CN1049177C - 可固化模塑制品的制造方法 - Google Patents
可固化模塑制品的制造方法 Download PDFInfo
- Publication number
- CN1049177C CN1049177C CN93112848A CN93112848A CN1049177C CN 1049177 C CN1049177 C CN 1049177C CN 93112848 A CN93112848 A CN 93112848A CN 93112848 A CN93112848 A CN 93112848A CN 1049177 C CN1049177 C CN 1049177C
- Authority
- CN
- China
- Prior art keywords
- acid
- resin
- composition
- method described
- mole
- 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.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 239000003822 epoxy resin Substances 0.000 claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000945 filler Substances 0.000 claims abstract description 15
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 13
- 239000004593 Epoxy Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 238000000465 moulding Methods 0.000 claims abstract description 8
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 4
- 239000011342 resin composition Substances 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- -1 aromatic glycidyl ethers Chemical class 0.000 claims description 24
- 150000008065 acid anhydrides Chemical class 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 5
- 230000008602 contraction Effects 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 230000029936 alkylation Effects 0.000 claims description 4
- 238000005804 alkylation reaction Methods 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 claims description 3
- 229930185605 Bisphenol Natural products 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 2
- MYPXYQMABPTFFN-UHFFFAOYSA-N 4-phenoxybenzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1OC1=CC=CC=C1 MYPXYQMABPTFFN-UHFFFAOYSA-N 0.000 claims description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- YTFJQDNGSQJFNA-UHFFFAOYSA-L benzyl phosphate Chemical compound [O-]P([O-])(=O)OCC1=CC=CC=C1 YTFJQDNGSQJFNA-UHFFFAOYSA-L 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- QLMGIWHWWWXXME-UHFFFAOYSA-N 2-(3,5-ditert-butyl-4-hydroxyphenyl)acetic acid Chemical class CC(C)(C)C1=CC(CC(O)=O)=CC(C(C)(C)C)=C1O QLMGIWHWWWXXME-UHFFFAOYSA-N 0.000 claims 1
- 230000000640 hydroxylating effect Effects 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 3
- 150000004714 phosphonium salts Chemical class 0.000 abstract description 2
- 229920005862 polyol Polymers 0.000 abstract description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 abstract 1
- 238000009472 formulation Methods 0.000 abstract 1
