUHKDNLEB-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- XZAHJRZBUWYCBM-UHFFFAOYSA-N [1-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1(CN)CCCCC1 XZAHJRZBUWYCBM-UHFFFAOYSA-N 0.000 description 1
- YXEBFFWTZWGHEY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohex-3-en-1-yl]methanol Chemical compound OCC1(CO)CCC=CC1 YXEBFFWTZWGHEY-UHFFFAOYSA-N 0.000 description 1
- SEQAMYJUOBIYPB-UHFFFAOYSA-N [4-(hydroxymethyl)-7-oxabicyclo[4.1.0]heptan-4-yl]methanol Chemical compound C1C(CO)(CO)CCC2OC21 SEQAMYJUOBIYPB-UHFFFAOYSA-N 0.000 description 1
- NIYNIOYNNFXGFN-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol;7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound OCC1CCC(CO)CC1.C1C(C(=O)O)CCC2OC21.C1C(C(=O)O)CCC2OC21 NIYNIOYNNFXGFN-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007630 basic procedure Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- AIXMJTYHQHQJLU-UHFFFAOYSA-N chembl210858 Chemical compound O1C(CC(=O)OC)CC(C=2C=CC(O)=CC=2)=N1 AIXMJTYHQHQJLU-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- VKONPUDBRVKQLM-UHFFFAOYSA-N cyclohexane-1,4-diol Chemical compound OC1CCC(O)CC1 VKONPUDBRVKQLM-UHFFFAOYSA-N 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BQQUFAMSJAKLNB-UHFFFAOYSA-N dicyclopentadiene diepoxide Chemical compound C12C(C3OC33)CC3C2CC2C1O2 BQQUFAMSJAKLNB-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- WJSATVJYSKVUGV-UHFFFAOYSA-N hexane-1,3,5-triol Chemical compound CC(O)CC(O)CCO WJSATVJYSKVUGV-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- BYVVEGMFBFDFHN-UHFFFAOYSA-N n'-methylpentane-1,5-diamine Chemical class CNCCCCCN BYVVEGMFBFDFHN-UHFFFAOYSA-N 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical class CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- ZMVMYBGDGJLCHV-UHFFFAOYSA-N n-methyl-4-[[4-(methylamino)phenyl]methyl]aniline Chemical compound C1=CC(NC)=CC=C1CC1=CC=C(NC)C=C1 ZMVMYBGDGJLCHV-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- NIXKBAZVOQAHGC-UHFFFAOYSA-N phenylmethanesulfonic acid Chemical class OS(=O)(=O)CC1=CC=CC=C1 NIXKBAZVOQAHGC-UHFFFAOYSA-N 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- 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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0005—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fibre reinforcements
-
- 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
- B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
- B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
- B29C70/48—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs and impregnating the reinforcements in the closed mould, e.g. resin transfer moulding [RTM], e.g. by vacuum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5026—Amines cycloaliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/687—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- 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
- B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
-
- 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
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
-
- 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
- B29K2307/00—Use of elements other than metals as reinforcement
- B29K2307/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
Definitions
- the present invention relates to a process for the preparation of fiber reinforced composite articles by using a multiple component thermosetting resin composition which facilitates manufacturing of composite articles with reduced cycle times.
- the composite articles obtained exhibit excellent mechanical properties and can be used for the construction of mass transportation vehicles, in particular in automotive and aerospace industry.
- RTM resin transfer molding
- HP-RTM high-pressure resin transfer molding
- HP-CRTM high-pressure compression resin transfer molding
- VARTM vacuum-assisted resin transfer molding
- Newly developed high-pressure RTM equipment technology allows injection of highly reactive resin compositions under high flow rate into the mold cavity.
- the combination of high-pressure pumps for dosing components of the fast reacting resin composition and their impingement mixing in self-cleaning high-pressure mixing heads guarantees precise component mixing along with fast materials injection into the mold at defined flow rates.
- the mold can be evacuated. Complex three dimensional cavities are filled faster, fiber preforms are properly impregnated and air entrapments are avoided.
- HP-CRTM high-pressure compression resin transfer molding
- the preform is placed into the mold cavity and the mold is closed partially, leaving a small gap between the upper mold surface and the fiber preform.
- the resin is introduced into this gap, flows easily over the preform and partially impregnates it.
- the mold is closed further and high compression pressure is applied to squeeze the resin into the preform, especially in the vertical z-direction.
- the preform is compacted to achieve the desired part thickness and fiber volume fraction.
- the part is demolded after curing.
- RTM resin transfer molding
- a fibrous reinforcement preform is placed in a mold, the mold is closed, the components of the resin composition are mixed before entering the mold inlet and after mixing injected into the mould cavity at the injection gate to impregnate the fiber preform and fill the mold. Since the resin is mixed with the catalyst or curing agent before or as it enters the mould cavity, the setting or curing process starts as the resin begins to flow into the mould. Therefore, it is essential that the resin reaches the edges of the mold cavity before it sets.
