CA2313359A1 - Curable blends of hydrolysable polyoxypropylenes and epoxy resins - Google Patents
Curable blends of hydrolysable polyoxypropylenes and epoxy resins Download PDFInfo
- Publication number
- CA2313359A1 CA2313359A1 CA002313359A CA2313359A CA2313359A1 CA 2313359 A1 CA2313359 A1 CA 2313359A1 CA 002313359 A CA002313359 A CA 002313359A CA 2313359 A CA2313359 A CA 2313359A CA 2313359 A1 CA2313359 A1 CA 2313359A1
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- CA
- Canada
- Prior art keywords
- group
- molecular weight
- polymer
- curing
- silicon atom
- 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.)
- Abandoned
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 41
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 title abstract description 38
- 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 title description 23
- -1 polyoxypropylenes Polymers 0.000 title description 12
- 229920001451 polypropylene glycol Polymers 0.000 title description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 65
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011342 resin composition Substances 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 125000000524 functional group Chemical group 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000000945 filler Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 150000004756 silanes Chemical class 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 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 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 150000003377 silicon compounds Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 235000014692 zinc oxide Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 230000006399 behavior Effects 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003302 alkenyloxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 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 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-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
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- WGRZHLPEQDVPET-UHFFFAOYSA-N 2-methoxyethoxysilane Chemical compound COCCO[SiH3] WGRZHLPEQDVPET-UHFFFAOYSA-N 0.000 description 1
- OVEUFHOBGCSKSH-UHFFFAOYSA-N 2-methyl-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound CC1=CC=CC=C1N(CC1OC1)CC1OC1 OVEUFHOBGCSKSH-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
- 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 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- QJIVRICYWXNTKE-UHFFFAOYSA-N 4-(8-methylnonoxy)-4-oxobutanoic acid Chemical compound CC(C)CCCCCCCOC(=O)CCC(O)=O QJIVRICYWXNTKE-UHFFFAOYSA-N 0.000 description 1
- VNGLVZLEUDIDQH-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;2-methyloxirane Chemical compound CC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 VNGLVZLEUDIDQH-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 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
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 238000005937 allylation reaction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- MQPPCKJJFDNPHJ-UHFFFAOYSA-K aluminum;3-oxohexanoate Chemical class [Al+3].CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O MQPPCKJJFDNPHJ-UHFFFAOYSA-K 0.000 description 1
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- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
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- 125000005013 aryl ether group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical class FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000013522 chelant Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
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- 238000000748 compression moulding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 1
- XYYQWMDBQFSCPB-UHFFFAOYSA-N dimethoxymethylsilane Chemical compound COC([SiH3])OC XYYQWMDBQFSCPB-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
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- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
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- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000000937 inactivator Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000009191 jumping Effects 0.000 description 1
- 150000004658 ketimines Chemical class 0.000 description 1
- YMQPOZUUTMLSEK-UHFFFAOYSA-L lead(2+);octanoate Chemical compound [Pb+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O YMQPOZUUTMLSEK-UHFFFAOYSA-L 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 1
- GIVYYRXQBRMFEQ-UHFFFAOYSA-N n-butylbutan-1-amine;octan-1-amine Chemical compound CCCCCCCCN.CCCCNCCCC GIVYYRXQBRMFEQ-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- XZZXKVYTWCYOQX-UHFFFAOYSA-J octanoate;tin(4+) Chemical compound [Sn+4].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O XZZXKVYTWCYOQX-UHFFFAOYSA-J 0.000 description 1
- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- BPJZKLBPJBMLQG-KWRJMZDGSA-N propanoyl (z,12r)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OC(=O)CC BPJZKLBPJBMLQG-KWRJMZDGSA-N 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- ACECBHHKGNTVPB-UHFFFAOYSA-N silylformic acid Chemical class OC([SiH3])=O ACECBHHKGNTVPB-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
This invention provides a curable resin composition which has a low viscosity, hence is easy to handle, before curing and, after curing, gives cured products having good tensile characteristics and, in addition good chemical resistance and water resistance.
This composition comprises (A) an oxypropylene polymer having at least one silicon atom-containing group with a hydroxyl group or a hydrolyzable group being bound to the silicon atom and having an Mw/Mn ratio of not more than 1.6 and a number average molecular weight of not less than 6,000, and (B) an epoxy resin.
This invention provides a curable resin composition which has a low viscosity, hence is easy to handle, before curing and, after curing, gives cured products having good tensile characteristics and, in addition good chemical resistance and water resistance.
This composition comprises (A) an oxypropylene polymer having at least one silicon atom-containing group with a hydroxyl group or a hydrolyzable group being bound to the silicon atom and having an Mw/Mn ratio of not more than 1.6 and a number average molecular weight of not less than 6,000, and (B) an epoxy resin.
This composition comprises (A) an oxypropylene polymer having at least one silicon atom-containing group with a hydroxyl group or a hydrolyzable group being bound to the silicon atom and having an Mw/Mn ratio of not more than 1.6 and a number average molecular weight of not less than 6,000, and (B) an epoxy resin.
This invention provides a curable resin composition which has a low viscosity, hence is easy to handle, before curing and, after curing, gives cured products having good tensile characteristics and, in addition good chemical resistance and water resistance.
This composition comprises (A) an oxypropylene polymer having at least one silicon atom-containing group with a hydroxyl group or a hydrolyzable group being bound to the silicon atom and having an Mw/Mn ratio of not more than 1.6 and a number average molecular weight of not less than 6,000, and (B) an epoxy resin.
Description
DESCRIPTION
CURABLE BLENDS OF HYDROLYSABLE
POLYOXYPROPYLENES AND EPOXY RESINS
This application is a division of Canadian Patent Application No. 2,056,360, filed April 3, 1991.
TECHNICAL FIELD
This invention relates to a novel curable resin composition comprising a reactive silicon group-containing oxypropylene polymer and an epoxy resin.
BACKGROUND ART
So far, epoxy resins have been used widely in such fields as various molding materials, adhesives, paints, plywoods and laminates. However, there are problems common to these applications; disadvantageously, cured products are brittle or fragile and, when epoxy resins are used in adhesives, the peel strength is low.
Meanwhile, oxypropylene polymers having a reactive silicon group (a group which is a silicon atom-containing group with a hydroxyl group or a hydrolyzable group being bound to the silicon atom and can form a siloxane bond) have interesting characteristics in that they can be cured at ambient temperature to give rubber-like elastic substances.
Generally, however, they are disadvantageous in that the strength of cured products is low, so that their applications are restricted.
For markedly improving the disadvantageous properties of both, namely the brittleness of cured epoxy resins and the insufficient strength of cured oxypropylene polymers, curable resin compositions in which an epoxy resins and a reactive silicon group-containing oxypropylene polymer are combined have been proposed (e.g. Japanese Kokai Patent Publication No.
61-247723 and No. 61-268720).
However, it has so far been difficult to produce oxypropylene polymers having a high molecular weight with a narrow molecular weight distribution (high monodispersity) and accordingly only reactive silicon group-containing oxypropylene polymers having a broad molecular weight distribution (high poiydispersity) have been known.
Composition in which such oxypropylene polymers having a broad molecular weight distribution cause various inconveniences in practical use thereof; for instance they have a high viscosity and are not easy to handle before curing.
Recently, it has been reported that polyoxypro-pylenes showing a narrow molecular weight distribution can be produced. The present inventors found that compositions comprising an epoxy resin and a polymer derived from an oxypropylene polymer with a narrow molecular weight distribution, which is used as the main chain, by introducing a reactive silicon group either internally or at the terminal of said chain, have a low viscosity and are easy to handle before curing and, after curing, give cured products having excellent tensile character-istics and furthermore good chemical resistance and water resistance. This finding has now led to comple-tion of the present invention.
DISCLOSURE OF INVENTION
The curable resin composition of the invention comprises (A) an oxyprapylene polymer which contains, in its main polymer chain, a repeating unit of the formula I
and which has at least one silicon atom-containing group (reactive silicon group) with a hydroxyl group or a hydrolyzable group being bound to the silicon atom and has an Mw/Mn (weight average molecular weight/
number average molecular weight) ratio of not more than 1.6 and a number average molecular weight (Mn) of not less than 6,000, and (B) an epoxy resin.
BEST MODE FOR CARRYING OUT THE INVENTION
The reactive silicon group contained in the oxypropylene polymer, namely component (A), to be used in the practice of the invention is not limited to any particular species but may typically include, for example, groups of the following general formula (1) R 2 _ b R 3 _ a I
S i - O S i - X $ --- --- ( i Xb m In the above formula, RI and R2 each is an alkyl group containing 1 to 20 carbon atoms, an aryl group containing 6 to 20 carbon atoms, an aralkyl group containing 7 to 20 carbon atoms or a triorganosiloxy group of the formula (R')3Si0-. Where there are two or more R1 or R2 groups, they may be the same or differ-ent. R' is a monovalent hydrocarbon group containing 1 to 20 carbon atoms. The three R' groups may be the same or different. X is a hydroxyl group or a hydro-lyzable group and, where there are two or more X
groups, they may be the same or different. a is 0, 1, 2 or 3 and b is 0, 1 or 2. The number b may vary in the m groups of the formula i R 2 - b I
- S i - O -I
X b m is an integer of 0 to 19. The following condition shall be satisfied: a + Eb >-_ 1.