- 239000004033 plastic Substances 0.000 abstract 1
- 229920003023 plastic Polymers 0.000 abstract 1
- 150000003077 polyols Chemical class 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000006114 decarboxylation reaction Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000004848 polyfunctional curative Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 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 3
- 238000004519 manufacturing process Methods 0.000 description 3
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 239000012963 UV stabilizer Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- DCKDPDONFMIQBA-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;phthalic acid Chemical compound OCC(C)(C)CO.OC(=O)C1=CC=CC=C1C(O)=O DCKDPDONFMIQBA-UHFFFAOYSA-N 0.000 description 1
- NGAVZFBDWDNHFD-UHFFFAOYSA-N 3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propanoic acid Chemical compound CC1=CC(CCC(O)=O)=C(O)C(C(C)(C)C)=C1 NGAVZFBDWDNHFD-UHFFFAOYSA-N 0.000 description 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 1
- LYWVNPSVLAFTFX-UHFFFAOYSA-N 4-methylbenzenesulfonate;morpholin-4-ium Chemical compound C1COCCN1.CC1=CC=C(S(O)(=O)=O)C=C1 LYWVNPSVLAFTFX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- IYOCVADXMWADFF-UHFFFAOYSA-M C(C)(=O)[O-].NC(=N)N.C[N+](C)(C)C Chemical compound C(C)(=O)[O-].NC(=N)N.C[N+](C)(C)C IYOCVADXMWADFF-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical class NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 1
- ABTPXCYMQJLEKE-UHFFFAOYSA-N benzyl-dodecyl-diethylazanium Chemical compound CCCCCCCCCCCC[N+](CC)(CC)CC1=CC=CC=C1 ABTPXCYMQJLEKE-UHFFFAOYSA-N 0.000 description 1
- 229910052626 biotite Inorganic materials 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
- 150000001656 butanoic acid esters Chemical class 0.000 description 1
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical class CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000021003 saturated fats Nutrition 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/247—Heating methods
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
-
- 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
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/003—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor characterised by the choice of material
- B29C39/006—Monomers or prepolymers
-
- 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
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
-
- 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