- the resin will be introduced unheated into a preheated mould, and the reactivity of the curing agent and the temperature of the mold will be adjusted so that the resin is able to flow into the edges of the mold, but begins to set immediately after it reaches the edges.
- the temperature initially drops sharply when the unheated resin is introduced.
- the temperature of the resin at the injection gate rises until it reaches a temperature at which it starts to cure.
- the resin which has reached the edges of the mold has already set at the time when the resin at the injection gate starts to cure. This may result in
- WO2008153542 describes an RTM process using epoxy resin compositions wherein gemdi(cyclohexylamine)- substituted alkanes are used as the hardener.
- an ideal process which is suitable to manufacture in particular large composite articles would comprise a resin system with sufficient open time to allow for complete filling of the mold and impregnation of the fiber preform, which resin system cures rapidly after filling is complete, while avoiding
- Another objective is to provide the said fiber reinforced composite articles which exhibit excellent mechanical properties, especially elongation and fracture toughness.
- the said composite articles can be used for the construction of mass transportation vehicles, such as in automotive or aerospace industry, in particular, for the construction of cars.
- the present invention relates to a process for the preparation of a fiber reinforced composite article comprising the steps of
- thermosetting resin composition comprises
- an accelerator comprising at least one compound selected from the group sulfonic acid and imidazolium salt of a sulfonic acid
- the process according to the present invention is useful to form various types of composite products, and provides several advantages. Cure times tend to be very short, with good development of polymer properties, such as glass transition temperature Tg. This allows for faster demold times and shorter cycle times. The slower build-up of viscosity permits lower operating pressures to be used.
- the liquid epoxy resin (b1 ) is a liquid at room temperature ( ⁇ 20°C). If required the epoxy resin contains an epoxy diluent component.
- the epoxy diluent component is, for example, a glycidyl terminated compound. Especially preferred are compounds containing a glycidyl or ⁇ -methylglycidyl groups directly attached to an atom of oxygen, nitrogen, or sulfur.
- Such resins include polyglycidyl and poly(p- methylglycidyl) esters obtainable by the reaction of a substance containing two or more carboxylic acid groups per molecule with epichlorohydrin, glycerol dichlorohydrin, or ⁇ - methylepichlorohydrin in the presence of alkali.
- the polyglycidyl esters may be derived from aliphatic carboxylic acids, e.g. oxalic acid, succinic acid, adipic acid, sebacic acid, or dimerised or trimerised linoleic acid, from cycloaliphatic carboxylic acids such as hexahydro- phthalic, 4-methylhexahydrophthalic, tetrahydrophthalic, and 4-methyltetrahydrophthalic acid, or from aromatic carboxylic acids, such as phthalic acid, isophthalic acid, and terephthalic acid.
- aliphatic carboxylic acids e.g. oxalic acid, succinic acid, adipic acid, sebacic acid, or dimerised or trimerised linoleic acid
- cycloaliphatic carboxylic acids such as hexahydro- phthalic, 4-methylhexahydrophthalic, tetrahydrophthalic, and 4-methyltetra
- liquid epoxy resin (b1 ) there come into consideration epoxy resins which contain an average of at least 0.1 hydroxyl groups per molecule.
- the epoxy resin used herein comprises at least one compound or mixture of compounds having an average functionality of at least 2.0 epoxide groups per molecule.
- the epoxy resin or mixture thereof may have an average of up to 4.0 epoxide groups per molecule. It preferably has an average of from 2.0 to 3.0 epoxide groups per molecule.
- the epoxy resin may have an epoxy equivalent weight of about 150 to about 1 ,000, preferably about 160 to about 300, more preferably from about 170 to about 250. If the epoxy resin is halogenated, the equivalent weight may be somewhat higher.
- epoxide resins which may be used include polyglycidyl and poly(p-methylglycidyl) ethers obtainable by the reaction of substances containing per molecule, two or more alcoholic hydroxy groups, or two or more phenolic hydroxy groups, with epichlorohydrin, glycerol dichlorohydrin, or ⁇ -methylepichlorohydrin, under alkaline conditions or, alternatively, in the presence of an acidic catalyst with subsequent treatment with alkali.
- Such polyglycidyl ethers may be derived from aliphatic alcohols, for example, ethylene glycol and poly(oxyethylene)glycols such as diethylene glycol and triethylene glycol, propylene glycol and poly(oxypropylene)glycols, propane-1 ,3-diol, butane-1 ,4-diol, pentane-1 ,5-diol, hexane-1 ,6-diol, hexane-2,4,6-triol, glycerol, 1 ,1 ,1-trimethylolpropane, and pentaerythritol; from cycloaliphatic alcohols, such as quinitol, 1 ,1 bis(hydroxymethyl)cyclohex-3-ene, bis(4- hydroxycyclohexyl)methane, and 2,2-bis(4-hydroxycyclohexyl)-propane; or from alcohols containing aromatic nuclei, such as
- the polyglycidyl ethers are derived from substances containing two or more phenolic hydroxy groups per molecule, for example, resorcinol, catechol, hydroquinone, bis(4-hydroxyphenyl)methane (bisphenol F), 1 ,1 ,2,2-tetrakis(4-hydroxyphenyl)ethane, 4,4'- dihydroxydiphenyl, bis(4-hydroxyphenyl)sulphone (bisphenol S), 1 ,1 -bis(4-hydroxylphenyl)-1 - phenyl ethane (bisphenol AP), 1 ,1 -bis(4-hydroxylphenyl)ethylene (bisphenol AD), phenol- formaldehyde or cresol-formaldehyde novolac resins, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), and 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane.