The hydrolyzable group represented by the above-mentioned X is not particularly limited but may be any hydrolyzable group known in the art. More specifical-ly, there may be mentioned a hydrogen atom, a halogen atom, an alkoxy group; an acyloxy group, a ketoximato group, an amino group, an amido group, an acid amido group, an aminoxy group, a mercapto group, an alkenyl-oxy group and the like. Among these, the hydrogen atom and alkoxy, acyloxy, ketaximato, amino, amido, aminoxy, mercapto and alkenyloxy groups are preferred. From the viewpoint of mild hydrolyzability and easy handling, alkoxy groups, for example methoxy, are particularly preferred.
One to three such hydrolyzable groups or~hydroxyl groups may be bound to one silicon atom, and (a + Eb) is preferably equal to 1 to 5. Where there are two or more hydrolyzable groups or hydroxyl groups in the reactive silicon group, they may be the same or differ-ent.
The reactive silicon group may contain one silicon atom or two or more silicon atoms. In the case of a reactive silican group comprising silicon atoms linked to one another via a siloxane bonding or the like, said group may contain about 20 silicon atoms.
Reactive silicon groups of the following general formula (2) are preferred because of ready availabili-ty.
R 3 - a ... ...
- S i - X a In the above formula, R2, X and a are as defined above.
Specific examples of R1 and R2 appearing in the general formula .(1) given hereinabove include, among others, alkyl groups, such-as methyl and ethyl, cyclo-alkyl groups, such as cyclohexyl, aryl groups, such as phenyl, aralkyl groups, such as benzyl, and triorgano-siloxy groups of the formula (R')3Si0- in which R' is methyl or phenyl. The methyl group is particularly preferred as R1, R2 and/or R'.
The oxypropylene polymer should recommendably contain at least one, preferably i.l to S reactive silicon groups per molecule thereof. When the number of reactive silicon groups contained in the polymer on the per-molecule basis is less than 1, the curability becomes inadequate and a good rubber elastic behavior can hardly be developed.
_ 7 The reactive silicon group may be positioned terminally or internally to the molecular chain of the oxypropylene polymer. When the reactive silicon group occurs terminally to the molecular chain, the oxypro-pylene polymer component contained in the finally formed cured product can have an increased number of effective network chains and therefore a rubber-like cured product showing high strength, high elongation and low elasticity can readily be obtained.
The oxypropylene polymer, which constitutes the main polymer chain in the component (A) to be used in the practice of the invention, contains a repeating unit of the formula C H
This oxypropylene polymer may be straight-chained or branched, or a mixture of these. It may further contain another monomer unit or the like. It is preferable, however, that the polymer contains the monomer unit represented by the above formula in an amount of at least 50°s by weight, more preferably at least 80~ by weight.
The oxypropylene polymer that can effectively be used has a number average molecular weight (Mn) of not less than 6,400, preferably 6,000 to 30,000. Further-more, in this oxypropylene polymer, the weight average molecular weight/number average molecular weight ratio (Mw/Mn) is not more than 1.6, hence the molecular weight distribution is very narrow (the polymer is highly monodisperse). The value of Mw/Mn should preferably be not higher than 1.5, more preferably not higher than 1.4. The molecular weight distribution can be measured by various methods. Generally, however, the measurement method most commonly used is gel permeation chromatography (GPC). Since the molecular weight distribution is narrow in that manner despite the great number average molecular weight, the compo-sition of the invention has a low viscosity before curing, hence is easy to handle and, after curing, shows a good.rubber-like elastic behavior and When used as an adhesive, produces an excellent adhesive streng-th.
The reactive silicon group-containing oxypropylene polymer to be used as component (A) in the practice of the invention is preferably prepared by introducing a reactive silicon group into an oxypropylene polymer having a functional group.
Oxypropylene polymers having a high molecular weight with a narrow molecular weight distribution and having a functional group can hardly be obtained by the conventional method of polymerizing oxypropylene (anionic polymerization using a caustic alkali) or by the chain extension reaction method using oxypropylene polymers obtained by said conventional method as starting materials. They can be obtained, however, by such special polymerization methods as those described in Japanese Rokai Patent Publications Nos. 61-197631, 61-215622, 61-215623 and 61-218632 and Japanese Patent Publications Nos. 46-27250 and 59-15336 and elsewhere.
Since introduction of a reactive silicon group tends to result in a broadened molecular weight distribution as compared with that before introduction, the molecular weight distribution of the polymer before introduction should preferably be as narrow as possible_ The reactive silicon group introduction can be carried out by any appropriate known method. Thus, for example, the following methods may be mentioned.
(1) Rn oxypropylene polymer having a terminal func-tional group, for example a hydroxyl group, is reacted with an organic compound having an active group or unsaturated group reactive with said function group and then the resulting reaction product is hydrosilylated by treatment with a hydrosilane having a hydrolyzable group.
(2) An oxypropylene polymer having a terminal func-tional group (hereinafter referred to as functional group Y), such as a hydroxyl, epoxy or isocyanato group, is reacted with a compound having a functional group (hereinafter referred to as functional group Y') reactive with said functional group Y and a reactive silicon group.
Typical examples of the silicon compound having the functional group Y' include, but are not limited to, amino group-containing silanes, such as y-(2-amino-ethyl)aminopropyltrimethoxysilane, Y-(2-aminoethyl)-aminopropylmethyldimethoxysilane and Y-aminopropyl-triethoxysilane; mercapto group-containing silanes, such as Y-mercaptopropyltrimethoxysilane and y-mer-captopropylmethyldimethoxysilane; epoxysilanes, such as Y-glycidoxypropyltrimethoxysilane and S-(3,4-epoxy cyclohexyl)ethyltrimethoxysilane; vinyl type unsatu-rated group-containing silanes, such as vinyltri-ethoxysilane, Y-methacryloyloxypropyltrimethoxysilane and Y-acryloyloxypropylmethyldimethoxysilane; chlorine atom-containing silanes, such as Y-chloropropyltri-methoxysilane; isocyanato-containing silanes, such as Y-isocyanatopropyltriethoxysilane and Y-isocyanatopro-pylmethyldimethoxysilane; and hydrosilanes, such as methyldimethoxysilane, trimethoxysilane and methyl-diethoxysilane.
Among the methods mentioned above, the method (1), and the method (2) comprising the reaction between a polymer having a terminal hydroxyl group and a compound having an isocyanato group and a reactive silicon group are preferred.
As examples of the epoxy resin which is to be used as component (B) in the practice of the invention, there may be mentioned epichlorohydrin-bisphenol A type epoxy resins, epichlorohydrin-bisphenol F type epoxy resins, tetrabromobisphenol A glycidyl ether and like flame-resistant epoxy resins, novolak type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol A-propylene oxide adduct glycidyl ether type epoxy resins, p-hydroxybenzoic acid glycidyl ether ester type epoxy resins, m-aminophenol-based epoxy resins, diaminodiphenylmethane-based epoxy resins, urethane-modified epoxy resins, various alicyclic epoxy resins, N,N-diglycidylaniline, N,N-diglycidyl-o-tolui-dine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, other glycidyl ethers with a poly-hydric alcohol such as glycerol, hydantoin type epoxy resins, and epoxidation products from unsaturated polymers such as petroleum resin. These are not limitative examples but those epoxy resins that are in general use can be used. Among these epoxy resins, those that have, in their molecule, at least two epoxy groups of the formula -CH - CIi2 O
are preferred.since they are highly reactive in curing and cured products therefrom can readily form a three-dimensional network. As more preferred ones, there may be mentioned bisphenol A type epoxy resins and novolak type epoxy resins.
In the practice of the invention, it is of course possible to use a curing agent for curing the epoxy resin. Usable epoxy resin curing agents are those epoxy curing agents that are commonly used. Such curing agents include, but are not limited to, amines, such as triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, m-xylylenediamine, m-phenylenediamine, diaminodiphenyl-methane, diaminodiphenyl sulfone, isophoronediamine and 2,4,6-tris(dimethylaminomethyl)phenol; tertiary amine salts; polyamide resins; imidazoles; dicyandiamides;
ketimines; boron trifluoride complexes; carboxylic acid anhydrides, such as phthalic anhydride, hexahydrophtha-lic anhydride, tetrahydrophthalic anhydride, endo-methylenetetrahydrophthalic anhydride, dodecylsuccinic anhydride, pyromellitic anhydride and chlorendic an-hydride; alcohols; phenols; carboxylic acids; and the like compounds.