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
- B29C67/246—Moulding high reactive monomers or prepolymers, e.g. by reaction injection moulding [RIM], liquid injection moulding [LIM]
-
- 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
-
- 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
-
- 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
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Sealing Material Composition (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
一种制造固化模塑制品的方法。该法包括:将预热的可固化树脂组合物引入一只较热的、温度高到足以引发树脂固化的塑模中,在压力下提供更多树脂以补偿组合物的收缩。其中可固化树脂是含以下物质的组成物;芳香缩水甘油醚环氧树脂,惰性填充剂,作为促进剂的季铵盐或季盐、含量为每摩尔环氧树脂含0.5-1.2摩尔的饱和环脂族酸酐和以每摩尔环氧树脂含0.05-0.5摩尔羧基的含量存在的优选衍生于多羟化物的反应的多元酸。
Description
本发明涉及使用含环氧树脂的可固化组合物制造模塑制品。
环氧树脂通过称之为自动加压固化(APG)的工艺可用来制造模塑制品。在GB1323343和EP0333456中所描述的方法中,环氧树脂和固化剂在液态、常常是40-60℃的温度下混合,然后,混合物在微微加压下进入塑模,该塑模具有足以使混合物发生胶化和固化的温度。并且为了补偿组合物的收缩,在加压状态下提供更多的混合物到塑模中,直到组合物定型。
依所制模为厚壁还是薄壁模而定,使用的技术略有不同。为生产厚壁硬塑模制品,将预热的在3-60分钟内可定型的液体铸模树脂组合物在极小的压力下注入预热的塑模,并基本上将塑模充满,塑模温度足以使树脂组合物开始硬化,组合物的温度至少低于塑模温度的10%,上述温度均为摄氏度。选择塑模温度和树脂组合物的温度,以便于塑模制品组合物的中心温度不会达到塑模壁的组合物的温度,直到组合物已充分定型使之能从塑模中脱出。为了补偿组合物的收缩,更多的组合物在加压状态下进入塑模,直至组合物定型,其后,定型的模制品脱离塑模。
为生产薄壁硬塑模制品,使预热并脱气的、于60分钟内可定型的树脂组合物在压力下进入更热的预热塑模中的制品形状的塑模空腔,并基本将空腔充满。当组合物充满空腔时,气体从中排出。在组合物固化期间需限制气体进入塑模空腔,然后在压力下使更多的组合物进入塑模空腔,以补偿组合物的收缩,直到组合物固化。此外,组合物预热到50℃-120℃,在至少28kPa(4psi)的压力下进入塑模空腔。塑模空腔的最高温度是170-200℃。控制塑模的温度以维持组合物连续的温度梯度,该组合物具有其进入塑模空腔入口处的最低温度和远离入口处的空腔外围区域的最高温度,借此,组合物从远离入口处到入口处直到塑模空腔,都在进行组合物定型过程。
普遍接受的观点是:固化的芳香缩水甘油醚环氧树脂受阳光和紫外线影响,产生的有害结果首先是灰化和/或褪色,现已提出许多方法来改善其性能。
特殊的非芳香环氧树脂已用来作为替代物,例如,户外电绝缘器中的环脂族树脂和耐候性涂粉中的三缩水甘油异氰脲酸酯。在工艺过程中,可替代加入抗氧化剂和UV稳定剂之类的特殊添加剂。
当环脂族树脂与酸酐硬化剂一起使用时,普遍认为如果硬化剂也完全被饱和,紫外稳定剂将达到最大量。
现在,我们惊讶地发现,饱和脂环系酸酐硬化剂与双酚A环氧树脂共同使用时,产生的固化产品显示出比其与双键不饱和物产生的固化产品大得多的抵抗其在阳光下变黄的能力。这种抗变黄的能力可以通过抗氧化剂和紫外稳定剂的结合使用而得到进一步改善。
以液态双酚环氧树脂和饱和的环脂族酸酐硬化剂为基础的可固化组合物通常被使用,尤其在铸模技术中。然而,对于那些涉及到在高温下迅速固化的工艺,例如,用APG工艺铸模薄壁构件时,标准的饱和环脂族酸酐有一个严重的缺点,即它们有经历碱催化的分子内缩合并脱去二氧化碳气体的倾向。树脂聚合期间的副反应将导致在固化产品中形成气泡。
我们发现,这种影响可以通过羧酸基团或脂肪羟基化合物的引入而极大降低,后者能够与酸酐原位反应产生酸,这将在很大程度上控制过量二氧化碳的逸出。此外,我们发现,二氧化碳的逸出可以进一步借助于自由基清除剂,例如位阻酚和位阻胺来控制。
对于快速循环APG的工艺来说,以用饱和酸酐硬化剂(该硬化剂含有羧酸改性剂和常规的叔胺或咪唑促进剂)固化的环氧树脂为基础的体系,使用上的另一限制是发生初始固化的速度较慢,它十分不利地影响着脱模时间和整个工艺的经济状况。我们发现,通过加入合适的季铵盐或季鏻盐作为促进剂或助促进剂,基本上能够加速最初的固化,而混合物的使用寿命不会受到严重损害。
因此,本发明提供了一种制造固化塑模制品的方法,该方法为:将预热的可固化的树脂组合物引入一温度高到足以发生树脂的固化的较热的塑模中,并在压力下提供更多的树脂以补偿组合物的收缩,在此,可固化树脂是包含下列物质的组成物:芳香缩水甘油醚环氧树脂、惰性填充物、作为促进剂的季铵盐或季鏻盐、含量为每摩尔环氧树脂中含0.5-1.2摩尔的饱和环脂族酸酐和以每摩尔环氧树脂含0.05-0.5摩尔羧基的量存在的多元羧酸(最好由多羟化物的反应衍生而来)。