- bisphenol F bis(4-hydroxyphenyl)
- poly(N-glycidyl) compounds such as are, for example, obtained by the dehydrochlorination of the reaction products of epichlorohydrin and amines containing at least two hydrogen atoms directly attached to nitrogen, such as aniline, n- butylamine, bis(4-aminophenyl)methane, bis(4-aminophenyl)sulphone, and bis(4- methylaminophenyl)methane.
- poly(N-glycidyl) compounds that may be used include triglycidyl isocyanurate, ⁇ , ⁇ '-diglycidyl derivatives of cyclic alkylene ureas such as ethyleneurea and 1 ,3-propyleneurea, and ⁇ , ⁇ '-diglycidyl derivatives of hydantoins such as 5,5-dimethylhydantoin.
- Epoxide resins obtained by the epoxidation of cyclic and acrylic polyolefins may also be employed, such as vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, 3,4-epoxydihydrodicyclopentadienyl glycidyl ether, the bis(3,4-epoxydihydrodicyclopenta- dienyl)ether of ethylene glycol, 3,4-epoxycyclohexylmethyl 3 ,4'-epoxycyclohexane- carboxylate and its 6,6'-dimethyl derivative, the bis(3,4-epoxycyclohexanecarboxylate) of ethylene glycol, the acetal formed between 3,4-epoxycyclohexanecarboxyaldehyde and 1 ,1 - bis(hydroxymethyl)-3,4-epoxycyclohexane, bis(2,3-epoxycyclopentyl)ether
- the liquid epoxy resin (b1 ) is the diglycidyl ether of a polyhydric phenol represented by formula (1 ) wherein (Ri) m independently denotes m substituents selected from the group consisting of CrC 4 alkyl and halogen, (R 2 ) n independently denotes n substituents selected from from the group consisting of Ci-C 4 alkyl and halogen, each B independently is -S-, -S-S-, -SO-, -S0 2 -, - C0 3 -, -CO-, -0-, or a CrC 6 (cylo)alkylene radical.
- m independently denotes m substituents selected from the group consisting of CrC 4 alkyl and halogen
- R 2 ) n independently denotes n substituents selected from from the group consisting of Ci-C 4 alkyl and halogen
- each B independently is -S-, -S-S-, -SO-
- Each m and each n are independently an integer 0, 1 , 2, 3 or 4 and q is a number of from 0 to 5.
- q is the average number of hydroxyl groups in the epoxy resin of formula (1 ).
- Ri and R 2 in the meaning of halogen are, for example, chlorine or bromine.
- Ri and R 2 in the meaning of CrC 4 alkyl are, for example, methyl, ethyl, n-propyl or iso-propyl.
- each B independently in the meaning of a CrC 6 (cylo)- alkylene radical is, for example, methylene, 1 ,2-ethylene, 1 ,3-propylene, 1 ,2-propylene, 2,2- propylene, 1 ,4-butylene, 1 ,5-pentylene, 1 ,6-hexylene or 1 ,1 -cyclohexylene.
- each B independently is methylene, 2,2-propylene or -S0 2 -.
- each m and each n are independently an integer 0, 1 or 2, more preferably 0.
- suitable epoxy resins include diglycidyl ethers of dihydric phenols such as bisphenol A, bisphenol F and bisphenol S, and mixtures thereof.
- Preferred epoxy resins of this type are those in which q is at least 0.1 , especially those in which q is from 0.1 to 2.5.
- Epoxy resins of this type are commercially available, including diglycidyl ethers of bisphenol A resins.
- Suitable halogenated epoxy resins, wherein at least one of Ri and R 2 are halogen, are described in, for example, in US4251594, US4661568, US4713137 and US4868059, and Lee and Neville, Handbook of Epoxy Resins, McGraw-Hill (1982), all of which are incorporated herein by reference.
- the epoxy resins indicated are either commercially available or can be prepared according to the processes described in the cited documents.
- the epoxy resin of formula (1 ) is a diglycidyl ether of bisphenol A.
- the epoxy resin (b1 ) is used in an amount of from 60 to 90 weight%, preferably 75 to 90 weight% and more preferably 80 to 85 weight% based on the total weight of the thermosetting resin composition.
- the curing agent (b2) comprises 1 ,3- bis(aminomethyl)cyclo-hexane.
- 1 ,3-bis(aminomethyl)cyclohexane is used alone or in combination with other curing agents, for example, primary or secondary amines.
- curing agents for example, primary or secondary amines.