4ahen the curing agent mentioned above is used, its amount to be employed may vary depending on the kind of epoxy resin and the kind of curing agent. Recommend-ably, the curing agent should be used in an amount within the range of 0.1 to 300 parts (parts by weight;
hereinafter the same shall apply) per 100 parts of component (B).
In the composition of the invention, it is prefer-ably, for improving the strength of cured products, to use, as component (C), a silicone compound containing a functional group capable of reacting with the epoxy group and a reactive silicon group within its molecule.
The functional group contained in said silicon compound and capable of reacting with the epoxy group more specifically includes, among others, primary, secondary and tertiary amino groups; mercapto group;
epoxy group; and carboxyl group. As the reactive silicon group, there may be mentioned the same reactive silicon groups that have been mentioned in the descrip-tion of the afore-mentioned component (A). From the easy handling and other viewpoints, alkoxysilyl groups are preferred, however.
As typical examples of such silicon compound, there may be mentioned amino-containing silanes, such as y-aminopropyltrimethoxysilane, y-aminopropyltri-ethoxysilane, y-aminopropylmethyldimethoxysilane, y-(2-aminoethyl)aminopropyltrimethoxysilane, y-(2-aminoethyl)aminopropylmethyldimeth,oxysilane, y-(2-aminoethyl)aminogropyltriethoxysilane, y-ureidopropyl-triethoxysilane, N-~-(N-vinylbenzylaminoethyl)-y-amino-propyltrimethoxysilane and y-anilinopropyltrimethoxy-silane; mercapto-containing silanes, such as y-mercapto-propyltrimethoxysilane, y-mercaptopropyltriethoxy-silane, y-mercaptopropylmethyldimethoxysilane and y-mercaptopropylmethyldiethoxysilane; epoxy bond-containing silanes, such as y-glyeidoxypropyltri-methoxysilane, y-glycidoxypropylmethyldimethoxysilane, y-glycidoxypropyltriethoxysilane and ~-(3,4-epoxy-cyclohexyl)ethyltrimethoxysilane; and carboxysilanes, such as ~-carboxyethyltriethoxysilane, S-carboxy-ethylphenylbis(2-methoxyethoxy)silane and N-~-(N-carb-oxymethylaminoethyl)-y-aminopropyltrimethoxysilane.
These silicon compounds may be used either singly or in combination in the form of a mixture of two or more of them.
It is preferred that the ratio between component (A) and component (B) to be used in the composition of the invention be (A)/(B)=100/1 to 1/100 by weight.
When the ratio (A)/(B) is below 1/100, the impact strength and toughness of cured epoxy resin products can hardly be improved effectively. When the ratio (A)/(B) exceeds 100/1, the strength of cured oxypropylene polymers becomes insufficient. The preferred ratio between component (A) and component (B) may vary depending on the use of the curable resin composition and other factors and therefore cannot be specified without reserve. For instance, for improving the impact resistance, flexibility, toughness, peel strength and other characterisitics of cured epoxy resins, the component (A) should recommendably be used in an amount of 1 to 100 parts, preferably 5 to 100 parts, per 100 parts of component (B). For improving the strength of cured products from a reactive silicon group-containing oxypropylene polymer, which is the component (A), it is recommendable that the component (B) be used in an amount of 1 to 200 parts, preferably to 100 parts, per 100 parts of component (A).
The above-mentioned silicon compound (component (c)) is used preferably in an amount such that the weight ratio relative to components (A) and (B) falls within the range of ((A) + (B))/(C) - 100/0.1 to 100/20, more preferably ((A) + (B))/(C) - 100/0.2 to 100/10.
The method of preparing the curable composition of the invention is not particularly limited but any conventional method can be employed: for example, the components mentioned above are combined and kneaded up in a mixer, roll or kneader at ambient temperature or under heating, or the components are dissolved in a small amount of an appropriate solvent for attaining admixing. Furthermore, it is also possible to prepare one-can or two-can formulas by appropriately combining those components.
The curable resin composition of the invention may contain a silanol condensing catalyst (curing cata-lyst). When a siianol condensing catalyst is used, it may be selected from a wide variety of known ones. As typical examples thereof, there may be mentioned such silanol condensing catalysts as titanate esters, such as tetrabutyl titanate and tetrapropyl titanate; tin carboxylate salts, such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octanoate and tin naphthenate; reaction products from dibutyltin oxide and phthalate esters; dibutyltin diacetylaceto-nate; organic aluminum compounds, such as aluminum trisacetyl-acetonate, aluminum tris(ethyl acetoacetate) and diisopropoxyaluminum ethyl acetoacetate; chelate compounds such as zirconium tetracetylaeetonate and titanium tetracetylacetonate; lead octanoate; amine compounds, such as butylamine, octylamine dibutyl-amine, monoethanolamine, diethanolamine, triethanol-amine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylamino-propylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylamino-methyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole and 1,8-diazabicycloE5.4.0]undecene-7 (DBU), and salts of such amine compounds with carboxy-lic acids and so forth; low molecular weight polyamide resins obtained from an excess of a polyamine and a polybasic acid; reaction products from an excess of a polyamine and an epoxy compound; amino-containing silane coupling agents, such as Y-aminopropyltrimethoxy-silane and N-(ø-aminoethyl)aminopropylmethyldimethoxy-silane; and other known silanol condensing catalysts, such as acid catalysts and basic catalysts. These catalysts may be used either singly or in combination in the form of a mixture of two or more of them.
These silanol condensing catalysts are used preferably in an amount of about 0.1 to 20 parts, more preferably about 1 to 10 parts, per 100 parts of the oxypropylene polymer. When the amount of the silanol condensing catalyst is too small as compared with the oxypropylene polymer, the rate of reaction may be slow in certain instances and the curing reaction can hardly proceed to a satisfactory extent in some instances. On the other hand, if the amount of the silanol condensing catalyst is too large relative to the oxypropylene polymer, local heat generation and/or foaming may occur during curing, unfavorably making it difficult to obtain good cured products.
The curable resin composition of the invention may be modified by incorporating thereinto various fillers.
Usable as the fillers are reinforcing fillers such as fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid and carbon black; fillers such as calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, active zinc white, and "Shirasu" balloons; and fibrous fillers such as asbestos, glass fibers and filaments.
For obtaining cured compositions affording high strength using such fillers, a filler selected from among fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, carbon black, *Trade mark surface-treated finely divided calcium carbonate, calcined clay, clay, active zinc white and the like is used in the main in an amount within the range of 1 to 100 parts per 100 parts of the reactive silicon group-containing oxypropylene polymer to give favorable results. For obtaining cured compositions affording low strength and high elongation, a filler selected from among titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide,"shirasu"
balloons and the like is used in the main in an amount within the range of 5 to 200 parts per 100 parts of the reactive silicon group-containing oxypropylene polymer to give favorable results. Of course, these ffillers may be used either alone or in combination as a mixture of two or more of them .
In using the reactive silicon group-containing oxypropylene polymer in accordance with the invention, a plasticizer may be used more effectively in combina-tion with the filler since the use thereof may provide the cured products with an increased elongation and/or allow incorporation of fillers in large amounts. This plasticizer is any one in common and general use.
Thus, for instance, phthalate esters, such as dioctyl phthalate, dibutyl phthalate and butyl benzyl phtha-late; aliphatic dibasic acid esters, such as dioctyl adipate, isodecyl succinate and dibutyl sebacate;
glycol esters, such as diethylene glycol dibenzoate and pentaerythritol esters; aliphatic esters, such as butyl oleate and methyl acetylricinoleate; phosphate esters, such as tricresyl phosphate, trioctyl phosphate and octyl diphenyl phosphate; epoxy plasticizers, such as epoxidized soybean oil, and benzyl epoxystearate;
polyester plasticizers, such as polyesters from a dibasic acid and a dihydric alcohol; polyethers, such as polypropylene glycol and derivatives thereof;
polystyrenes, such as poly-cx-methylstyrene and poly-styrene; polybutadiene, butadiene-acrylonitrile copo-lymer, polychloroprene, polyisoprene, polybutene, chlorinated paraffin, and so forth may be used either singly or in combination in the form of a mixture of two or more of them, as desired. Favorable results are obtained when the plasticizes is used in an amount within the range of 0 to 100 parts per 100 parts of the reactive silicon group-containing oxypropylene polymer.
In using the curable resin composition of the invention, various additives, such as adhesion impro-vers, physical property modifiers, storage stability improvers, antioxidants, ultraviolet absorbers, metal inactivators, antiozonants, light stabilizers, amine type radical chain inhibitors, phosphorus-containing peroxide decomposing agents, lubricants, pigments, blowing agents, etc., may be added to said composition as necessary each in an appropriate amount.