酸的官能组分可作为独立成分加入和/或可以通过先与亚化学计量量的多羟化物缩合,在硬化剂组分中形成,和/或可以在树脂/硬化剂混合期间或之后由多羟化物形成,该多羟化物预先已与树脂结合或作为独立组分与树脂—硬化剂混合物一起加入。
每摩尔环氧树脂最好含有0.5-0.85摩尔酸酐和0.1-0.25摩尔酸。
填充物的总量可为组合物重量的40-85%,最好是50-80%。
合适的环氧树脂是聚缩水甘油和聚(β-甲基缩水甘油)醚,它们可由每分子中至少含二个游离酚羟基的化合物与适当的3-氯-1,2-环氧丙烷在碱性条件下反应产生。反应条件也可改为在酸性催化剂的存在下再用碱处理。这些醚可由单核酚、例如间苯二酚和氢醌制成,也可由多核酚,例如双(4-羟苯基)甲烷,4,4′-二羟联苯,1,1,2,2-四(4-羟苯基)乙烷、2,2-双(4-羟苯基)丙烷和2,2-双(3,5-二溴-4-羟苯基)丙烷而来。最好的环氧树脂是2,2-双(4-羟苯基)丙烷的缩水甘油醚。
饱和酸酐最好是饱和的环状酸酐。如六氢邻苯二甲酸酐和甲基六氢邻苯二甲酸酐或是它们的混合物。饱和酸酐可以含最多20%(重量)的不饱和酸酐。
可在很宽范围内使用任何多羟化物,包括链脂族和环状多元醇。这类化合物的合适的例子包括:乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、三羟甲基丙烷、甘油、新戊二醇、季戊四醇,分子量范围在1000以内的聚乙二醇和聚丙二醇以及氢化双酚A。
合适的季铵和鏻化合物包括卤化物和乙酸盐,例如氯化四甲铵,氯化四乙铵,氯化苄基三甲基铵,氯化十二烷基苄基二乙基铵,四甲铵基乙酸盐、氯化四丁基鏻和氯化乙基三苯基鏻。
每100份重的液态环氧树脂可以含有至多5份重的促进剂,最好是含0.2-0.8份重。
也可以存在其它促进剂。例子包括叔胺或咪唑和它们与酚或酸的盐,烷基二甲胺—三氯化硼络合物、辛酸锌、辛酸亚锡和碱金属的烷氧化物。
组合物也可以含抗氧化剂。
合适的抗氧化剂包括:烷基化单酚、烷基硫代甲基酚、氢醌和烷基化氢醌、羟基化的硫代二苯醚、亚烷基双酚、O-,N-,S-苄基化合物,羟苄基化的丙二酸盐,羟苄基芳香化合物、三嗪化合物、苄基磷酸盐、酰氨酚、β-(3,5-二叔丁基-4-羟苯基)丙酸的酯和酰胺、β-(5-叔丁基-4-羟基-3-甲苯基)丙酸的酯、β-(3,5-二环己基-4-羟苯基)丙酸酯、3,5-二叔丁基-4-羟苯基)乙酸酯和3,3-双(3′-叔丁基-4′-羟苯基)丁酸酯。
抗氧化剂可以与一种或多种紫外吸收剂和光稳定剂结合使用。合适的UV吸收剂和光稳定剂的例子有:2-(2′-羟苯基)苯并三唑、2-羟基二苯酮、取代和未取代的苯甲酸酯、氰基丙烯酸酯、镍化合物、空间位阻胺、草酸二酰胺和2-(2-羟苯基)-1,3,5-三嗪。
可以使用的填充剂范围很大,包括细颗粒和粗颗粒,填充剂可以是无机物,如瓷土,煅烧瓷土,石英粉,方晶石,白垩,云母粉,玻璃粉,玻璃珠,粉状玻璃纤维,氧化铝,硅灰石和氢氧化镁。填充物也可以是有机物,例如粉状聚氯乙烯、尼龙、聚乙烯、聚酯或固化环氧树脂,还可以使用阻燃填充剂,如三水合铝。
可以使用填充剂的混合物。例如,为使模制品产生类似花岗岩的效果,可以将煅烧瓷土与相当大颗粒,如约0.5mm的黑云母混合使用。
可以用硅烷或有机铁酸盐偶合剂处理填充剂表面。
一般来说,可用的填充剂颗粒大小从10-3000微米,最好是从50-700微米。
组合物可分成二部分或更多份,一份含环氧树脂,另一份含酸酐。
抗氧化剂在二部份内都可存在,但最好和酸酐一起存在于酸酐部分。
填充剂最好是在环氧部分,因为其粘度很高,足以防止填充剂下沉。但是某些甚至所有填充剂存在于酸酐部分也是可能的。
促进剂在二部分内均可存在,只要它在树脂部分的含量还不足以使混合物变成不能接受的不稳定状态。
其它在模塑树脂组合物中常规使用的添加剂也可包括在组合物中,这些添加剂的例子有:颜料、染料、纤维(如玻璃纤维和碳纤维)、阻燃剂、表面活性剂、消泡剂、增韧剂(如橡胶和壳—芯高聚物)以及其它如低级羧酸那样的稳定剂。
为了固化组合物,所有组分都被混合在一起,然后通入塑模中,该塑模的温度高到足以固化组合物,如在140-200℃之间。
本发明使用的配方允许模塑工艺在直至200℃的高温下操作而不会脱羧,它对于快速生产同样有效,模塑产品易于脱模,因为一旦固化开始,它们立刻变得非常坚韧。最终得到的模塑产品也具有很好的韧性和优良的UV稳定性。
本发明的工艺可用于生产薄壁或厚壁(指横断面)的模制品,尤其适于生产有很大表面积、至少有较大线形空间或复杂形状的模制品。该工艺可以用于以下诸方面的模制品的制作,例如,洗涤槽、浴缸、淋浴支架、脸盆等家庭卫生器具,家用操作台(worktop)等用于制品生产的sheet slabstock,用于汽车和其它车辆的象油箱这样的抗化学腐蚀的容器和输送腐蚀液体及抗冲击的泵、阀门和管道等零部件以及电力设备。
本发明的工艺克服了依赖于被制造的物件是薄壁还是厚壁而需要使用不同技术的缺点,这使得薄厚部分都有的模制品能够方便地制造出来。
本发明用下列实施方案来说明,其中份数为重量份。
实施例中使用的材料:
环氧树脂I:=29.3%液态双酚A环氧树脂。环氧量为5.2摩
尔/千克。
0.036%氯化四甲铵
11.8%二氧化钛
58.8%经200目筛过筛的煅烧瓷土
0.14%ByK W935,市售表面活性剂
环氧树脂II:=27.6%液态双酚A环氧树脂,环氧量为5.2
摩尔/千克
0.033%氯化四甲铵
70.8%经200目筛过筛的硅石粉
1.4%沉淀的碳酸钙
0.14%ByK W935市售表面活性剂
85ppm碳黑
1.0ppm酞菁兰
环氧树脂III:=27.4%液态双酚A环氧树脂,环氧量为5.2
摩尔/千克
0.033%氯化四甲铵
71.2%过200目筛的硅石粉
0.68%煅烧瓷土,1-2mm聚集体
0.54%疏水胶态二氧化硅
0.14%牌号为ByK W935的市售表面活性剂
38ppm碳黑
环氧树脂IV:=26.2%液态双酚A环氧树脂,环氧量为5.