- primary or secondary amines for example, primary or secondary amines.
- the identity of many of these amines and their curing mechanisms are discussed in Lee and Neville, Handbook of Epoxy Resins, McGraw-Hill (1982).
- Suitable amines for use in combination with 1 ,3-bis(aminomethyl)cyclohexane there may be mentioned aliphatic, cycloaliphatic or araliphatic primary and secondary amines, including mixtures of these amines.
- Typical amines include monoethanolamine, N-aminoethyl ethanolamine, ethylenediamine, hexamethylenediamine, trimethylhexamethylenediamines, methylpentamethylenediamines, diethylenetriamine, triethylenetetramine, tetraethylene- pentamine, N,N-dimethylpropylenediamine-1 ,3, N,N-diethylpropylenediamine-1 ,3, bis(4- amino-3-methylcyclohexyl)methane, bis(p-aminocyclohexyl)methane, 2,2-bis-(4- aminocyclohexyl)propane, 3,5,5-trimethyl-s-(aminomethyl)cyclohexylamine, 1 ,2- diaminocyclohexane, 1 ,4-diaminocyclohexane, 1 ,4-bis(aminomethyl)cyclohexane, N- aminoethyl
- Preferred amines include 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2- methylpentamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylene- pentamine, 1 ,2-diaminocyclohexane, bis(p-aminocyclohexyl)methane, m-xylene diamine, norbornene diamine, 3(4),8(9)-bis-(aminomethyl)-tricyclo-[5.2.1 .02,6]decane (TCD-diamine), isophorone diamine and 1 ,4-bis(aminomethyl)cyclohexane.
- Especially preferred amines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1 ,2-diaminocyclohexane, m-xylene diamine, norbornene diamine, 3(4),8(9)-bis-(aminomethyl)-tricyclo- [5.2.1 .02,6]decane (TCD-diamine) and isophorone diamine.
- the curing agent (b2) is 1 ,3-bis(aminomethyl)cyclohexane, which is used as the single curing agent (b2), and not applied in admixture with other curing agents.
- the curing agent (b2) is used in an amount of from 10 to 40 weight%, preferably 10 to 25 weight% and more preferably 15 to 20 weight% based on the total weight of the thermosetting resin composition.
- the accelerator (b3) comprises at least one compound selected from the group sulfonic acid and imidazolium salt of a sulfonic acid.
- At least one sulfonic acid is used as the accelerator (b3), for example, one sulfonic acid or two different sulfonic acids.
- Suitable sulfonic acids are, for example, methane sulfonic acid and toluene sulfonic acids, such as p- toluene sulfonic acid, and, preferably, as p-toluene sulfonic acid.
- the sulfonic acid is used alone or in combination with other accelerators suitable to increase the cure rate of epoxy resin systems, for example, guanidines, calcium nitrate, imidazoles, cyanamide compounds, such as dicyanamide, dicyandiamide and cyanamide, boron halide complexes and tertiary amines.
- accelerators suitable to increase the cure rate of epoxy resin systems for example, guanidines, calcium nitrate, imidazoles, cyanamide compounds, such as dicyanamide, dicyandiamide and cyanamide, boron halide complexes and tertiary amines.
- At least one imidazolium salt of a sulfonic acid is used as the accelerator (b3), for example, one imidazolium salt or two different imidazolium salts.
- the imidazolium salt is used alone or in combination with other accelerators suitable to increase the cure rate of epoxy resin systems, for example, guanidines, calcium nitrate, imidazoles, cyanamide compounds, such as dicyanamide, dicyandiamide and cyanamide, boron halide complexes and tertiary amines.
- the imidazolium salt of a sulfonic acid is advantageously provided as an ionic liquid, so that it can be processed in accordance with the inventive process by means of the apparatus described hereafter, for example, as a liquid imidazolium salt of p-toluene sulfonic acid or methane sulfonic acid, such as 1 -methylimidazolium p-toluene sulfonate or 1 ,3- dimethylimidazolium methyl sulfate.
- the accelerator (b3) is used in an amount of from 0.05 to 5 weight%, preferably of from 0.1 to 3 weight% and more preferably of from 0.15 to 2.0 weight% based on the total weight of the thermosetting resin composition.
- the accelerator (b3) is p-toluene sulfonic acid (PTSA), a liquid imidazolium salt of p-toluene sulfonic acid, or methane sulfonic acid, such as 1 -methylimidazolium p-toluene sulfonate or 1 ,3-dimethylimidazolium methyl sulfate, which is used as the single accelerator (b3), and not applied in admixture with other accelerators.
- PTSA p-toluene sulfonic acid
- methane sulfonic acid such as 1 -methylimidazolium p-toluene sulfonate or 1 ,3-dimethylimida
- p-toluene sulfonic acid is commercially available, for example, as the monohydrate.
- Liquid imidazolium salts of sulfonic acids are commercially available, for example, from EMD Chemicals Inc., or can be prepared by mixing stoichiometric (equimolar) amounts of a mono- or disubstituted imidazole derivative and sulfonic acid.