The curable composition of the invention is curable at a temperature as low as room temperature.
It is also possible to cause rapid curing at a high temperature of about 100 to 150°C. Therefore, said composition can be subjected to curing within a wide temperature_range from such low temperature to such high temperature depending on the purpose. Parti-cularly when an epoxy resin/epoxy resin curing agent combination capable of curing at room temperature is selected, the curable composition of the invention will produce an interesting feature iri that said composition gives high-strength cured products after room tempera-ture curing. Furthermore, when a liquid type epoxy resin is used, another feature will be produced that solvent-free curable compositions can readily be prepared.
The method of molding the curable resin composi-tion of the invention is not critical. However, when the amount of the epoxy resin is greater than that of the reactive silicon group-containing oxypropylene polymer, those methods that are generally used for epoxy resin molding, for example compression molding, transfer molding and injection molding, are preferred and, when molded by such methods, said composition gives moldings, copper-clad laminates, reinforced wood products and other laminated moldings improved in impact resistance, flexibility, toughness and so on.
In addition, when it is formulated as mentioned above, the composition may also be, suitably used as an adhe-sive improved in peel strength, a foaming material improved in flexibility, a binder for fiber boards and particle boards, a paint, a binder for shell molds, a binder for brake linings, a binder for abrasives, a composite material prepared by combining with glass fiber or carbon fiber, and so on.
On the other hand, when the amount of the reactive silicon group-containing oxypropylene polymer is greater than that of the epoxy resin; those molding methods that are generally used in molding solid rubbers such as natural rubber or in molding rubber-like liquid polymers such as polyurethanes are prefer-red and these molding methods give shaped rubber articles, rubber-like foamed products and so on im-proved in strength etc. When the amount of the reac-tive silicon group-containing oxypropylene polymer is greater than that of the epoxy resin, the composition may also be suitably used as a rubber-type adhesive, a sealant, a sticking agent, or the like.
For further illustrating the invention, the following examples are given.
Synthesis Example 1 A flask equipped with a stirrer was charged with 220 g (0.0447 equivalent) of polyoxypropylene triol having a number average molecular weight of 15,000 (Mw/Mn = 1.38, viscosity = 89 poises) and 0.02 g of dibutyltin dilaurate and, in a nitrogen atmosphere, 8.45 g (0.0447 equivalent) of y-isocyanatopropyl-methyldimethoxysilane was added dropwise at room temperature. After completion of the dropping, the reaction was conducted at 75°C for 1.5 hours. IR
spectrum measurement was performed and, after confir-oration of the disappearance of the NCO absorption at about 2280 cm 1 and of the formation of a C=O absorption at about 1730 cm 1, the reaction was discontinued. A
colorless and transparent polymer (2i3 g) was obtained.
Synthesis Example 2 A 1.5-liter pressure-resistant glass reaction vessel was charged with 401 g (0.081 equivalent) of polyoxypropylene triol having a molecular weight of 15,000 (Mw/Mn = 1.38, viscosity = 89 poises) and the contents were placed in a nitrogen atmosphere.
At 137°C, 19.1 g (0.099 equivalent) of a 28$
solution of sodium methoxide in methanol was added dropwise from a dropping funnel, then the reaction was conducted for 5 hours and thereafter the reaction mixture was placed under reduced pressure for volatile matter removal. Again in a nitrogen atmosphere, 9.0 g (0.118 equivalent) of allyl chloride was added drop-wise, the reaction was conducted for 1.5 hours and then the allylation was further carried out using 5.6 g (0.029 equivalent) of a 28% solution of sodium methox-ide in methanol and 2.? g (0.035 equivalent) of allyl chloride.
The reaction product was dissolved in hexane and subjected to adsorption treatment with aluminum sili-cate. The subsequent removal of the hexane under reduced pressure gave 311 g of a yellow and transparent polymer (viscosity = 68 poises).
A pressure-resistant glass reaction vessel was charged with 270 g (0.065 equivalent) of this polymer and the contents were placed in a nitrogen atmosphere.
A chloroplatinic acid catalyst solution (prepared by dissolving 25 g of H2PtC16~6H20 in 500 g of isopropyl alcohol; 0.075 ml) was added and the mixture was stirred for 30 minutes. Dimethoxymethylsilane (6.24 g, 0.059 equivalent) was added from a dropping funnel and the reaction was conducted at 90°C for 4 hours. The subsequent volatile matter removal gave 260 g of a yellow and transparent polymer.
Comparative Synthesis Example 1 A pressure-resistant reaction vessel equipped with a stirrer was charged with 800 g of polypropylene oxide having a number average molecular weight of 8,000 as obtained by subjecting 90 parts of polypropylene glycol (number average molecular weight = 2,500) and 10 parts of polypropylene triol (number average molecular weight - 3,000) (starting materials) to molecular weight jumping reaction using methylene chloride and then capping the molecular chain terminals with allyl chloride to thereby introduce aryl ether groups into 99~ of all terminals. Then, 20 g of methyldimethoxy-silane was added to the vessel. After further addition of 0.40 ml of a chloroplatinic acid catalyst solution (prepared by dissolving 8.9 g of H2PtC16~6H20 in 18 ml of isopropyl alcohol and 160 ml of tetrahydrofuran), the reaction was conducted at 80°C for 6 hours.
The silicon hydride group remaining in the reac-tion mixture was assayed by IR spectrometry and found to be little. As a result of silicon group assay by the NMR method, the product was found to be polypro-pylene oxide containing, terminally to the molecule thereof, about 1.75 groups of the formula ( C H 3 O ) 2 S i C H 2 C H 2 C H 2 O -per molecule.
The viscosity of each of the polymers obtained in Synthesis Examples 1 and 2 and Comparative Synthesis Example 1 was determined at 23°C using a type B visco-meter (BM type rotar No. 4, 12 rpm). Each polymer was also analyzed for number average molecular weight (Mn) and molecular weight distribution (MwlMn) by GPC. The GPC was performed at an oven temperature of 40°C using a column packed with a polystyrene gel (Tosoh Corpora-tion) and tetrahydrofuran as the eluent. The results are shown in Table 1.
Table 1 Viscosity Number average Molecular weight Polymer (Poises) molecular weight distribution (Mn) (Mw/Mn) Synthesis Example 1 150 1.7 x 104 1.4 Synthesis Example 2 88 1.8 x 104 1.5 Comparative Synthesis 240 1.5 x 104 2.3 Example 1 Examples 1 and 2 and Comparative Example 1 One hundred (100) parts of each of the polymers obtained in Synthesis Examples 1 and 2 and Comparative Synthesis Example 1 was thoroughly kneaded with 50 parts of Epikote 828 (bisphenol A type epoxy resin produced by Yuka Shell Epoxy), 1 part of Nocrac*
SP (monophenolic antioxidant produced by Ouchi Shinko Ragaku Rogyo), 5 parts of 2,4,6-tris(dimethylamino-methyl)phenol (DMP-30), 1 part of N-~-(aminoethyl)-Y-aminopropyltrimethoxysilane, 1 part of #918 (organotin compound produced by Sankyo Yuki Gosei) and 0.4 part of water. Among the compositions thus obtained, the compositions of Examples 1 and 2 (in which the polymers of Synthesis Examples 1 and 2 were used, respectively) were lower in viscosity and easier to hand than the composition of Comparative Example 1 (in which the polymer of Comparative Synthesis Example 1 was used).
The compositions obtained were evaluated as adhesives in the following manner.
For tensile shear strength measurement, test samples were prepared according to JIS K 6850 using JIS
H 4000 aluminum plates A-1050P (test pieces 100 x 25 x 2 mm in size) and sticking two plates together with each composition applied with a spatula, under manual pressure.
For T-peel bonding strength evaluation, a T peel *Trade mark a~
test was performed according to JIS K 6854. JIS H 4000 aluminum plates A-1050P (test pieces 200 x 25 x 0.1 mm in size) were used. Each composition mentioned above was applied to a thickness of about 0.5 mm and, after contacting, pressure was applied five times using a 5 kg hand roller and avoiding going and returning in the lengthwise direction.
These adhesion test samples were cured at 23°C for 2 days and further at 50°C for 3 days and then sub-jected to tensile testing. The rate of pulling was adjusted to 50 mm/min for tensile shear testing and 200 mm/min for T peel testing. The results are shown in Table 2.
Table 2 Example 1 Example 2 Comparative Example 1 Polymer used Synthesis Synthesis Comparative Example 1 Example 2 Synthesis Example 1 Tensile shear strength (kg/cm2) 78 76 78 T-peel strength 12 12 13 (kg/25 mm) Examples 3 and 4 and Com arative Exam le 2 The compositions prepared in Examples 1 and 2 and Comparative Example 1 were each spread to give a sheet _ 2g _ having a thickness of 2 mm and cured at 23°C for 2 days and further at 50°C for 3 days. Small pieces (1 cm x 1 cm) were cut out from these sheet-like cured products, weighed, then immersed in 10 ml of 10~ aqueous acetic acid solution and stored at 50°C.