35mol/kg
64.3%过200目筛的硅石粉
9.2%二氧化钛,金红石
0.26%ByKW980市售表面活性剂
0.63%ByK A501市售空气释放剂
2.4ppm酞菁兰
方法:在65℃时,真空下混合,制成单一混合物。硬化剂—组合物的重量份:
制备方法:
A | B | C | D | E | F | G | H | J | K | |
六氢苯二甲酸酐 | 57.4 | 57.4 | 57.4 | 57.4 | 57.4 | 57.4 | 57.4 | 57.4 | - | 49.6 |
甲基六氢苯二甲酸酐 | 24.6 | 24.6 | 24.6 | 24.6 | 24.6 | 24.6 | 24.6 | 24.6 | - | 39.6 |
甲基四氢苯二甲酸酐 | - | - | - | - | - | - | - | - | 80.8 | 9.9 |
新戊二醇 | 0 | 2 | 2.46 | 3.6 | 4.4 | 4.4 | 4.4 | 7.2 | - | 5.4 |
双四氢苯二甲酸新戊二醇单酯 | - | - | - | - | - | - | - | - | 18.7 | - |
三氯化硼辛二甲胺络台物(促进剂M) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.58 |
苄基二甲胺(促进剂N) | - | - | - | - | - | - | - | - | 0.09 | - |
季戊四醇-四-3-( 3-二叔丁基-4-羟苯基)丙酸酯(抗氧化剂P) | 2 | 2 | 2 | 2 | 2 | - | - | 2 | 2 | - |
3,3-双(3-叔丁基-4-羟苯基)乙烯丁酸酯(抗氧化剂Q) | - | - | - | - | - | 1.35 | - | - | - | - |
氯化苄苄三乙基铵 | - | - | - | - | - | - | - | - | - | 0.3 |
A.单一混合物。抗氧化剂在80℃时溶于酸酐,然后50℃下溶
入促进剂M
B.酸酐加热到120℃,加入新戊二醇,在120℃反应2小时,
在80℃下溶入抗氧化剂,50℃时溶入促进剂M。
C.新戊二醇和四氢苯二甲酸酐摩尔比1∶2,它们与促进剂N
在120℃结合,然后于150℃反应1小时,80℃下溶入抗氧
化剂,50℃下溶入促进剂M。铸模方法:
配制的环氧树脂成分加热至70℃,加入硬化剂。每摩尔环氧中用1摩尔酸酐与硬化剂A-H一起使用,不必考虑新戊二醇含量,硬化剂J以每百份液态环氧树脂用80份的含量使用。在50℃下,混合物在真空下搅拌,然后以100-250kPa的压力注入二件钢制塑模底边的中心。该塑模提供了容积约为5.6升的异型腔,腔的整体高为900mm,宽600mm,厚度均匀为0.6mm。塑模温度可以调节以便于基本保持顶部比底部热。将混合物充满塑模约需1-2分钟。此后,维持此压力至树脂混合物已充分固化,且塑模被打开,铸件脱模。然后将铸件随意放入一只空气循环烘箱内,在135℃进行2小时二次固化。实施例1:
环氧树脂I和II用硬化剂A、B、C、F、G、H和K处理产生亮白色铸件,检查其中夹带的二氧化碳汽泡,并用Minolta比色计检查颜色。之后,用合成日光照射铸模,监视颜色随时间延长而变化的情况。结果列于表1
表1
实施例 | 树脂 | 硬化剂 | 塑模温度℃顶部 底部最高温 最低温 | 最小脱模时间(分钟) | 气泡含量 | 天数增加泛黄指数(b值)的变化 |
1 UNIT 3UNITS | ||||||
1 | I | J | 190 160 | 10 | 无 | 8 12 |
2 | I | A | 190 147 | 10.5 | 明显 | 23 >120 |
3 | I | A | 170 127 | 17 | 无 | - - |
4 | I | B | 190 147 | 9.0 | 无 | 23 75 |
5 | I | C | 187 156 | 9.5 | 无 | - - |
6 | I | F | 199 155 | 8 | 无 | - - |
7 | I | G | 199 155 | 8.5 | 无 | - - |
8 | I | H | 190 147 | 10 | 无 | - - |
9 | IV | K | 170 150 | 9.5 | 无 | 25 >40 |
实施例1.结果表明使用不饱和硬化剂可以迅速脱模而不致脱
羧,但光稳定性差。
实施例2.结果证明使用饱和酸酐能够得到满意的光稳定性。
含羧基部分也不用改性,但产品易脱羧。
实施例3.结果显示出,降低塑模温度可以防止脱羧,但脱模
时间延长了。
实施例4-9.结果表明:合适地选择组合物能够获得满意的
耐脱羧性、光稳定性和固化速度。尤其是实施例
6,表明10千克铸件脱模时间为8分钟这样的
优异成果。实施例2.