- 1 -methylimidazolium p- toluene sulfonate is used as an ionic liquid.
- the process is a resin transfer molding process (RTM).
- the process is a high- pressure resin transfer molding process (HP-RTM), or a high-pressure compression resin transfer molding process (HP-CRTM).
- the process is a vacuum-assisted resin transfer molding process (VARTM), also designated vacuum-assisted resin infusion process (VARI).
- the resin transfer molding processes indicated above generally, involve two basic procedures, (i) fabricating a fiber preform in the shape of a finished article and (ii) impregnating the preform with a thermosetting resin, commonly called a matrix resin.
- the first step in resin transfer molding processes is to fabricate a fiber preform in the shape of the desired article.
- the preform generally comprises a plurality of fabric layers or plies that impart the desired reinforcing properties to a resulting composite article.
- the preform is placed in a cavity mold.
- the mold is closed and the matrix resin is injected into the mold to initially wet and impregnate the preform.
- the matrix resin is injected under pressure into the mold and afterwards cured to produce the final composite article.
- the preform is covered by flexible sheet or liner. The flexible sheet or liner is clamped onto the mold to seal the preform in an envelope.
- a catalyzed matrix resin is then introduced into the envelope to wet the preform.
- a vacuum is applied to the interior of the envelope via a vacuum line to collapse the flexible sheet against the preform.
- the vacuum draws the resin through the preform and helps to avoid the formation of air bubbles or voids in the finished article.
- the matrix resin cures while being subjected to the vacuum.
- the application of the vacuum draws off any fumes produced during the curing process.
- injection of the thermosetting resin composition into the mold comprises varying the concentration of accelerator (b3) in the course of injecting the resin to increase the cure rate of the resin composition, wherein injection is initiated with a resin composition which contains no accelerator (b3) or the accelerator (b3) in a low concentration, and wherein injection is completed with a resin composition which contains the accelerator (b3) in a high concentration.
- the variation from a resin composition which initially contains no accelerator (b3) or the accelerator (b3) in a low concentration to a resin composition which finally contains the accelerator (b3) in a high concentration is accomplished as required, for example, by a linear or piecewise linear increase according to the concentration/time-dependency schemes illustrated by S. Kim et al (International Journal of Heat and Mass Transfer 46, 2003, 3747- 3754).
- the linear concentration/time-dependency scheme is depicted by a straight line of a positive gradient, whereas the piecewise linear concentration/time-dependency scheme is depicted, for example, by at least two meeting straight lines with distinct positive gradients.
- the change may also be accomplished in one or more discrete steps, wherein the concentration of the accelerator (b3) in the resin is increased stepwise, for example, by a sudden increase of the concentration which is followed by a phase, wherein the
- concentration of the accelerator (b3) ist kept constant.
- This scheme is appropriately considered an embodiment of the piecewise linear concentration/time-dependency scheme.
- the variation may be accomplished in accordance with a non-linear scheme, for example, an exponential, quadratic or cubic growth scheme.
- the resin composition which contains no accelerator (b3) or the accelerator (b3) in a low concentration comprises an amount of accelerator (b3), for example, of from 0 to 0.75 weight%, preferably of from 0 to 0.5 weight%, and more preferably of from 0 to 0.25 weight%, based on the total weight of the thermosetting resin composition.
- the resin composition which contains the accelerator (b3) in a high concentration comprises an amount of accelerator (b3), for example, of from 0.75 to 5 weight%, preferably of from 0.5 to 3 weight%, and more preferably of from 0.25 to 2.5 weight%, based on the total weight of the thermosetting resin composition. It is understood that each of the highest amounts of accelerator (b3) indicated for the resin composition which contains the accelerator (b3) in a low concentration is lower than each of the lowest amounts of accelerator (b3) indicated for the resin composition which contains the accelerator (b3) in a high concentration.
- VARICAT process The process which comprises varying the concentration of accelerator (b3) in the course of injecting the resin into the mold is referred to hereafter as VARICAT process.
- An apparatus to carry out the process according to the present invention comprises a reservoir for each of the components (b1 ), (b2) and (b3), feed lines which connect the reservoirs with the mixing head and the inlet of the mold, and pumps which provide for transportation of each of the components from their reservoirs to the mixing head.
- the mixing head is, for example, a static mixer or a self-cleaning high pressure mixing head, which is placed at the injection gate of the mold, and provides for mixing of the components before the resin composition enters the mold.
- the accelerator (b3) is, for example, feeded into the feed line of the curing agent (b2) before the curing agent (b2) is feeded into the mixing head, i.e.
- the accelerator (b3) is, for example, feeded into the feed line of the liquid epoxy resin (b1 ), before the liquid epoxy resin (b1 ) is feeded into the mixing head, i.e. before the feed line of the liquid epoxy resin (b1 ) arrives at the mixing head.
- the accelerator (b3) is, for example, feeded directly into the mixing head, separately from the liquid epoxy resin (b1 ) and the curing agent (b2), i.e. all components are feeded by separate feed lines which, for example, join at the mixing head.