After 14 days, the cured product pieces were taken out and their surfaces were observed. The results are shown in Table 3. In the table,,o means no change and x means surface dissolution.
Table 3 Polymer used Surface condition of cured product piece Example 3 Synthesis Example 1 0 Example 4 Synthesis Example 2 0 Comparative Comparative Example 2 Synthesis Example 1 The surface of the pieces of Comparative Example 2 was sticky and had been dissolved. On the contrary, the pieces of Examples 3 and 4 showed little changes.
Therefore, it was found that the acid resistance had been markedly improved by the present invention.
INDUSTRIAL APPLICABILITY
The reactive silicon group-containing oxypropylene polymer to be used as component (A) in the curable resin ..
composition of the invention has a narrow molecular weight distribution despite of its high number average molecular weight. Therefore, before curing, the composition of the invention is lower in viscosity and easier to handle than compositions containing the conventional reactive silicon group-containing oxypro-pylene polymers having the same molecular weight but showing a broader molecular weight distribution.
The low viscosity before curing as mentioned above not only improves the processability but also enables incorporation of a large amount of filler to give an excellent room temperature curable composition.
After curing, the crosslinking network becomes uniform and the cured products show good rubber-Iike elastic behaviors, for example imgroved elongation characteristics. Thus, when the composition of the invention is used as an adhesive, good bonding strengths are developed.
Furthermore, the chemical resistance, in parti-cular acid resistance, is improved to an unexpectedly great extent. The solvent resistance and water resis-tance are also good.
As mentioned above, the curable resin composition of the invention is of very high practical value.
CURABLE BLENDS OF HYDROLYSABLE
POLYOXYPROPYLENES AND EPOXY RESINS
This application is a division of Canadian Patent Application No. 2,056,360, filed April 3, 1991.
TECHNICAL FIELD
This invention relates to a novel curable resin composition comprising a reactive silicon group-containing oxypropylene polymer and an epoxy resin.
BACKGROUND ART
So far, epoxy resins have been used widely in such fields as various molding materials, adhesives, paints, plywoods and laminates. However, there are problems common to these applications; disadvantageously, cured products are brittle or fragile and, when epoxy resins are used in adhesives, the peel strength is low.
Meanwhile, oxypropylene polymers having a reactive silicon group (a group which is a silicon atom-containing group with a hydroxyl group or a hydrolyzable group being bound to the silicon atom and can form a siloxane bond) have interesting characteristics in that they can be cured at ambient temperature to give rubber-like elastic substances.
Generally, however, they are disadvantageous in that the strength of cured products is low, so that their applications are restricted.
For markedly improving the disadvantageous properties of both, namely the brittleness of cured epoxy resins and the insufficient strength of cured oxypropylene polymers, curable resin compositions in which an epoxy resins and a reactive silicon group-containing oxypropylene polymer are combined have been proposed (e.g. Japanese Kokai Patent Publication No.
61-247723 and No. 61-268720).
However, it has so far been difficult to produce oxypropylene polymers having a high molecular weight with a narrow molecular weight distribution (high monodispersity) and accordingly only reactive silicon group-containing oxypropylene polymers having a broad molecular weight distribution (high poiydispersity) have been known.
Composition in which such oxypropylene polymers having a broad molecular weight distribution cause various inconveniences in practical use thereof; for instance they have a high viscosity and are not easy to handle before curing.
Recently, it has been reported that polyoxypro-pylenes showing a narrow molecular weight distribution can be produced. The present inventors found that compositions comprising an epoxy resin and a polymer derived from an oxypropylene polymer with a narrow molecular weight distribution, which is used as the main chain, by introducing a reactive silicon group either internally or at the terminal of said chain, have a low viscosity and are easy to handle before curing and, after curing, give cured products having excellent tensile character-istics and furthermore good chemical resistance and water resistance. This finding has now led to comple-tion of the present invention.
DISCLOSURE OF INVENTION
The curable resin composition of the invention comprises (A) an oxyprapylene polymer which contains, in its main polymer chain, a repeating unit of the formula I
and which has at least one silicon atom-containing group (reactive silicon group) with a hydroxyl group or a hydrolyzable group being bound to the silicon atom and has an Mw/Mn (weight average molecular weight/
number average molecular weight) ratio of not more than 1.6 and a number average molecular weight (Mn) of not less than 6,000, and (B) an epoxy resin.
BEST MODE FOR CARRYING OUT THE INVENTION
The reactive silicon group contained in the oxypropylene polymer, namely component (A), to be used in the practice of the invention is not limited to any particular species but may typically include, for example, groups of the following general formula (1) R 2 _ b R 3 _ a I
S i - O S i - X $ --- --- ( i Xb m In the above formula, RI and R2 each is an alkyl group containing 1 to 20 carbon atoms, an aryl group containing 6 to 20 carbon atoms, an aralkyl group containing 7 to 20 carbon atoms or a triorganosiloxy group of the formula (R')3Si0-. Where there are two or more R1 or R2 groups, they may be the same or differ-ent. R' is a monovalent hydrocarbon group containing 1 to 20 carbon atoms. The three R' groups may be the same or different. X is a hydroxyl group or a hydro-lyzable group and, where there are two or more X
groups, they may be the same or different. a is 0, 1, 2 or 3 and b is 0, 1 or 2. The number b may vary in the m groups of the formula i R 2 - b I
- S i - O -I
X b m is an integer of 0 to 19. The following condition shall be satisfied: a + Eb >-_ 1.
The hydrolyzable group represented by the above-mentioned X is not particularly limited but may be any hydrolyzable group known in the art. More specifical-ly, there may be mentioned a hydrogen atom, a halogen atom, an alkoxy group; an acyloxy group, a ketoximato group, an amino group, an amido group, an acid amido group, an aminoxy group, a mercapto group, an alkenyl-oxy group and the like. Among these, the hydrogen atom and alkoxy, acyloxy, ketaximato, amino, amido, aminoxy, mercapto and alkenyloxy groups are preferred. From the viewpoint of mild hydrolyzability and easy handling, alkoxy groups, for example methoxy, are particularly preferred.
One to three such hydrolyzable groups or~hydroxyl groups may be bound to one silicon atom, and (a + Eb) is preferably equal to 1 to 5. Where there are two or more hydrolyzable groups or hydroxyl groups in the reactive silicon group, they may be the same or differ-ent.
The reactive silicon group may contain one silicon atom or two or more silicon atoms. In the case of a reactive silican group comprising silicon atoms linked to one another via a siloxane bonding or the like, said group may contain about 20 silicon atoms.
Reactive silicon groups of the following general formula (2) are preferred because of ready availabili-ty.
R 3 - a ... ...
- S i - X a In the above formula, R2, X and a are as defined above.
Specific examples of R1 and R2 appearing in the general formula .(1) given hereinabove include, among others, alkyl groups, such-as methyl and ethyl, cyclo-alkyl groups, such as cyclohexyl, aryl groups, such as phenyl, aralkyl groups, such as benzyl, and triorgano-siloxy groups of the formula (R')3Si0- in which R' is methyl or phenyl. The methyl group is particularly preferred as R1, R2 and/or R'.
The oxypropylene polymer should recommendably contain at least one, preferably i.l to S reactive silicon groups per molecule thereof. When the number of reactive silicon groups contained in the polymer on the per-molecule basis is less than 1, the curability becomes inadequate and a good rubber elastic behavior can hardly be developed.
_ 7 The reactive silicon group may be positioned terminally or internally to the molecular chain of the oxypropylene polymer. When the reactive silicon group occurs terminally to the molecular chain, the oxypro-pylene polymer component contained in the finally formed cured product can have an increased number of effective network chains and therefore a rubber-like cured product showing high strength, high elongation and low elasticity can readily be obtained.
The oxypropylene polymer, which constitutes the main polymer chain in the component (A) to be used in the practice of the invention, contains a repeating unit of the formula C H
This oxypropylene polymer may be straight-chained or branched, or a mixture of these. It may further contain another monomer unit or the like. It is preferable, however, that the polymer contains the monomer unit represented by the above formula in an amount of at least 50°s by weight, more preferably at least 80~ by weight.
The oxypropylene polymer that can effectively be used has a number average molecular weight (Mn) of not less than 6,400, preferably 6,000 to 30,000. Further-more, in this oxypropylene polymer, the weight average molecular weight/number average molecular weight ratio (Mw/Mn) is not more than 1.6, hence the molecular weight distribution is very narrow (the polymer is highly monodisperse). The value of Mw/Mn should preferably be not higher than 1.5, more preferably not higher than 1.4. The molecular weight distribution can be measured by various methods. Generally, however, the measurement method most commonly used is gel permeation chromatography (GPC). Since the molecular weight distribution is narrow in that manner despite the great number average molecular weight, the compo-sition of the invention has a low viscosity before curing, hence is easy to handle and, after curing, shows a good.rubber-like elastic behavior and When used as an adhesive, produces an excellent adhesive streng-th.