树脂II和III具有极相似的组合物,只不过树脂III中存在少量粗惰性聚集体。树脂II与硬化剂C一起使用,而树脂III则与硬化剂F共用。结果列于表2。
表2
实施例 | 树脂 | 硬化剂 | 塑模温度℃ | 最小脱模时间(分钟) | 气泡含量 | |
上部最高 温 | 底部最高 温 | |||||
1 | II | C | 191 | 157 | 10.5 | 明显 |
2 | II | C | 176 | 142 | 12.5 | 轻微 |
3 | II | C | 169 | 144 | 13 | 极少 |
4 | III | F | 162 | 144 | 12 | 无 |
5 | III | F | 170 | 154 | 10 | 无 |
6 | III | F | 180 | 164 | 8 | 无 |
实施例4-6与1-3比较证明,提高羧基含量可有效地抑制脱羧,从而可使构件迅速脱模。
Claims (10)
1.一种制造固化塑模制品的方法,该法包括:将预热的可固化树脂组合物引入一只较热、温度高到足以引发树脂固化的塑模中,并在加压下提供更多的树脂以补偿组合物的收缩,其中可固化树脂是包含以下物质的组合物:芳香缩水甘油醚环氧树脂,惰性填充剂,作为促进剂的季铵盐或季鏻盐、含量为每摩尔环氧含0.5-1.2摩尔的饱和环脂族酸酐和含量为每摩尔环氧0.05-0.5摩尔的羧基的多羧酸。
2.权利要求1中所述方法,其中,每一当量环氧树脂含0.5-0.85摩尔酸酐和0.1-0.25摩尔酸。
3.如权利要求1或2中所述方法,其中环氧树脂是2,2-双(4-羟苯基)丙烷的缩水甘油醚。
4.权利要求1中所述方法,其中,饱和环脂族酸酐是六氢邻苯二甲酸酐,甲基六氢邻苯二甲酸酐或它们的混合物。
5.权利要求1所述方法,其中饱和环脂族酸酐含有最多为20%(重量)的不饱和酸酐。
6.权利要求1中所述的方法,其中,酸来自环脂族酸酐与多羟化物的反应,多羟化物可选自乙二醇,1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、三羟甲基丙烷、甘油、新戊二醇、季戊四醇、分子量范围在1000以内的聚乙二醇和聚丙二醇以及氢化双酚A。
7.权利要求1中所述的方法,其中,组合物也含有抗氧化剂。
8.如权利要求7所述的方法,其中,抗氧化剂选自烷基化单酚,烷基硫代甲酚,氢醌和烷基化氢醌,羟基化硫代二苯醚,亚烷基双酚,O-,N-,S-苄基化合物,羟苄基化丙二酸盐,羟苄基芳香物,三嗪化合物,苄基磷酸盐,酰氨基酚,β-(3,5-二叔丁基-4-羟苯基)丙酸的酯和酰胺,β-(5-叔丁基-4-羟基-3-甲苯基)丙酸酯,β-(3,5-二环已基-4-羟苯基)丙酸酯和3,5-二叔丁基-4-羟苯基乙酸酯。
9.权利要求1中所述方法,其中,填充剂的含量为组合物重量的40-85%。
10.权利要求1中所述方法,该法可在直至200℃的模塑温度下操作。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9226500.8 | 1992-12-19 | ||
GB929226500A GB9226500D0 (en) | 1992-12-19 | 1992-12-19 | Curable compositions |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1089543A CN1089543A (zh) | 1994-07-20 |
CN1049177C true CN1049177C (zh) | 2000-02-09 |
Family
ID=10726878
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN93112848A Expired - Fee Related CN1049177C (zh) | 1992-12-19 | 1993-12-17 | 可固化模塑制品的制造方法 |
Country Status (17)
Country | Link |
---|---|
US (1) | US5505895A (zh) |
EP (1) | EP0604089B1 (zh) |
JP (1) | JP3203460B2 (zh) |
KR (1) | KR100289105B1 (zh) |
CN (1) | CN1049177C (zh) |
AT (1) | ATE171670T1 (zh) |
AU (1) | AU668612B2 (zh) |
CA (1) | CA2111719A1 (zh) |
DE (1) | DE69321330T2 (zh) |
ES (1) | ES2121957T3 (zh) |
GB (1) | GB9226500D0 (zh) |
HK (1) | HK1008669A1 (zh) |
IL (1) | IL108070A0 (zh) |
MY (1) | MY109507A (zh) |
NO (1) | NO934683L (zh) |
TW (1) | TW288026B (zh) |
ZA (1) | ZA939451B (zh) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9512533D0 (en) * | 1995-06-20 | 1995-08-23 | Ciba Geigy Ag | Curable compositions |
US6290202B1 (en) | 1997-11-20 | 2001-09-18 | Kewaunee Scientific Corporation | Apparatus for molding thin resin sheets |
WO2001051272A1 (en) * | 2000-01-14 | 2001-07-19 | Abb Power T & D Company Inc. | Transparent epoxy structures |
DE10027206A1 (de) * | 2000-05-31 | 2001-12-13 | Osram Opto Semiconductors Gmbh | Alterungsstabile Epoxidharzsysteme, daraus hergestellte Formstoffe und Bauelemente und deren Verwendung |
DE60223646T3 (de) | 2001-03-30 | 2015-02-26 | Toray Industries, Inc. | Epoxidharzzusammensetzung, verfahren zur herstellung von faserverstärkten verbundwerkstoffen und faserstärkte verbundwerkstoffe |
WO2005061620A1 (en) | 2003-12-23 | 2005-07-07 | Valorbec Societe En Commandite | Method and system for making high performance epoxies, and high performance epoxies obtained therewith |