- the pumps are controlled by a computer system equipped with suitable software to operate the pumps, i.e. control the pump rate. The software controls the pump rate of each pump in order to appropriately dose each of the components into the mixing head in accordance with the desired concentration/time-dependency scheme. Suitable software is commercially available.
- the accelerator (b3) is a solid, such as p-toluene sulfonic acid
- it is advantageously dissolved, for example, in the liquid curing agent (b2) in appropriate amounts to provide a solution which can be processed in accordance with the inventive process by means of the apparatus described above, for example, by feeding the solution of accelerator (b3) in curing agent (b2) separately from the liquid epoxy resin (b1 ) and the curing agent (b2).
- the concentration of the liquid epoxy resin (b1 ) in the thermosetting resin composition is kept constant in the course of injecting the resin into the mold, while the concentration of the accelerator is increased as described above.
- the concentration of the curing agent (b2) in the thermosetting resin composition is kept constant in the course of injecting the resin into the mold, while the concentration of the accelerator is increased as described above.
- thermosetting resin composition are kept constant in the course of injecting the resin into the mold, while the concentration of the accelerator is increased as described above.
- the inventive process is a VARICAT process, wherein the multiple component thermosetting resin composition comprises (b1 ) a diglycidylether of bisphenol A as the liquid epoxy resin, optionally used in admixture with other liquid epoxy resins, preferably a diglycidylether of bisphenol A,
- (b2) 1 ,3-bis(aminomethyl)cyclohexane as the curing agent, optionally used in admixture with other curing agents, preferably 1 ,3-bis(aminomethyl)cyclohexane,
- the inventive process is a VARICAT process, wherein the multiple component thermosetting resin composition comprises
- the shelf life may be insufficient, and precipitation may occur during transportation or storage in the reservoir.
- Such precipitation of the accelerator (b3) is not desired, since it may result in failure of pumps and clogging of feed lines.
- the cure kinetics of the thermosetting resin composition obtained may be adversely affected and the composite article prepared therefrom may become inhomogeneous.
- water is added to the liquid curing agent (b2) before or after the accelerator (b3) is dissolved.
- the amount of water added is, for example, in the range of from 0.5 to 1.5 weight%, preferably of from 0.8 to 1.2 weight%, based on the total weight of the solution of the sulfonic acid in the curing agent (b2).
- stable, concentrated solutions of accelerator (b3) in the liquid curing agent (b2) with a very good shelf life are prepared by applying the sulfonic acid as an ionic liquid, for example, an imidazolium salt of a sulfonic acid.
- the ionic liquid is an imidazolium salt of p-toluene sulfonic acid or methane sulfonic acid, for example, 1 - methylimidazolium p-toluene sulfonate or 1 ,3-dimethylimidazolium methyl sulfate.
- 1 -methylimidazolium p-toluene sulfonate is used as an ionic liquid.
- concentrated solution shall mean an amount of accelerator (b3), for example, p- toluene sulfonic acid, in the curing agent (b2) in the amount of up to 55 weight%, preferably up to 50 weight%, based on the total weight of the concentrated solution of accelerator (b3) in the curing agent (b2) at room temperature.
- accelerator (b3) for example, p- toluene sulfonic acid
- the ionic liquid can be applied directly as the accelerator (b3) in accordance with the inventive process without being dissolved in the liquid curing agent (b2).
- curing step d i.e. curing of the resin impregnated preform
- curing step d is carried out under isothermal conditions at a temperature of from 80 to 140°C, preferably of from 105 to 125°C
- the process according to the present invention allows for uniform cure for a given mold geometry, cure cyle and preform.
- Fiber reinforced composite articles with excellent mechanical properties, especially elongation and fracture toughness and a high Tg can be prepared within a cycle time of less than 5 minutes, preferably less than 4 minutes and most preferably less than 3 minutes.
- the resin composition applied according to inventive process has an appropriate open time after mixing of the components at the injection gate, but the ability to cure rapidly without the need of post-curing.
- the present invention is also directed to the composite articles obtained by the inventive process.
- the present invention is directed to the use of the composite articles obtained according to the inventive process for the construction of mass transportation vehicles, in particular in automotive and aerospace industry.
- Test specimens are prepared by filling into a mold a composition of 83.33 parts of bisphenol A diglycidylether (ARALDITE® LY 1 135-1 A), 16.17 parts of 1 ,3-bis(aminomethyl)cyclo- hexane and 0.50 parts of p-toluene sulfonic acid mono hydrate (PTSAx H 2 0).
- the compositions are cured at 1 10°C. During curing viscosity build-up at 1 10°C, gelation time and DSC isotherm are measured.
- Test specimens are prepared by filling into a mold a composition of 82.17 parts of bisphenol A diglycidylether (ARALDITE® LY 1 135-1 A) and 16.05 parts of 1 ,3-bis(aminomethyl)cyclo- hexane and 1 .78 parts of p-toluene sulfonic acid mono hydrate (PTSAx H 2 0).