The reactive silicon group-containing oxypropylene polymer to be used as component (A) in the practice of the invention is preferably prepared by introducing a reactive silicon group into an oxypropylene polymer having a functional group.
Oxypropylene polymers having a high molecular weight with a narrow molecular weight distribution and having a functional group can hardly be obtained by the conventional method of polymerizing oxypropylene (anionic polymerization using a caustic alkali) or by the chain extension reaction method using oxypropylene polymers obtained by said conventional method as starting materials. They can be obtained, however, by such special polymerization methods as those described in Japanese Rokai Patent Publications Nos. 61-197631, 61-215622, 61-215623 and 61-218632 and Japanese Patent Publications Nos. 46-27250 and 59-15336 and elsewhere.
Since introduction of a reactive silicon group tends to result in a broadened molecular weight distribution as compared with that before introduction, the molecular weight distribution of the polymer before introduction should preferably be as narrow as possible_ The reactive silicon group introduction can be carried out by any appropriate known method. Thus, for example, the following methods may be mentioned.
(1) Rn oxypropylene polymer having a terminal func-tional group, for example a hydroxyl group, is reacted with an organic compound having an active group or unsaturated group reactive with said function group and then the resulting reaction product is hydrosilylated by treatment with a hydrosilane having a hydrolyzable group.
(2) An oxypropylene polymer having a terminal func-tional group (hereinafter referred to as functional group Y), such as a hydroxyl, epoxy or isocyanato group, is reacted with a compound having a functional group (hereinafter referred to as functional group Y') reactive with said functional group Y and a reactive silicon group.
Typical examples of the silicon compound having the functional group Y' include, but are not limited to, amino group-containing silanes, such as y-(2-amino-ethyl)aminopropyltrimethoxysilane, Y-(2-aminoethyl)-aminopropylmethyldimethoxysilane and Y-aminopropyl-triethoxysilane; mercapto group-containing silanes, such as Y-mercaptopropyltrimethoxysilane and y-mer-captopropylmethyldimethoxysilane; epoxysilanes, such as Y-glycidoxypropyltrimethoxysilane and S-(3,4-epoxy cyclohexyl)ethyltrimethoxysilane; vinyl type unsatu-rated group-containing silanes, such as vinyltri-ethoxysilane, Y-methacryloyloxypropyltrimethoxysilane and Y-acryloyloxypropylmethyldimethoxysilane; chlorine atom-containing silanes, such as Y-chloropropyltri-methoxysilane; isocyanato-containing silanes, such as Y-isocyanatopropyltriethoxysilane and Y-isocyanatopro-pylmethyldimethoxysilane; and hydrosilanes, such as methyldimethoxysilane, trimethoxysilane and methyl-diethoxysilane.
Among the methods mentioned above, the method (1), and the method (2) comprising the reaction between a polymer having a terminal hydroxyl group and a compound having an isocyanato group and a reactive silicon group are preferred.
As examples of the epoxy resin which is to be used as component (B) in the practice of the invention, there may be mentioned epichlorohydrin-bisphenol A type epoxy resins, epichlorohydrin-bisphenol F type epoxy resins, tetrabromobisphenol A glycidyl ether and like flame-resistant epoxy resins, novolak type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol A-propylene oxide adduct glycidyl ether type epoxy resins, p-hydroxybenzoic acid glycidyl ether ester type epoxy resins, m-aminophenol-based epoxy resins, diaminodiphenylmethane-based epoxy resins, urethane-modified epoxy resins, various alicyclic epoxy resins, N,N-diglycidylaniline, N,N-diglycidyl-o-tolui-dine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, other glycidyl ethers with a poly-hydric alcohol such as glycerol, hydantoin type epoxy resins, and epoxidation products from unsaturated polymers such as petroleum resin. These are not limitative examples but those epoxy resins that are in general use can be used. Among these epoxy resins, those that have, in their molecule, at least two epoxy groups of the formula -CH - CIi2 O
are preferred.since they are highly reactive in curing and cured products therefrom can readily form a three-dimensional network. As more preferred ones, there may be mentioned bisphenol A type epoxy resins and novolak type epoxy resins.
In the practice of the invention, it is of course possible to use a curing agent for curing the epoxy resin. Usable epoxy resin curing agents are those epoxy curing agents that are commonly used. Such curing agents include, but are not limited to, amines, such as triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, m-xylylenediamine, m-phenylenediamine, diaminodiphenyl-methane, diaminodiphenyl sulfone, isophoronediamine and 2,4,6-tris(dimethylaminomethyl)phenol; tertiary amine salts; polyamide resins; imidazoles; dicyandiamides;
ketimines; boron trifluoride complexes; carboxylic acid anhydrides, such as phthalic anhydride, hexahydrophtha-lic anhydride, tetrahydrophthalic anhydride, endo-methylenetetrahydrophthalic anhydride, dodecylsuccinic anhydride, pyromellitic anhydride and chlorendic an-hydride; alcohols; phenols; carboxylic acids; and the like compounds.
4ahen the curing agent mentioned above is used, its amount to be employed may vary depending on the kind of epoxy resin and the kind of curing agent. Recommend-ably, the curing agent should be used in an amount within the range of 0.1 to 300 parts (parts by weight;
hereinafter the same shall apply) per 100 parts of component (B).
In the composition of the invention, it is prefer-ably, for improving the strength of cured products, to use, as component (C), a silicone compound containing a functional group capable of reacting with the epoxy group and a reactive silicon group within its molecule.
The functional group contained in said silicon compound and capable of reacting with the epoxy group more specifically includes, among others, primary, secondary and tertiary amino groups; mercapto group;
epoxy group; and carboxyl group. As the reactive silicon group, there may be mentioned the same reactive silicon groups that have been mentioned in the descrip-tion of the afore-mentioned component (A). From the easy handling and other viewpoints, alkoxysilyl groups are preferred, however.
As typical examples of such silicon compound, there may be mentioned amino-containing silanes, such as y-aminopropyltrimethoxysilane, y-aminopropyltri-ethoxysilane, y-aminopropylmethyldimethoxysilane, y-(2-aminoethyl)aminopropyltrimethoxysilane, y-(2-aminoethyl)aminopropylmethyldimeth,oxysilane, y-(2-aminoethyl)aminogropyltriethoxysilane, y-ureidopropyl-triethoxysilane, N-~-(N-vinylbenzylaminoethyl)-y-amino-propyltrimethoxysilane and y-anilinopropyltrimethoxy-silane; mercapto-containing silanes, such as y-mercapto-propyltrimethoxysilane, y-mercaptopropyltriethoxy-silane, y-mercaptopropylmethyldimethoxysilane and y-mercaptopropylmethyldiethoxysilane; epoxy bond-containing silanes, such as y-glyeidoxypropyltri-methoxysilane, y-glycidoxypropylmethyldimethoxysilane, y-glycidoxypropyltriethoxysilane and ~-(3,4-epoxy-cyclohexyl)ethyltrimethoxysilane; and carboxysilanes, such as ~-carboxyethyltriethoxysilane, S-carboxy-ethylphenylbis(2-methoxyethoxy)silane and N-~-(N-carb-oxymethylaminoethyl)-y-aminopropyltrimethoxysilane.
These silicon compounds may be used either singly or in combination in the form of a mixture of two or more of them.
It is preferred that the ratio between component (A) and component (B) to be used in the composition of the invention be (A)/(B)=100/1 to 1/100 by weight.
When the ratio (A)/(B) is below 1/100, the impact strength and toughness of cured epoxy resin products can hardly be improved effectively. When the ratio (A)/(B) exceeds 100/1, the strength of cured oxypropylene polymers becomes insufficient. The preferred ratio between component (A) and component (B) may vary depending on the use of the curable resin composition and other factors and therefore cannot be specified without reserve. For instance, for improving the impact resistance, flexibility, toughness, peel strength and other characterisitics of cured epoxy resins, the component (A) should recommendably be used in an amount of 1 to 100 parts, preferably 5 to 100 parts, per 100 parts of component (B). For improving the strength of cured products from a reactive silicon group-containing oxypropylene polymer, which is the component (A), it is recommendable that the component (B) be used in an amount of 1 to 200 parts, preferably to 100 parts, per 100 parts of component (A).
The above-mentioned silicon compound (component (c)) is used preferably in an amount such that the weight ratio relative to components (A) and (B) falls within the range of ((A) + (B))/(C) - 100/0.1 to 100/20, more preferably ((A) + (B))/(C) - 100/0.2 to 100/10.
The method of preparing the curable composition of the invention is not particularly limited but any conventional method can be employed: for example, the components mentioned above are combined and kneaded up in a mixer, roll or kneader at ambient temperature or under heating, or the components are dissolved in a small amount of an appropriate solvent for attaining admixing. Furthermore, it is also possible to prepare one-can or two-can formulas by appropriately combining those components.
The curable resin composition of the invention may contain a silanol condensing catalyst (curing cata-lyst). When a siianol condensing catalyst is used, it may be selected from a wide variety of known ones. As typical examples thereof, there may be mentioned such silanol condensing catalysts as titanate esters, such as tetrabutyl titanate and tetrapropyl titanate; tin carboxylate salts, such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octanoate and tin naphthenate; reaction products from dibutyltin oxide and phthalate esters; dibutyltin diacetylaceto-nate; organic aluminum compounds, such as aluminum trisacetyl-acetonate, aluminum tris(ethyl acetoacetate) and diisopropoxyaluminum ethyl acetoacetate; chelate compounds such as zirconium tetracetylaeetonate and titanium tetracetylacetonate; lead octanoate; amine compounds, such as butylamine, octylamine dibutyl-amine, monoethanolamine, diethanolamine, triethanol-amine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylamino-propylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylamino-methyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole and 1,8-diazabicycloE5.4.0]undecene-7 (DBU), and salts of such amine compounds with carboxy-lic acids and so forth; low molecular weight polyamide resins obtained from an excess of a polyamine and a polybasic acid; reaction products from an excess of a polyamine and an epoxy compound; amino-containing silane coupling agents, such as Y-aminopropyltrimethoxy-silane and N-(ø-aminoethyl)aminopropylmethyldimethoxy-silane; and other known silanol condensing catalysts, such as acid catalysts and basic catalysts. These catalysts may be used either singly or in combination in the form of a mixture of two or more of them.
These silanol condensing catalysts are used preferably in an amount of about 0.1 to 20 parts, more preferably about 1 to 10 parts, per 100 parts of the oxypropylene polymer. When the amount of the silanol condensing catalyst is too small as compared with the oxypropylene polymer, the rate of reaction may be slow in certain instances and the curing reaction can hardly proceed to a satisfactory extent in some instances. On the other hand, if the amount of the silanol condensing catalyst is too large relative to the oxypropylene polymer, local heat generation and/or foaming may occur during curing, unfavorably making it difficult to obtain good cured products.
The curable resin composition of the invention may be modified by incorporating thereinto various fillers.
Usable as the fillers are reinforcing fillers such as fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid and carbon black; fillers such as calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, active zinc white, and "Shirasu" balloons; and fibrous fillers such as asbestos, glass fibers and filaments.
For obtaining cured compositions affording high strength using such fillers, a filler selected from among fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, carbon black, *Trade mark surface-treated finely divided calcium carbonate, calcined clay, clay, active zinc white and the like is used in the main in an amount within the range of 1 to 100 parts per 100 parts of the reactive silicon group-containing oxypropylene polymer to give favorable results. For obtaining cured compositions affording low strength and high elongation, a filler selected from among titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide,"shirasu"
balloons and the like is used in the main in an amount within the range of 5 to 200 parts per 100 parts of the reactive silicon group-containing oxypropylene polymer to give favorable results. Of course, these ffillers may be used either alone or in combination as a mixture of two or more of them .
In using the reactive silicon group-containing oxypropylene polymer in accordance with the invention, a plasticizer may be used more effectively in combina-tion with the filler since the use thereof may provide the cured products with an increased elongation and/or allow incorporation of fillers in large amounts. This plasticizer is any one in common and general use.
Thus, for instance, phthalate esters, such as dioctyl phthalate, dibutyl phthalate and butyl benzyl phtha-late; aliphatic dibasic acid esters, such as dioctyl adipate, isodecyl succinate and dibutyl sebacate;
glycol esters, such as diethylene glycol dibenzoate and pentaerythritol esters; aliphatic esters, such as butyl oleate and methyl acetylricinoleate; phosphate esters, such as tricresyl phosphate, trioctyl phosphate and octyl diphenyl phosphate; epoxy plasticizers, such as epoxidized soybean oil, and benzyl epoxystearate;
polyester plasticizers, such as polyesters from a dibasic acid and a dihydric alcohol; polyethers, such as polypropylene glycol and derivatives thereof;
polystyrenes, such as poly-cx-methylstyrene and poly-styrene; polybutadiene, butadiene-acrylonitrile copo-lymer, polychloroprene, polyisoprene, polybutene, chlorinated paraffin, and so forth may be used either singly or in combination in the form of a mixture of two or more of them, as desired. Favorable results are obtained when the plasticizes is used in an amount within the range of 0 to 100 parts per 100 parts of the reactive silicon group-containing oxypropylene polymer.
In using the curable resin composition of the invention, various additives, such as adhesion impro-vers, physical property modifiers, storage stability improvers, antioxidants, ultraviolet absorbers, metal inactivators, antiozonants, light stabilizers, amine type radical chain inhibitors, phosphorus-containing peroxide decomposing agents, lubricants, pigments, blowing agents, etc., may be added to said composition as necessary each in an appropriate amount.
The curable composition of the invention is curable at a temperature as low as room temperature.
It is also possible to cause rapid curing at a high temperature of about 100 to 150°C. Therefore, said composition can be subjected to curing within a wide temperature_range from such low temperature to such high temperature depending on the purpose. Parti-cularly when an epoxy resin/epoxy resin curing agent combination capable of curing at room temperature is selected, the curable composition of the invention will produce an interesting feature iri that said composition gives high-strength cured products after room tempera-ture curing. Furthermore, when a liquid type epoxy resin is used, another feature will be produced that solvent-free curable compositions can readily be prepared.
The method of molding the curable resin composi-tion of the invention is not critical. However, when the amount of the epoxy resin is greater than that of the reactive silicon group-containing oxypropylene polymer, those methods that are generally used for epoxy resin molding, for example compression molding, transfer molding and injection molding, are preferred and, when molded by such methods, said composition gives moldings, copper-clad laminates, reinforced wood products and other laminated moldings improved in impact resistance, flexibility, toughness and so on.
In addition, when it is formulated as mentioned above, the composition may also be, suitably used as an adhe-sive improved in peel strength, a foaming material improved in flexibility, a binder for fiber boards and particle boards, a paint, a binder for shell molds, a binder for brake linings, a binder for abrasives, a composite material prepared by combining with glass fiber or carbon fiber, and so on.
On the other hand, when the amount of the reactive silicon group-containing oxypropylene polymer is greater than that of the epoxy resin; those molding methods that are generally used in molding solid rubbers such as natural rubber or in molding rubber-like liquid polymers such as polyurethanes are prefer-red and these molding methods give shaped rubber articles, rubber-like foamed products and so on im-proved in strength etc. When the amount of the reac-tive silicon group-containing oxypropylene polymer is greater than that of the epoxy resin, the composition may also be suitably used as a rubber-type adhesive, a sealant, a sticking agent, or the like.
For further illustrating the invention, the following examples are given.
Synthesis Example 1 A flask equipped with a stirrer was charged with 220 g (0.0447 equivalent) of polyoxypropylene triol having a number average molecular weight of 15,000 (Mw/Mn = 1.38, viscosity = 89 poises) and 0.02 g of dibutyltin dilaurate and, in a nitrogen atmosphere, 8.45 g (0.0447 equivalent) of y-isocyanatopropyl-methyldimethoxysilane was added dropwise at room temperature. After completion of the dropping, the reaction was conducted at 75°C for 1.5 hours. IR
spectrum measurement was performed and, after confir-oration of the disappearance of the NCO absorption at about 2280 cm 1 and of the formation of a C=O absorption at about 1730 cm 1, the reaction was discontinued. A
colorless and transparent polymer (2i3 g) was obtained.
Synthesis Example 2 A 1.5-liter pressure-resistant glass reaction vessel was charged with 401 g (0.081 equivalent) of polyoxypropylene triol having a molecular weight of 15,000 (Mw/Mn = 1.38, viscosity = 89 poises) and the contents were placed in a nitrogen atmosphere.
At 137°C, 19.1 g (0.099 equivalent) of a 28$
solution of sodium methoxide in methanol was added dropwise from a dropping funnel, then the reaction was conducted for 5 hours and thereafter the reaction mixture was placed under reduced pressure for volatile matter removal. Again in a nitrogen atmosphere, 9.0 g (0.118 equivalent) of allyl chloride was added drop-wise, the reaction was conducted for 1.5 hours and then the allylation was further carried out using 5.6 g (0.029 equivalent) of a 28% solution of sodium methox-ide in methanol and 2.? g (0.035 equivalent) of allyl chloride.
The reaction product was dissolved in hexane and subjected to adsorption treatment with aluminum sili-cate. The subsequent removal of the hexane under reduced pressure gave 311 g of a yellow and transparent polymer (viscosity = 68 poises).
A pressure-resistant glass reaction vessel was charged with 270 g (0.065 equivalent) of this polymer and the contents were placed in a nitrogen atmosphere.
A chloroplatinic acid catalyst solution (prepared by dissolving 25 g of H2PtC16~6H20 in 500 g of isopropyl alcohol; 0.075 ml) was added and the mixture was stirred for 30 minutes. Dimethoxymethylsilane (6.24 g, 0.059 equivalent) was added from a dropping funnel and the reaction was conducted at 90°C for 4 hours. The subsequent volatile matter removal gave 260 g of a yellow and transparent polymer.
Comparative Synthesis Example 1 A pressure-resistant reaction vessel equipped with a stirrer was charged with 800 g of polypropylene oxide having a number average molecular weight of 8,000 as obtained by subjecting 90 parts of polypropylene glycol (number average molecular weight = 2,500) and 10 parts of polypropylene triol (number average molecular weight - 3,000) (starting materials) to molecular weight jumping reaction using methylene chloride and then capping the molecular chain terminals with allyl chloride to thereby introduce aryl ether groups into 99~ of all terminals. Then, 20 g of methyldimethoxy-silane was added to the vessel. After further addition of 0.40 ml of a chloroplatinic acid catalyst solution (prepared by dissolving 8.9 g of H2PtC16~6H20 in 18 ml of isopropyl alcohol and 160 ml of tetrahydrofuran), the reaction was conducted at 80°C for 6 hours.
The silicon hydride group remaining in the reac-tion mixture was assayed by IR spectrometry and found to be little. As a result of silicon group assay by the NMR method, the product was found to be polypro-pylene oxide containing, terminally to the molecule thereof, about 1.75 groups of the formula ( C H 3 O ) 2 S i C H 2 C H 2 C H 2 O -per molecule.
The viscosity of each of the polymers obtained in Synthesis Examples 1 and 2 and Comparative Synthesis Example 1 was determined at 23°C using a type B visco-meter (BM type rotar No. 4, 12 rpm). Each polymer was also analyzed for number average molecular weight (Mn) and molecular weight distribution (MwlMn) by GPC. The GPC was performed at an oven temperature of 40°C using a column packed with a polystyrene gel (Tosoh Corpora-tion) and tetrahydrofuran as the eluent. The results are shown in Table 1.
Table 1 Viscosity Number average Molecular weight Polymer (Poises) molecular weight distribution (Mn) (Mw/Mn) Synthesis Example 1 150 1.7 x 104 1.4 Synthesis Example 2 88 1.8 x 104 1.5 Comparative Synthesis 240 1.5 x 104 2.3 Example 1 Examples 1 and 2 and Comparative Example 1 One hundred (100) parts of each of the polymers obtained in Synthesis Examples 1 and 2 and Comparative Synthesis Example 1 was thoroughly kneaded with 50 parts of Epikote 828 (bisphenol A type epoxy resin produced by Yuka Shell Epoxy), 1 part of Nocrac*
SP (monophenolic antioxidant produced by Ouchi Shinko Ragaku Rogyo), 5 parts of 2,4,6-tris(dimethylamino-methyl)phenol (DMP-30), 1 part of N-~-(aminoethyl)-Y-aminopropyltrimethoxysilane, 1 part of #918 (organotin compound produced by Sankyo Yuki Gosei) and 0.4 part of water. Among the compositions thus obtained, the compositions of Examples 1 and 2 (in which the polymers of Synthesis Examples 1 and 2 were used, respectively) were lower in viscosity and easier to hand than the composition of Comparative Example 1 (in which the polymer of Comparative Synthesis Example 1 was used).
The compositions obtained were evaluated as adhesives in the following manner.
For tensile shear strength measurement, test samples were prepared according to JIS K 6850 using JIS
H 4000 aluminum plates A-1050P (test pieces 100 x 25 x 2 mm in size) and sticking two plates together with each composition applied with a spatula, under manual pressure.
For T-peel bonding strength evaluation, a T peel *Trade mark a~
test was performed according to JIS K 6854. JIS H 4000 aluminum plates A-1050P (test pieces 200 x 25 x 0.1 mm in size) were used. Each composition mentioned above was applied to a thickness of about 0.5 mm and, after contacting, pressure was applied five times using a 5 kg hand roller and avoiding going and returning in the lengthwise direction.
These adhesion test samples were cured at 23°C for 2 days and further at 50°C for 3 days and then sub-jected to tensile testing. The rate of pulling was adjusted to 50 mm/min for tensile shear testing and 200 mm/min for T peel testing. The results are shown in Table 2.
Table 2 Example 1 Example 2 Comparative Example 1 Polymer used Synthesis Synthesis Comparative Example 1 Example 2 Synthesis Example 1 Tensile shear strength (kg/cm2) 78 76 78 T-peel strength 12 12 13 (kg/25 mm) Examples 3 and 4 and Com arative Exam le 2 The compositions prepared in Examples 1 and 2 and Comparative Example 1 were each spread to give a sheet _ 2g _ having a thickness of 2 mm and cured at 23°C for 2 days and further at 50°C for 3 days. Small pieces (1 cm x 1 cm) were cut out from these sheet-like cured products, weighed, then immersed in 10 ml of 10~ aqueous acetic acid solution and stored at 50°C.
After 14 days, the cured product pieces were taken out and their surfaces were observed. The results are shown in Table 3. In the table,,o means no change and x means surface dissolution.
Table 3 Polymer used Surface condition of cured product piece Example 3 Synthesis Example 1 0 Example 4 Synthesis Example 2 0 Comparative Comparative Example 2 Synthesis Example 1 The surface of the pieces of Comparative Example 2 was sticky and had been dissolved. On the contrary, the pieces of Examples 3 and 4 showed little changes.
Therefore, it was found that the acid resistance had been markedly improved by the present invention.
INDUSTRIAL APPLICABILITY
The reactive silicon group-containing oxypropylene polymer to be used as component (A) in the curable resin ..
composition of the invention has a narrow molecular weight distribution despite of its high number average molecular weight. Therefore, before curing, the composition of the invention is lower in viscosity and easier to handle than compositions containing the conventional reactive silicon group-containing oxypro-pylene polymers having the same molecular weight but showing a broader molecular weight distribution.
The low viscosity before curing as mentioned above not only improves the processability but also enables incorporation of a large amount of filler to give an excellent room temperature curable composition.
After curing, the crosslinking network becomes uniform and the cured products show good rubber-Iike elastic behaviors, for example imgroved elongation characteristics. Thus, when the composition of the invention is used as an adhesive, good bonding strengths are developed.
Furthermore, the chemical resistance, in parti-cular acid resistance, is improved to an unexpectedly great extent. The solvent resistance and water resis-tance are also good.
As mentioned above, the curable resin composition of the invention is of very high practical value.
Claims (4)
1. A curable resin composition which comprises:
(A) an oxypropylene polymer which contains, in its main polymer chain, a repeating unit of the formula and which has at least one silicon atom-containing group with a hydroxyl group or a hydrolyzable group being bound to the silicon atom and has an Mw/Mn ratio of not more than 1.6 and a number average molecular weight of not less than 6,000, and (B) an epoxy resin.
(A) an oxypropylene polymer which contains, in its main polymer chain, a repeating unit of the formula and which has at least one silicon atom-containing group with a hydroxyl group or a hydrolyzable group being bound to the silicon atom and has an Mw/Mn ratio of not more than 1.6 and a number average molecular weight of not less than 6,000, and (B) an epoxy resin.
2. A curable resin composition as claimed in claim 1, wherein the component (A) polymer has an Mw/Mn ratio of not more than 1.5.
3. A curable resin composition as claimed in claim 1, wherein the component (A) polymer has a number average molecular weight of 6,000 to 30,000.
4. A curable resin composition as claimed in claim 1, 2 or 3, wherein the silicon atom-containing group occurs at the terminal of the molecular chain.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2-89713 | 1990-04-03 | ||
JP8971390 | 1990-04-03 | ||
CA002056360A CA2056360C (en) | 1990-04-03 | 1991-04-03 | Curable blends of hydrolysable polyoxypropylenes and epoxy resins |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002056360A Division CA2056360C (en) | 1990-04-03 | 1991-04-03 | Curable blends of hydrolysable polyoxypropylenes and epoxy resins |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2313359A1 true CA2313359A1 (en) | 1991-10-04 |
Family
ID=25674874
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA002313359A Abandoned CA2313359A1 (en) | 1990-04-03 | 1991-04-03 | Curable blends of hydrolysable polyoxypropylenes and epoxy resins |
Country Status (1)
Country | Link |
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CA (1) | CA2313359A1 (en) |
-
1991
- 1991-04-03 CA CA002313359A patent/CA2313359A1/en not_active Abandoned
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