CN101072808B (zh) * | 2004-12-21 | 2010-08-11 | 日立化成工业株式会社 | 酸酐类环氧树脂固化剂的制造方法、酸酐类环氧树脂固化剂、环氧树脂组合物、其固化物和光半导体装置 |
KR101297740B1 (ko) * | 2005-09-02 | 2013-08-20 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | 에폭시수지 조성물 |
JP2007131829A (ja) * | 2005-10-12 | 2007-05-31 | Hitachi Chem Co Ltd | エポキシ樹脂組成物及び絶縁処理された電気電子部品 |
JP2007277469A (ja) * | 2006-04-11 | 2007-10-25 | Kyocera Chemical Corp | 注形用エポキシ樹脂組成物及び電気・電子部品装置 |
JP2007284627A (ja) * | 2006-04-19 | 2007-11-01 | Toshiba Corp | 加圧ゲル化用エポキシ樹脂組成物およびこれを用いた加圧ゲル化法注形品 |
WO2009084014A2 (en) * | 2007-12-31 | 2009-07-09 | Amit Dixit | An epoxy resin composition |
US20120208924A1 (en) * | 2009-07-14 | 2012-08-16 | Abb Research Ltd | Epoxy resin composition |
AT508943B1 (de) * | 2009-10-01 | 2011-05-15 | Karl Dr Vorlicek | Lautsprechergehäuseelemente und lautsprechergehäuse |
JP2012111088A (ja) * | 2010-11-22 | 2012-06-14 | Panasonic Corp | 注型成形品の製造方法 |
GB201209970D0 (en) * | 2012-06-06 | 2012-07-18 | Jacuzzi Uk Group Plc | Improvements in the manufacture of sinks |
CN103917146B (zh) | 2012-10-25 | 2017-03-15 | 科勒公司 | 工程复合材料和由其生产的产品 |
US9382472B2 (en) * | 2013-12-18 | 2016-07-05 | Rohm And Haas Electronic Materials Llc | Transformative wavelength conversion medium |
CN104031243A (zh) * | 2014-06-24 | 2014-09-10 | 上海大学 | 季铵盐类环氧树脂固化促进剂及其制备方法 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2947717A (en) * | 1956-06-11 | 1960-08-02 | Devoe & Raynolds Co Inc | Epoxide resin compositions |
CH509139A (de) * | 1969-06-19 | 1971-06-30 | Ciba Geigy Ag | Verfahren zur Herstellung von gehärteten Kunststoff-Formkörpern |
USRE28498E (en) * | 1969-06-19 | 1975-07-29 | Method of producing a thick-walled cured plastics moulding | |
BE791129A (fr) * | 1971-11-10 | 1973-05-09 | Ciba Geigy | Melanges durcissables a chaud a base de resines epoxydiques |
US3954712A (en) * | 1971-11-10 | 1976-05-04 | Ciba-Geigy Corporation | Hot-curable mixtures based on epoxide resin |
JPS59129224A (ja) * | 1983-01-17 | 1984-07-25 | Hitachi Ltd | 樹脂組成物 |
JPS59140220A (ja) * | 1983-01-31 | 1984-08-11 | Hitachi Chem Co Ltd | エポキシ樹脂組成物 |
JPS59152921A (ja) * | 1983-02-18 | 1984-08-31 | Hitachi Chem Co Ltd | エポキシ樹脂組成物 |
DE3326532A1 (de) * | 1983-07-22 | 1985-01-31 | Siemens AG, 1000 Berlin und 8000 München | Verfahren zur herstellung von epoxidharzformstoffen |
US4581293A (en) * | 1985-02-05 | 1986-04-08 | Westinghouse Electric Corp. | Coating powder |
DE3616708A1 (de) * | 1986-05-20 | 1987-11-26 | Siemens Ag | Hitzehaertbare epoxidharzmassen, haerter fuer derartige epoxidharzmassen und dessen herstellung |
GB8806299D0 (en) * | 1988-03-17 | 1988-04-13 | Glynwed Consumer & Building | Process of manufacturing thin-walled plastics moulding |
-
1992
- 1992-12-19 GB GB929226500A patent/GB9226500D0/en active Pending
-
1993
- 1993-12-02 MY MYPI93002556A patent/MY109507A/en unknown
- 1993-12-13 AT AT93310029T patent/ATE171670T1/de not_active IP Right Cessation
- 1993-12-13 EP EP93310029A patent/EP0604089B1/en not_active Expired - Lifetime
- 1993-12-13 ES ES93310029T patent/ES2121957T3/es not_active Expired - Lifetime
- 1993-12-13 DE DE69321330T patent/DE69321330T2/de not_active Expired - Fee Related