- the compositions are cured at 1 10°C. During curing viscosity build-up at 1 10°C, gelation time and DSC isotherm are measured.
- Test specimens are prepared by filling into a mold a composition of 83.68 parts of bisphenol A diglycidylether (ARALDITE® LY 1 135-1 A) and 16.32 parts of 1 ,3-bis(aminomethyl)cyclo- hexane.
- the compositions are cured at 1 10°C. During curing viscosity build-up at 1 10°C, gelation time and DSC isotherm are measured.
- thermosetting resin composition Table 3: Viscosity build-up at 1 10°C (time to 600 mPa s)
- thermosetting resin composition * wt% based on the total weight of the thermosetting resin composition
- thermosetting resin composition * wt% based on the total weight of the thermosetting resin composition
- Viscosity build-up is measured on a Brookfield CAP 2000+ (plate-cone #1 ). Gelation time is measured manually on a hot plate using an electronic clock. Differential Scanning
- thermosetting resin composition Table 6: Glass transition temperature (Tg) after 2h cure at 180°C
- thermosetting resin composition *wt% based on the total weight of the thermosetting resin composition
- Glass transition temperature (Tg) of test specimens prepared as 6 plies CFRP (carbon fiber reinforced polymer) composite (40 weight% resin content) in accordance with the Examples above is measured by Dynamic Mechanical Analysis (DMA) on a Perkin Elmer 8000 (range: 20 to 210°C at 10°C min "1 ).
- DMA Dynamic Mechanical Analysis
- Diglycidyl ether of bisphenol A (ARALDITE® LY 1 135-1 A) is charged to a reservoir and heated to 70°C with stirring.
- a solution of 30 parts of p-toluene sulfonic acid mono hydrate (PTSAx H 2 0) in 70 parts of 1 ,3-bis(aminomethyl)cyclohexane is charged to a reservoir and heated to 50°C with stirring.
- 1 ,3-bis(aminomethyl)cyclohexane is charged to a reservoir and heated to 50°C with stirring.
- a pre-formed carbon-fibre reinforcement mat is then positioned manually into a vented mold of a car roof, and the mold is closed.
- the diglycidyl ether of bisphenol A, the curing agent and the concentrated solution of p-toluene sulfonic acid mono hydrate in the curing agent are injected into the mold through a static mixer dispensing unit or a self-cleaning high pressure mixing head. Air is removed from upper side vents of the mold, or the mold is evacuated.
- the weight ratio of epoxy resin / curing agent / p-toluene sulfonic acid is 83.33/16.17/0.5.
- Pouring time is 40 sec.
- the mold is preheated to 1 10°C and maintained at that temperature during the curing process.
- Demold time is about 2.5 minutes after end of pouring.
- the Tg of the polymer phase for a typical part made in this manner is about 1 15°C.
- Part thickness is approximately 2 mm. Similar results are obtained when the epoxy resin composition is used to make articles for cars of a different geometry.
- Diglycidyl ether of bisphenol A (ARALDITE® LY 1 135-1 A) is charged to a reservoir and heated to 70°C with stirring.
- a solution of 30 parts of p-toluene sulfonic acid mono hydrate (PTSAx H 2 0) in 70 parts of 1 ,3-bis(aminomethyl)cyclohexane is charged to a reservoir and heated to 50°C with stirring.
- 1 ,3-bis(aminomethyl)cyclohexane is charged to a reservoir and heated to 50°C with stirring.
- a pre-formed carbon-fibre reinforcement mat is then positioned manually into a vented mold of a car side frame, and the mold is closed.
- the diglycidyl ether of bisphenol A, the curing agent and the concentrated solution of p-toluene sulfonic acid mono hydrate in the curing agent are injected into the mold through a static mixer dispensing unit or a self-cleaning high pressure mixing head. Air is removed from upper side vents of the mold, or the mold is evacuated.
- the weight ratio of epoxy resin / curing agent / p-toluene sulfonic acid is
- Test specimens are prepared by filling into a mold a composition of ARALDITE® LY 1 135-1 A (bisphenol A diglycidylether: Bis A), 1 ,3-bis(aminomethyl)cyclo- hexane (1 ,3-BAC) and 1 -Methylimidazolium p-toluene sulfonate as an ionic liquid (IL), which is prepared by mixing equimolar amounts of p-toluene sulfonic acid mono hydrate (PTSAx H 2 0) and 1 -Methylimidazole. The amount of each component is given in Table 8. Epoxy equivalent weight of ARALDITE® LY 1 135-1 A is 181 . The compositions are cured as indicated below. Viscosity build-up at 1 10°C, gelation time, glass transition temperature and some mechanical properties are determined.
- IL ionic liquid
- Table 8 Compositions according to Examples 5 to 1 1
- thermosetting resin composition * wt% based on the total weight of the thermosetting resin composition
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Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
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MX2016011858A MX2016011858A (en) | 2014-03-28 | 2015-03-02 | A process for manufacturing a fiber reinforced epoxy composite article, the composite articles obtained and the use thereof. |
EP15706839.6A EP3122804A1 (en) | 2014-03-28 | 2015-03-02 | A process for manufacturing a fiber reinforced epoxy composite article, the composite articles obtained and the use thereof |
CN201580017087.6A CN106459450A (en) | 2014-03-28 | 2015-03-02 | A process for manufacturing a fiber reinforced epoxy composite article, the composite articles obtained and the use thereof |
CA2940132A CA2940132A1 (en) | 2014-03-28 | 2015-03-02 | A process for manufacturing a fiber reinforced epoxy composite article, the composite articles obtained and the use thereof |
US15/126,351 US20170081487A1 (en) | 2014-03-28 | 2015-03-02 | A process for the preparation of a fiber reinforced composite article, the composite articles obtained and the use thereof |
JP2017501475A JP2017509781A (en) | 2014-03-28 | 2015-03-02 | Method for producing fiber reinforced composite product, resulting composite product and use thereof |
KR1020167024034A KR20160140605A (en) | 2014-03-28 | 2015-03-02 | A process for manufacturing a fiber reinforced epoxy composite article, the composite articles obtained and the use thereof |
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US (1) | US20170081487A1 (en) |
EP (1) | EP3122804A1 (en) |
JP (1) | JP2017509781A (en) |
KR (1) | KR20160140605A (en) |
CN (1) | CN106459450A (en) |
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WO2018000125A1 (en) * | 2016-06-27 | 2018-01-04 | Evonik Degussa Gmbh | Room temperature ionic liquid curing agent |
JP2018135433A (en) * | 2017-02-21 | 2018-08-30 | 三菱瓦斯化学株式会社 | Epoxy resin curing agent, epoxy resin composition, and fiber-reinforced composite material |
KR20230042529A (en) | 2020-09-15 | 2023-03-28 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Use of Epoxy Resin Curing Agents, Epoxy Resin Compositions, and Amine Compositions |
KR20230042528A (en) | 2020-09-15 | 2023-03-28 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Use of Epoxy Resin Curing Agents, Epoxy Resin Compositions, and Amine Compositions |
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US10807277B2 (en) * | 2016-11-07 | 2020-10-20 | The Boeing Company | Resin-infused short fiber composite materials |
EP3450126A1 (en) * | 2017-09-01 | 2019-03-06 | Hexion Research Belgium SA | Multi-component mixing and metering equipment with online stoichiometry control |
US10507776B2 (en) * | 2017-10-12 | 2019-12-17 | GM Global Technology Operations LLC | Fiber-reinforced composite bumper beam and crush members |
KR102200972B1 (en) * | 2017-12-22 | 2021-01-08 | (주)엘지하우시스 | High pressure-resin transfer method for injection molded product with improved surface quality |
EP3936548A4 (en) | 2019-03-06 | 2022-04-27 | Mitsubishi Gas Chemical Company, Inc. | Epoxy resin composition and cured product thereof, and fiber-reinforced composite |
KR102209369B1 (en) * | 2019-12-31 | 2021-01-28 | 한화큐셀앤드첨단소재 주식회사 | Natural fiber composite molding method using t-rtm process |
EP3882294A1 (en) | 2020-03-18 | 2021-09-22 | Hilti Aktiengesellschaft | Hardener composition based on diaminomethylcyclohexane and 1,3-cyclo-hexane-bis(methylamine) for an epoxy resin composition, epoxy resin composition and multicomponent epoxy resin system |
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WO2018000125A1 (en) * | 2016-06-27 | 2018-01-04 | Evonik Degussa Gmbh | Room temperature ionic liquid curing agent |
JP2018135433A (en) * | 2017-02-21 | 2018-08-30 | 三菱瓦斯化学株式会社 | Epoxy resin curing agent, epoxy resin composition, and fiber-reinforced composite material |
KR20230042529A (en) | 2020-09-15 | 2023-03-28 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Use of Epoxy Resin Curing Agents, Epoxy Resin Compositions, and Amine Compositions |
KR20230042528A (en) | 2020-09-15 | 2023-03-28 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Use of Epoxy Resin Curing Agents, Epoxy Resin Compositions, and Amine Compositions |
EP4215560A4 (en) * | 2020-09-15 | 2024-02-28 | Mitsubishi Gas Chemical Company, Inc. | Epoxy resin curing agent, epoxy resin composition, and use of amine composition |
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US11976161B2 (en) | 2020-09-15 | 2024-05-07 | Mitsubishi Gas Chemical Company, Inc. | Epoxy resin curing agent, epoxy resin composition, and use of amine composition |
Also Published As
Publication number | Publication date |
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MX2016011858A (en) | 2016-12-02 |
US20170081487A1 (en) | 2017-03-23 |
CA2940132A1 (en) | 2015-10-01 |
CN106459450A (en) | 2017-02-22 |
KR20160140605A (en) | 2016-12-07 |
JP2017509781A (en) | 2017-04-06 |
EP3122804A1 (en) | 2017-02-01 |
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