- 1993-12-14 US US08/166,749 patent/US5505895A/en not_active Expired - Fee Related
- 1993-12-17 CA CA002111719A patent/CA2111719A1/en not_active Abandoned
- 1993-12-17 NO NO934683A patent/NO934683L/no unknown
- 1993-12-17 AU AU52487/93A patent/AU668612B2/en not_active Ceased
- 1993-12-17 CN CN93112848A patent/CN1049177C/zh not_active Expired - Fee Related
- 1993-12-17 IL IL10807093A patent/IL108070A0/xx unknown
- 1993-12-17 ZA ZA939451A patent/ZA939451B/xx unknown
- 1993-12-18 TW TW082110759A patent/TW288026B/zh active
- 1993-12-18 KR KR1019930028786A patent/KR100289105B1/ko not_active IP Right Cessation
- 1993-12-20 JP JP34481793A patent/JP3203460B2/ja not_active Expired - Fee Related
-
1998
- 1998-07-27 HK HK98109420A patent/HK1008669A1/xx not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
NO934683L (no) | 1994-06-20 |
ATE171670T1 (de) | 1998-10-15 |
IL108070A0 (en) | 1994-04-12 |
NO934683D0 (no) | 1993-12-17 |
CN1089543A (zh) | 1994-07-20 |
GB9226500D0 (en) | 1993-02-10 |
AU668612B2 (en) | 1996-05-09 |
ES2121957T3 (es) | 1998-12-16 |
HK1008669A1 (en) | 1999-05-14 |
TW288026B (zh) | 1996-10-11 |
CA2111719A1 (en) | 1994-06-20 |
DE69321330D1 (de) | 1998-11-05 |
AU5248793A (en) | 1994-06-30 |
JPH06220163A (ja) | 1994-08-09 |
MY109507A (en) | 1997-02-28 |
KR940014613A (ko) | 1994-07-19 |
KR100289105B1 (ko) | 2001-05-02 |
EP0604089A1 (en) | 1994-06-29 |
EP0604089B1 (en) | 1998-09-30 |
DE69321330T2 (de) | 1999-04-01 |
JP3203460B2 (ja) | 2001-08-27 |
ZA939451B (en) | 1994-08-09 |
US5505895A (en) | 1996-04-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1049177C (zh) | 可固化模塑制品的制造方法 | |
CN1152921C (zh) | 可固化的树脂组合物、其制备方法和由其制造的制品 | |
CN1052741C (zh) | 制备固化塑料模塑制件的方法 | |
CN1152904C (zh) | 不饱和聚酯的制造方法和不饱和聚酯树脂组合物 | |
US5856415A (en) | Optically transparent metal-containing polymers | |
CN1030713C (zh) | 含有相容性化合物的不饱和聚酯树脂组合物 | |
CA2010179C (en) | Resin composition and method of manufacturing the same | |
CN1214060A (zh) | 自二醇二酯制备的聚醚酯树脂 | |
US5904888A (en) | Curable compositions | |
CN1027278C (zh) | 热固化树脂组成物 | |
CN1075825C (zh) | 以不对称二醇和芳香二酸为基的用于聚酯树脂系统的低光滑度添加剂 | |
CN1098355A (zh) | 模压塑料的方法 | |
Kandelbauer et al. | Handbook of thermoset plastics: 6. Unsaturated polyesters and vinyl esters | |
JP2002061134A (ja) | 成形品 | |
CN1633467A (zh) | 液体硬质塑料 | |
JPH078901B2 (ja) | 熱硬化性組成物および硬化樹脂の製造方法 | |
JPH03128936A (ja) | 熱硬化性組成物および硬化樹脂の製法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C53 | Correction of patent of invention or patent application | ||
CB02 | Change of applicant information |
Address after: Basel Applicant after: Ciba Specialty Chemicals Co. Ltd. Address before: Basel Applicant before: Ciba-Geigy AG |
|
COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: CIBA-GEIGY AG TO: XIBA SPECIAL CHEMICAL COMPANY SHARES |
|
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C53 | Correction of patent of invention or patent application | ||
COR | Change of bibliographic data |
Free format text: CORRECT: PATENTEE; FROM: CIBA SC HOLDING AG TO: VANTICO AG |
|
CP01 | Change in the name or title of a patent holder |
Patentee after: Vandiek Inc Patentee before: Ciba-Geigy AG |
|
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |