JPS62265315A - Novel hydroxyl group-containing (meth)acrylate polymer - Google Patents
Novel hydroxyl group-containing (meth)acrylate polymerInfo
- Publication number
- JPS62265315A JPS62265315A JP10778186A JP10778186A JPS62265315A JP S62265315 A JPS62265315 A JP S62265315A JP 10778186 A JP10778186 A JP 10778186A JP 10778186 A JP10778186 A JP 10778186A JP S62265315 A JPS62265315 A JP S62265315A
- Authority
- JP
- Japan
- Prior art keywords
- group
- meth
- hydroxyl group
- acrylate
- alkenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 51
- 229920000058 polyacrylate Polymers 0.000 title claims description 13
- -1 alkenyl glycidyl ether Chemical compound 0.000 claims abstract description 31
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 12
- 150000001923 cyclic compounds Chemical class 0.000 claims abstract description 11
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 6
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical group CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical class O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 27
- 229920000642 polymer Polymers 0.000 abstract description 19
- 239000000178 monomer Substances 0.000 abstract description 15
- 125000000962 organic group Chemical group 0.000 abstract description 4
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 239000003607 modifier Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 239000003973 paint Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- FHGVOHPTNJPHNI-UHFFFAOYSA-N (1-hydroxycyclohexyl) prop-2-enoate Chemical compound C=CC(=O)OC1(O)CCCCC1 FHGVOHPTNJPHNI-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- MJYFYGVCLHNRKB-UHFFFAOYSA-N 1,1,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)CF MJYFYGVCLHNRKB-UHFFFAOYSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- DSZTYVZOIUIIGA-UHFFFAOYSA-N 1,2-Epoxyhexadecane Chemical compound CCCCCCCCCCCCCCC1CO1 DSZTYVZOIUIIGA-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- VLJLXEKIAALSJE-UHFFFAOYSA-N 13-oxabicyclo[10.1.0]tridecane Chemical compound C1CCCCCCCCCC2OC21 VLJLXEKIAALSJE-UHFFFAOYSA-N 0.000 description 1
- OLQFXOWPTQTLDP-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCO OLQFXOWPTQTLDP-UHFFFAOYSA-N 0.000 description 1
- RWXMAAYKJDQVTF-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl prop-2-enoate Chemical compound OCCOCCOC(=O)C=C RWXMAAYKJDQVTF-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- CWNOEVURTVLUNV-UHFFFAOYSA-N 2-(propoxymethyl)oxirane Chemical compound CCCOCC1CO1 CWNOEVURTVLUNV-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- CUFXMPWHOWYNSO-UHFFFAOYSA-N 2-[(4-methylphenoxy)methyl]oxirane Chemical compound C1=CC(C)=CC=C1OCC1OC1 CUFXMPWHOWYNSO-UHFFFAOYSA-N 0.000 description 1
- PGYJSURPYAAOMM-UHFFFAOYSA-N 2-ethenoxy-2-methylpropane Chemical compound CC(C)(C)OC=C PGYJSURPYAAOMM-UHFFFAOYSA-N 0.000 description 1
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- IYBOGQYZTIIPNI-UHFFFAOYSA-N 2-methylhexano-6-lactone Chemical compound CC1CCCCOC1=O IYBOGQYZTIIPNI-UHFFFAOYSA-N 0.000 description 1
- OELQSSWXRGADDE-UHFFFAOYSA-N 2-methylprop-2-eneperoxoic acid Chemical compound CC(=C)C(=O)OO OELQSSWXRGADDE-UHFFFAOYSA-N 0.000 description 1
- AAMHBRRZYSORSH-UHFFFAOYSA-N 2-octyloxirane Chemical compound CCCCCCCCC1CO1 AAMHBRRZYSORSH-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical class OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 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
- 150000002170 ethers Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- UCAOGXRUJFKQAP-UHFFFAOYSA-N n,n-dimethyl-5-nitropyridin-2-amine Chemical compound CN(C)C1=CC=C([N+]([O-])=O)C=N1 UCAOGXRUJFKQAP-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野〕
本発明は特定のヒドロキシル基含有アクリレートまたは
メタクリレ−１−（以下、ヒドロキシル基含有（メタ）
アクリレートと略記する。）を構成成分として導かれる
新規な重合体にＩＩＩｙる。更に詳しくは、分子中にヒ
ドロ主シル基と少なくとも１個のアルケニル基を含有す
る新規な（メタ）アクリレートを構成成分とする新規な
重合体に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a specific hydroxyl group-containing acrylate or methacrylate-1- (hereinafter, hydroxyl group-containing (meth)
Abbreviated as acrylate. ) to a novel polymer derived as a constituent component. More specifically, the present invention relates to a novel polymer whose constituent components are novel (meth)acrylates containing a hydro-based sil group and at least one alkenyl group in the molecule.
（従来の技術〕
ヒドロキシエチルアクリレートまたはヒト［ｌキシエヂ
ルメタクリレートのようなヒドロキシ７クリレートまた
はヒドロキシメタクリレート（以下、ヒドロキシ（メタ
）アクリレートと略記覆る。）にエチレンオキシドまた
はプロピレンオキシドを付加させたポリアルキレングリ
コール七ノ（メタ）アクリレート、また、ヒドロキシ（
メタ）アクリレートにε−カブロラク１−ンをイ寸加さ
せたε−力プロラクトン変性ヒドロキシ（メタ）アクリ
レート、さらに、ヒドロキシ（メタ）アクリレートにブ
ヂルグリシジルエーテルやフェニルグリシジルエーテル
を付加させたヒドロキシル基含有（メタ）アクリレート
も知られている。これら公知のヒドロキシル基含有（メ
タ）アクリレートを単独重合、あるいは他のビニルモノ
マーと共重合さけて得られる小合体は、塗料やｍ維改質
ｉ等に使用されたり、また、ポリイソシアネート、エポ
キシ化合物、アミン樹脂笠と反応させることにより秤々
の用途に使用されている。(Prior Art) A polyalkylene glycol obtained by adding ethylene oxide or propylene oxide to hydroxy 7-acrylate or hydroxy methacrylate (hereinafter abbreviated as hydroxy (meth)acrylate) such as hydroxyethyl acrylate or human[l-xyedyl methacrylate] Shichino(meth)acrylate, also hydroxy(
ε-prolactone-modified hydroxy(meth)acrylate, which is obtained by adding ε-cabrolacone to meth)acrylate, and a hydroxyl group obtained by adding butyl glycidyl ether or phenyl glycidyl ether to hydroxy(meth)acrylate. Containing (meth)acrylates are also known. Small polymers obtained by homopolymerizing these known hydroxyl group-containing (meth)acrylates or copolymerizing them with other vinyl monomers are used for paints, fiber modification, etc., and are also used as polyisocyanates and epoxy compounds. It is used in scale applications by reacting with amine resin shade.
しかしながら、これらはすべてヒドロキシル基の反応性
を利用しているものである。従って、これら公知のヒド
ロキシル基含有（メタ）アクリレートを構成成分とする
重合体の用途は限定されたものとなっており、そのため
新規な構造を右するビニルモノマーの開発が望まれてい
るのが現状である。However, all of these utilize the reactivity of hydroxyl groups. Therefore, the uses of polymers containing these known hydroxyl group-containing (meth)acrylates as constituent components are limited, and there is currently a desire to develop vinyl monomers with new structures. It is.
本発明者等は、これらの現状について鋭＠検討の結果、
新規な構造を右するじドロキシル基含有（メタ）アクリ
レートを既に出願している（特願昭６１−２５７８９号
）。本発明者等は、この新規なヒドロキシル基含有（メ
タ）アクリレートより４かれた新規重合体が種々の用途
に利用できることを見い出して、本発明に到達したもの
である。As a result of careful consideration of the current situation, the present inventors have found that
An application has already been filed for (meth)acrylate containing a droxyl group with a new structure (Japanese Patent Application No. 25789/1989). The present inventors have arrived at the present invention by discovering that a novel polymer derived from this novel hydroxyl group-containing (meth)acrylate can be used for various purposes.
寸なわら、前記の新規なヒドロキシル基含有（メタ）ア
クリレートは、分子中にヒドロキシル基と（メタ）アク
リロイル基とアルケニル基の三種類の反応性Ｕを有する
ものであるが、（メタ）アクリロイル基とアルケニル基
のラジカル重合反応性の差異を利用し、重合条件を選択
することにより、ヒドロキシル基とアルケニル基とを含
有する重合体を製造することができる。そして、このよ
うにして得られた重合体は、含有するヒドロキシル基の
反応性を利用して、ポリイソシアネート、エポキシ化合
物、アミノ樹脂等と組合せて、塗料、繊維改質剤、接着
剤等の用途に使用でき、また、アルケニル基の反応性を
利用して、空気硬化型の塗料用ビヒクルや表面改質剤と
して、さらにチオール類やアルキルハイドロジエンポリ
シロキサン等と傷用してコーキング剤や撥水性として使
用でき、また、アルケニル基に各種モノマーをグラフｉ
・反応させて樹脂改質剤として使用するなどの広い用途
を有するものである。The above-mentioned novel hydroxyl group-containing (meth)acrylate has three types of reactive U in the molecule: a hydroxyl group, a (meth)acryloyl group, and an alkenyl group, but the (meth)acryloyl group By utilizing the difference in radical polymerization reactivity between the hydroxyl group and the alkenyl group and selecting polymerization conditions, it is possible to produce a polymer containing a hydroxyl group and an alkenyl group. The polymer thus obtained can be used in applications such as paints, fiber modifiers, adhesives, etc. by combining it with polyisocyanates, epoxy compounds, amino resins, etc. by utilizing the reactivity of the hydroxyl groups it contains. Utilizing the reactivity of the alkenyl group, it can also be used as a vehicle for air-curing paints and as a surface modifier, and can also be used as a caulking agent and water repellent when used with thiols, alkylhydrodiene polysiloxanes, etc. It can also be used as a graph i to add various monomers to alkenyl groups.
・It has a wide range of uses, such as being reacted and used as a resin modifier.
したがって、本発明の目的は、種々の用途に有効に応用
できる新規なヒドロキシル基含有（メタ）アクリレート
重合体を提供することにある。Therefore, an object of the present invention is to provide a novel hydroxyl group-containing (meth)acrylate polymer that can be effectively applied to various uses.
〔問題点を解決するための手段および作用〕本発明は、
一般式
あり、Ｚは炭素数２〜８の二価の有機基を示し、（Ａ）
は下記の一般式（Ｉ）で表わされるアルケニルグリシジ
ルエーテル類の開環基、（Ｂ）は下記の一般式（ＩＩ）
で表わされるアルケニルグリシジルエーテル類を除く環
状化合物の開環基を示し、ｋは１〜２０の！１数、ｌは
Ｏまたは１〜２０の整数を示し、しかも（Ａ）、（Ｂ）
で示されるアルケニルグリシジルエーテル類または環状
化合物の開環基の配列は任意であり、×はラジカル重合
可能な二重結合を有する単量体の残基を示し、ｍは正の
整数、ｎは０または正の整数を示す。）
で表わされ、かつ数平均分子？が１０３〜１０６の範囲
にある新規ヒドロキシル基含有（メタ）アクリレート重
合体に関するものである。[Means and effects for solving the problems] The present invention has the following features:
There is a general formula, Z represents a divalent organic group having 2 to 8 carbon atoms, and (A)
is a ring-opening group of alkenyl glycidyl ethers represented by the following general formula (I), and (B) is the following general formula (II)
represents a ring-opening group of a cyclic compound other than alkenyl glycidyl ethers, where k is 1 to 20! 1 number, l indicates O or an integer from 1 to 20, and (A), (B)
The arrangement of the ring-opening group of the alkenyl glycidyl ether or cyclic compound represented by is arbitrary, × indicates a monomer residue having a radically polymerizable double bond, m is a positive integer, and n is 0. or indicates a positive integer. ) and is a number average molecule? The present invention relates to a novel hydroxyl group-containing (meth)acrylate polymer in which the number is in the range of 103 to 106.
（記）
♂＼ ・
Ｒ’ Ｈ−ＣＨ−ＣＨ２０Ｒ（Ｉｔ）〔ただ
し式中、Ｒは水素原子または炭素数２０以下の（ハロ置
換）炭化水素基であり、Ｒ２は炭素数２０以下のアルケ
ニル基である。〕本発明の新規ヒドロキシル基含有（メ
タ）アクリレート重合体は、一般式
〔ただし式中、Ｒは水素原子またはメチル基であり、Ｚ
は炭素数２〜８の二価の有機基を示し、（Ａ）は前記の
一般式（Ｉｆ＞で表わされるアルケニルグリシジルエー
テル類の１ｍ［４、（［３）は前記の一般式（ｎ）で表
わされるアルケニルグリシジルニーデル類を除く環状化
合物の開環基を示し、ｋは１〜２０の整数、ｌは０また
は１〜２０の整数を示し、しかも（Ａ） 、（Ｂ）で示
されるアルケニルグリシジルエーテル類または環状化合
物の開環基の配列は任意である。〕で表わされるヒドロ
キシル基含有（メタ）アクリレート単独、あるいはラジ
カル重合可能な二重結合を有する他の単量体と共に重合
させることによって得られるｂのである。(Note) ♂＼ ・R' H-CH-CH20R (It) [wherein, R is a hydrogen atom or a (halo-substituted) hydrocarbon group having 20 or less carbon atoms, and R2 is an alkenyl group having 20 or less carbon atoms It is. ] The novel hydroxyl group-containing (meth)acrylate polymer of the present invention has the general formula [wherein R is a hydrogen atom or a methyl group, and Z
represents a divalent organic group having 2 to 8 carbon atoms, (A) is an alkenyl glycidyl ether represented by the above general formula (If) 1m [4, ([3) is the above general formula (n)] represents a ring-opening group of a cyclic compound other than alkenylglycidyl needles represented by, k is an integer of 1 to 20, l is 0 or an integer of 1 to 20, and is represented by (A) or (B). The arrangement of the ring-opening groups of alkenyl glycidyl ethers or cyclic compounds is arbitrary.] Polymerization of the hydroxyl group-containing (meth)acrylate represented by the following alone or together with other monomers having a radically polymerizable double bond. is obtained by b.
本発明に用いる前記一般式（Ｉｆ）で表わされるヒドロ
キシル基含有（メタ）アクリレートは、例えば、一般式
〔ただし式中、Ｒは水素原子またはメチル基、Ｚは炭素
数２〜８の二価の有機基である。〕で表わされるヒドロ
キシ（メタ）アクリレート（イ）のヒドロキシル基に、
一般式
〔ただし式中、Ｒ１は水素原子または炭素数２０以下の
（ハロ置換）炭化水素基であり、Ｒ２は炭素数２０以下
のアルケニル基である。〕で示されるアルケニルグリシ
ジルエーテル類（ロ）および必要により前記一般式で示
されるアルケニルグリシジルエーテル類（ロ）を除く環
状化合物（ハ）を付加反応させる方法により得られる。The hydroxyl group-containing (meth)acrylate represented by the general formula (If) used in the present invention can be, for example, a hydroxyl group-containing (meth)acrylate represented by the general formula [wherein, R is a hydrogen atom or a methyl group, and Z is a divalent It is an organic group. ] to the hydroxyl group of hydroxy (meth)acrylate (a),
General Formula [In the formula, R1 is a hydrogen atom or a (halo-substituted) hydrocarbon group having 20 or less carbon atoms, and R2 is an alkenyl group having 20 or less carbon atoms. ] The alkenyl glycidyl ethers (b) represented by the above general formula and, if necessary, the cyclic compounds (c) other than the alkenyl glycidyl ethers (b) represented by the above general formula are subjected to an addition reaction.
ヒドロキシ（メタ）アクリレート（イ）の具体例として
は、ヒドロキシエチルアクリレート、ヒドロキシエチル
メタクリレート、ヒドロキシプロピルアクリレート、ヒ
ドロキシプロピルメタクリレート、ヒドロキシブチルア
クリレート、ヒドロキシブチルメタクリレート、ジエチ
レングリコールモノアクリレート、ジエチレングリコー
ルモノメタクリレート、ヒドロキシシクロへキシルアク
リレート、ヒドロキシシクロへキシルアクリレート等が
挙げられる。これらは甲独でも、あるいは混合物として
も用いられる。Specific examples of hydroxy(meth)acrylate (a) include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, and hydroxycyclohexyl. Examples include acrylate, hydroxycyclohexyl acrylate, and the like. These can be used either in Japanese or as a mixture.
ヒドロキシ（メタ）アクリレート（イ）へ付加反応させ
る化合物は、前記一般式で表わされるアルケニルグリシ
ジルエーテル類（ロ）および要すればアルケニルグリシ
ジルエーテル類（ロ）を除く環状化合物（ハ）から選ば
れる。The compound to be subjected to the addition reaction to the hydroxy(meth)acrylate (a) is selected from alkenyl glycidyl ethers (b) represented by the above general formula and, if necessary, cyclic compounds (c) excluding the alkenyl glycidyl ethers (b).
アルケニルグリシジルエーテル類（ロ）における（ハロ
置換）炭化水素基としては、例えば炭素数２０以下のア
ルキル基、アルケニル基、アリール基、水添アリール基
、アラルキル基等の炭化水素基あるいはそれらの炭化水
素基の水素原子の少なくとも１個がハロゲン原子で置換
されたへ〇置換炭化水素基が挙げられ、もちろん１べて
の水素原子がハロゲン原子で置換された基であってもよ
い。アルケニルグリシジルエーテル類（ロ）の例として
は、ビニルグリシジルエーテル、アリルグリシジルエー
テル、ブテニルグリシジルエーテル等が挙げられる。Examples of the (halo-substituted) hydrocarbon group in alkenyl glycidyl ethers (b) include hydrocarbon groups such as alkyl groups, alkenyl groups, aryl groups, hydrogenated aryl groups, and aralkyl groups having 20 or less carbon atoms, or their hydrocarbon groups. Examples include a 〇-substituted hydrocarbon group in which at least one hydrogen atom of the group is substituted with a halogen atom, and of course a group in which all hydrogen atoms are substituted with a halogen atom may be used. Examples of the alkenyl glycidyl ethers (b) include vinyl glycidyl ether, allyl glycidyl ether, butenyl glycidyl ether, and the like.
アルケニルグリシジルエーテル類（ロ）を除く環状化合
物（ハ）（以下、これを環状化合物（ハ）と略記する。Cyclic compounds (c) excluding alkenyl glycidyl ethers (b) (hereinafter abbreviated as cyclic compounds (c)).
）の例としては、エチレンオキシド、プロピレンオキシ
ド、１．２−ブチレンオキシド、１．２−エポキシデカ
ン、１．２−エポキシヘキサデカン等のようなアルキレ
ンオキシド類；ブタジェンモノキシド、１．２−エポキ
シ−５−ヘキセン等のようなアルケニルオキシド類；ス
チレンオキシド等のようなフェニルアルキレンオキシド
類；１゜５−シクロドデカジエン−９−１０−エポキシ
ド、１．２−エポキシシクロドデカン等のような水添ア
リールアルキレンオキシド
ン、メチル−ε−カプロラクトン等のようなε−カプロ
ラクトン類：テトラヒド口フラン：メチルグリシジルエ
ーテル、プロピルグリシジルエーテル、ブチルグリシジ
ルエーテル等のようなアルキルグリシジルエーテル類；
フェニルグリシジルエーテル、クレジルグリシジルエー
テル等のようなアリールグリシジルエーテル類；エピク
ロルヒドリン、エビブロモヒドリン等のようなエピハロ
ヒドリン類が挙げられる。) Examples include alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,2-epoxydecane, 1,2-epoxyhexadecane, etc.; butadiene monoxide, 1,2-epoxy- Alkenyl oxides such as 5-hexene; phenylalkylene oxides such as styrene oxide; hydrogenated aryls such as 1゜5-cyclododecadiene-9-10-epoxide, 1,2-epoxycyclododecane, etc. ε-caprolactones such as alkylene oxidone, methyl-ε-caprolactone, etc.; tetrahydrofuran; alkyl glycidyl ethers such as methyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, etc.;
Arylglycidyl ethers such as phenylglycidyl ether, cresylglycidyl ether, and the like; epihalohydrins such as epichlorohydrin, shrimp bromohydrin, and the like.
一般式（Ｉ）中のＸは、前記一般式（Ｉ［［）で表わさ
れるヒドロキ．シル基含有（メタ〉アクリレートと必要
により共重合して用いられるラジカル重合可能な二重結
合を有する他の単聞体の残基である。そのような他の単
品体としては、例えば、アクリル酸ブチル、アクリル酸
−２−エチルヘキシル等のアクリル酸エステル類：メタ
クリル酸メチル、メタクリル酸ブチル等のメタクリル酸
エステル類；アクリル酸、メタクリル酸、マレイン酸、
イタコン酸等の不飽和カルボン酸類；酢酸ビニル、プロ
ピオン酸ビニル等のビニルエステル類：スチレン、ビニ
ルトルエン等の芳香族ビニル類；アクリロニトリル、メ
タクリロニトリル等の不飽和ニトリル類；アクリルアミ
ド、Ｎ−メヂロールアクリルアミド等の不飽和アミド類
：エチレン、プロピレン、イソブチレン等のα−オレフ
ィン類；メチルビニルエーテル、エチルビニルエーテル
、ｔ−ブチルビニルエーテル等のビニルエーテル類；塩
化ビニル、塩化ごニリデン、フッ化ビニル、フッ化ビニ
リデン等の含ハロゲンα，βー不飽和単間体類；（メタ
）アクリル酸トリフルオロエチル、２、 ２， ３．
３−テトラフルオロプロピルアクリレ−］・、ＩＨ，Ｉ
Ｈ，２Ｈ，２Ｈ−へブタデカフルオロデシルアクリレー
ト、ＩＨ，ＩＨ１５Ｈ−オクタフルオロペンチルアクリ
レート等の含フッ素（メタ）アクリル酸エステル類；ビ
ニルトリエトキシシラン、γーメタクリロキシプロピル
トリメトキシシラン等の不飽和シラン類等が挙げられ、
これらの単量体成分の一種又は二種以上の混合物を使用
することができる。X in the general formula (I) is a hydroxy group represented by the general formula (I[[). It is a residue of another monomer having a radically polymerizable double bond, which is used by copolymerizing with sil group-containing (meth)acrylate if necessary.Such other monomers include, for example, acrylic acid Acrylic acid esters such as butyl and 2-ethylhexyl acrylate; Methacrylic acid esters such as methyl methacrylate and butyl methacrylate; Acrylic acid, methacrylic acid, maleic acid,
Unsaturated carboxylic acids such as itaconic acid; Vinyl esters such as vinyl acetate and vinyl propionate; Aromatic vinyls such as styrene and vinyltoluene; Unsaturated nitriles such as acrylonitrile and methacrylonitrile; acrylamide and N-medium Unsaturated amides such as roll acrylamide; α-olefins such as ethylene, propylene, and isobutylene; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and t-butyl vinyl ether; vinyl chloride, nylidene chloride, vinyl fluoride, vinylidene fluoride Halogen-containing α,β-unsaturated monomers such as trifluoroethyl (meth)acrylate, 2, 2, 3.
3-tetrafluoropropyl acrylate], IH,I
Fluorine-containing (meth)acrylic acid esters such as H,2H,2H-hebutadecafluorodecyl acrylate and IH,IH15H-octafluoropentyl acrylate; unsaturated compounds such as vinyltriethoxysilane and γ-methacryloxypropyltrimethoxysilane Examples include silanes,
One or a mixture of two or more of these monomer components can be used.
本発明の新規ヒドロキシル基含有（メタ）アクリレート
重合体は、前記の一般式（Ｉ）で表わされるものである
が、
で表わされる構成単位と
＋Ｘ→−
で表わされる構成単位とはどのような順序で結合してい
てもよい。The novel hydroxyl group-containing (meth)acrylate polymer of the present invention is represented by the above general formula (I), but in what order are the structural units represented by and the structural units represented by +X→- May be combined with
これら構成単位の結合数ｍおよびｎとしては、前者は正
の整数、後者はＯ又は正の整数であり、この範囲で求め
られる性能に応じて適宜法められるもノテある。中でも
、ｍ／（ｍ＋ｎ＞が０．０１〜１．Ｏの範囲のものが種
々の用途に用いられるに際してその性能が浸れており、
特に好ましいものである。The numbers m and n of bonds of these structural units are a positive integer for the former and O or a positive integer for the latter, and may be determined as appropriate depending on the performance required within this range. Among them, those in which m/(m+n> is in the range of 0.01 to 1.0) are known for their performance when used for various purposes,
This is particularly preferred.
本発明の新規ヒドロキシル基含有（メタ）アクリレート
重合体の数平均分子量は、１０３〜１０６の範囲内で適
宜調節することができる。数平均分子けがこの範囲外に
ある重合体を得ようとしても、ゲル化等のため重合反応
の制御が困難となり、前記した各種用途に有効な重合体
を実質上製造することが不可能である。The number average molecular weight of the novel hydroxyl group-containing (meth)acrylate polymer of the present invention can be adjusted as appropriate within the range of 103 to 106. Even if an attempt is made to obtain a polymer with a number average molecular weight outside this range, it will be difficult to control the polymerization reaction due to gelation, etc., and it will be virtually impossible to produce a polymer that is effective for the various uses mentioned above. .
本発明のヒドロキシル基含有（メタ）アクリレート重合
体は、塊状重合、溶液重合、乳化重合等従来公知の重合
方法によって製造することができる。重合開始剤として
は過酸化水素、ベンゾイルパーオキシド、キュメンハイ
ドロパーオキシド等の過酸化物、アゾビスイソブチロニ
トリル等のアゾ化合物、過硫酸アンモニウム等の過硫酸
塩等のラジカル発生剤を重合形態に応じて適宜使用する
ことができる。The hydroxyl group-containing (meth)acrylate polymer of the present invention can be produced by conventionally known polymerization methods such as bulk polymerization, solution polymerization, and emulsion polymerization. As a polymerization initiator, radical generators such as peroxides such as hydrogen peroxide, benzoyl peroxide, and cumene hydroperoxide, azo compounds such as azobisisobutyronitrile, and persulfates such as ammonium persulfate can be used in polymerized form. It can be used as appropriate.
反応温度は、室温から２００℃、好ましくは４０〜１２
０℃の温度で行われる。The reaction temperature is from room temperature to 200°C, preferably from 40 to 12
It is carried out at a temperature of 0°C.
（発明の効果）
本発明の新規な構造を有するヒドロキシル基含有（メタ
）アクリレート重合体は、分子中にヒドロキシル基とア
ルケニル基の二種類の反応性基を有するもので、これら
二種類の官能基を有効に利用して広い用途に使用可能な
ものである。(Effect of the invention) The hydroxyl group-containing (meth)acrylate polymer having a novel structure of the present invention has two types of reactive groups, a hydroxyl group and an alkenyl group, in the molecule, and these two types of functional groups It can be used effectively for a wide range of purposes.
本発明の重合体は、ヒドロキシル基の反応性を利用して
ポリイソシアネート、エポキシ化合物、アミン樹脂等と
組合せて塗料、繊維改質剤、接看剤等の用途に使用でき
、また、アルケニル基の反応性を利用して空気硬化型の
塗料用ビヒクルや表面改質剤として、さらにチオール類
やアルキルハイドロジエンポリシロキサン等と併用して
、コーキング剤や撥水剤として使用でき、また、アルケ
ニル基に各種モノマーをグラフト反応させて樹脂改質剤
として使用するなどの広い用途に利用できるものである
。The polymer of the present invention can be used for applications such as paints, fiber modifiers, and adhesives in combination with polyisocyanates, epoxy compounds, amine resins, etc. by utilizing the reactivity of the hydroxyl group. Utilizing its reactivity, it can be used as an air-curing paint vehicle or surface modifier, and in combination with thiols or alkylhydrodiene polysiloxanes, it can be used as a caulking agent or water repellent. It can be used for a wide range of purposes, such as grafting various monomers and using it as a resin modifier.
以下に実施例をあげて本発明を具体的に説明するが、こ
れらにより本発明は何ら限定を受けるｂのではない。尚
、例中の部はすべて重岱部を示すものとする。The present invention will be specifically explained below with reference to examples, but the present invention is not limited in any way by these examples. Note that all parts in the examples indicate heavy parts.
参考例 １
温度計、撹拌機、滴下ロート、ガス導入管および７ノメ
ーターを備えた反応容器に、２−ヒドロキシエチルメタ
クリレート１９５部（１，５モル）、重合防止剤として
ハイドロキノンモノメチルエーテル０．２１部、触媒と
してタンゲス１−ケイ酸２．８３部を仕込み、５０℃に
てアリルグリシジルエーテル５１３部（４，５モル）を
３時門を要して滴下したのら、更に５０℃にて１時間保
持して反応を完了した。つぎに吸着剤である粉末塩基性
マグネシウム・アルミニウム・ハイドレート・カーボネ
ート・ハイドレート２１部を添加し、６０℃で３０分間
撹拌したのち加圧濾過して精製を行い、無色透明液体の
反応生成物（以下ヒドロキシル基金イｉメタクリレート
（１）と叶ぶ。）６９４部（収率９８．０％）を得た。Reference Example 1 In a reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a gas introduction pipe and a 7-meter, 195 parts (1.5 mol) of 2-hydroxyethyl methacrylate and 0.21 parts of hydroquinone monomethyl ether as a polymerization inhibitor were added. 513 parts (4.5 mol) of allyl glycidyl ether were added dropwise at 50°C over a period of 3 hours. The reaction was completed after a period of time. Next, 21 parts of powdered basic magnesium aluminum hydrate carbonate hydrate, which is an adsorbent, was added, stirred at 60°C for 30 minutes, and purified by pressure filtration to obtain a reaction product as a colorless transparent liquid. (Hereinafter referred to as hydroxyl foundation methacrylate (1).) 694 parts (yield 98.0%) were obtained.
分析の結果、反応生成物は下記構造のヒドロキシル基含
有メタクリレ−１・であった。As a result of analysis, the reaction product was hydroxyl group-containing methacrylate-1 having the following structure.
ＣＨ３
Ｃｌ−１２＝Ｃ−Ｃ００ＣＩ−１２Ｃｌ−１２０−＋Ｃ
ｌ−１２Ｃ１ｌＯ＋−ｔｉＣｌ−１２
■
ＣＨ２
ＣＨ１
参河例 ２ ＣＨ２参考ＰＩ１
１と同様の反応容器に、２−ヒドロキシエチルアクリレ
ート１７４部（１，５モル）、重合防止剤としてハイド
ロキノンモノメチルエーテル０．２６部、触媒としてタ
ングストリン酸２．６部を仕込み、内温を３０〜４０℃
に保ちながら、アリルグリシジルエーテル１７１部（１
，５モル）を１時間で滴下した。滴下終了後、更に１．
５時間、４０℃に保って熟成した。つぎにプロピレンオ
キシド１７４部（３，０モル）を３０〜４０℃で２．５
時間を要して滴下したのち、更に２時間、４０℃に保っ
て熟成し、反応を完了した。粉末ケイ酸マグネシウム１
１部を添加したのち加圧濾過して精製し、無色透明液体
の反応生成物（以下ヒドロキシル基含有アクリレート（
２）と呼ぶ。）５１１部（収率９８．５％）を得た。分
析の結果、反応生成物は下記構造のヒト０キシル基含有
アクリレートであった。CH3Cl-12=C-C00CI-12Cl-120-+C
l-12C11O+-tiCl-12 ■ CH2 CH1 Sample example 2 CH2 reference PI1
174 parts (1.5 moles) of 2-hydroxyethyl acrylate, 0.26 parts of hydroquinone monomethyl ether as a polymerization inhibitor, and 2.6 parts of tungstophosphoric acid as a catalyst were placed in a reaction vessel similar to 1, and the internal temperature was adjusted to 30 ~40℃
171 parts of allyl glycidyl ether (1
, 5 mol) was added dropwise over 1 hour. After the dropping is completed, 1.
It was kept at 40°C for 5 hours and aged. Next, 174 parts (3.0 mol) of propylene oxide was added at 30 to 40°C for 2.5 parts.
After the dropwise addition took some time, the mixture was further aged at 40° C. for 2 hours to complete the reaction. Powdered magnesium silicate 1
After adding 1 part of hydroxyl group-containing acrylate (hereinafter referred to as hydroxyl group-containing acrylate), the reaction product was purified by pressure filtration.
2). ) 511 parts (yield 98.5%) were obtained. As a result of analysis, the reaction product was a human 0xyl group-containing acrylate having the following structure.
テ
ｌ−１２
Ｈ
Ｃ１（２
実施例 １
温度計、ｊマ流冷却器、滴下ｌ」−ト、窒素ガス導入菅
および撹拌機を備えた４つロフラスコに、参考ｐＡ１で
得たヒドロキシル基含有メタクリレ−１・（１）５部、
メチルメタクリレ−１・６５部、ブチルアクリレート２
５部、アクリルＲ５部、アゾビスイソブチロニトリル１
部及びトルエン２００部からなるＥツマ−混合液のうち
の２０ＴＩ１４♀％を仕込み、窒素雰囲気下、撹拌しな
がら８０℃に加熱した。同温度に３０分間保持した後、
モノマー混合液の残部を１時間で滴下した。滴下終了後
、温度を８０℃に保持しながら１時間撹拌を続けた時点
でイソプロピルアルコール１００部を加え、さらに同温
度で２時間撹拌を続けて重合反応を完了し、固形分２４
．９重囲％、粘度（２５℃、Ｂ型粘度ｆｆ＋ ）５２
ｃｐｓのヒドロキシル基含有メタクリレート重合体溶液
（１）を得た。この重合体の数平均分子岱をＧＰＣによ
り測定した結果、３５． ＯＯＯであった。なお、この
重合体の赤外吸収スペクトルを第１図に示した。Example 1 The hydroxyl group-containing methacrylate obtained in reference pA1 was placed in a four-bottle flask equipped with a thermometer, a flow condenser, a dropper, a nitrogen gas introduction tube, and a stirrer. -1・(1) 5 copies,
Methyl methacrylate 1.65 parts, butyl acrylate 2
5 parts, 5 parts of acrylic R, 1 part of azobisisobutyronitrile
20TI and 14♀% of an E-Zimmer mixture consisting of 200 parts and 200 parts of toluene were added, and the mixture was heated to 80° C. with stirring under a nitrogen atmosphere. After keeping at the same temperature for 30 minutes,
The remainder of the monomer mixture was added dropwise over 1 hour. After the dropwise addition was completed, stirring was continued for 1 hour while maintaining the temperature at 80°C, at which point 100 parts of isopropyl alcohol was added, and stirring was continued for another 2 hours at the same temperature to complete the polymerization reaction, resulting in a solid content of 24
．． 9%, viscosity (25°C, B type viscosity ff+) 52
A cps hydroxyl group-containing methacrylate polymer solution (1) was obtained. As a result of measuring the number average molecular weight of this polymer by GPC, it was found to be 35. It was OOO. The infrared absorption spectrum of this polymer is shown in FIG.
次に、１９られたヒドロキシル基含有メタクリレート重
合体溶液（１）１００耶、ＴＳＦ−４８４（メヂルハイ
ドロジエンボリ°シロキサン、東芝シ’Ｊ Ｄ −ン社
袈＞ １．３ 部及び５ＲＸ−２１２（白金系硬化触媒
、東しシリコーン社製） ０．０１部を混合して、表面
処理用混合液を調製した。。Next, 100 parts of the prepared hydroxyl group-containing methacrylate polymer solution (1), 1.3 parts of TSF-484 (medylhydrodiene bolysiloxane, 1.3 parts of 5RX-212), and 1.3 parts of 5RX-212 ( A surface treatment liquid mixture was prepared by mixing 0.01 part of a platinum-based curing catalyst (manufactured by Toshi Silicone Co., Ltd.).
この混合液をワイヤーバーを用いて、ポリエステルフィ
ルム上に乾燥膜厚が１．５μとなる様に塗布し、１２０
℃、１分間乾燥硬化した。得られた塗布フィルムの表面
は、Ｆｉ！！擦係数が０．０５であり、塗７１ｉ前のポ
リニスデルフィルム表面（摩擦係数０゜１５）に比較し
て階れた滑り性を示した。なお、摩擦係数は表面性測定
機（新東科学社装）を用いて測定した。This mixed solution was applied onto a polyester film using a wire bar so that the dry film thickness was 1.5 μm.
℃ for 1 minute. The surface of the obtained coated film is Fi! ! The coefficient of friction was 0.05, showing improved slipperiness compared to the polynisdel film surface before coating 71i (coefficient of friction 0°15). Note that the friction coefficient was measured using a surface property measuring device (Shinto Kagakushaso).
実施例 ２
実施例１と同様の反応容器にドデシルベンゼンスルホン
酸すトリウム０．５部、′ＡＩｖ！ｌ酸アンモニウム０
．４部及び脱イオン水１３０部を仕込み、撹拌下に反応
容器内を窒素置換した後、湯浴中で加熱して液温を６０
℃に保ちながら、参考例２で得たヒドロキシル塁金石ア
クリレート（２）１０部、ブチルアクリレート６０部、
メチルメタクリレート２８部及びアクリル１２部からな
る単ω体混合物と亜硫酸水素すトリウム１市吊％水溶液
２０部とを、それぞれ２時間にわたって滴下した８滴下
終了後、反応液を６０℃で２時間撹拌を続１ノで重合反
応を完了し、固形分３９．５重量％、ｐ Ｈ３，２、粘
度（２５℃、Ｂ型粘度計）４３ｃｐｓのヒドロニ１シル
基金石アクリレート重合体水性分散液（２）を１０だ。Example 2 In a reaction vessel similar to Example 1, 0.5 part of thorium dodecylbenzenesulfonate was added, 'AIv! Ammonium chloride 0
．． 4 parts and 130 parts of deionized water were charged, the inside of the reaction vessel was replaced with nitrogen while stirring, and heated in a hot water bath to bring the liquid temperature to 60%.
While keeping the temperature at
A single omega mixture consisting of 28 parts of methyl methacrylate and 12 parts of acrylic and 20 parts of a 1% aqueous solution of sodium bisulfite were each added dropwise over 2 hours. After the completion of the 8 dropwise additions, the reaction solution was stirred at 60°C for 2 hours. The polymerization reaction was completed in Step 1, and an aqueous dispersion of hydronitrate acrylate polymer (2) having a solid content of 39.5% by weight, a pH of 3.2, and a viscosity (25°C, Type B viscometer) of 43 cps was prepared. It's 10.
この重合体の数平均分子ｍは２５０． ＯＯＯであった
。The number average molecular m of this polymer is 250. It was OOO.
次に、１りられた水性分散液（２）をガラス仮に塗布し
て室温で２週間放置乾燥した塗膜は、ｌ・ルエンに対し
膨潤溶解することがなく、良好な耐溶剤性を有するもの
であった。Next, the aqueous dispersion (2) was temporarily applied to glass and left to dry at room temperature for two weeks.The coating film did not swell or dissolve in l.luene and had good solvent resistance. Met.
実施例 ３
実施例１と同様の反応容器に、実施例２で青た水性分散
液（２）１００部及びドデシルベンゼンスルホン酸ナト
リウム０．４部を溶解した水溶液６０部を仕込み、窒素
置換した後６０℃に胃温した。次いで、スチレン２４部
、アクリロニトリル８部及びメチルアクリレート８部か
らなるグラフト用単ｍ体混合物４０部、濃度０、５１
ｆｆｉ％の過硫酸アンモニウム水溶液２５部並びに濃度
０，５重量％の亜硫酸水素ナトリウム水溶液１０部をそ
れぞれ１．５時間かけて撹拌下に連続滴下し、固形分３
４．１重ω％、Ｄ Ｉ−（２，８、粘度（２５℃、Ｂ型
粘度計）２１ｃｐｓのグラフト共重合体水性分散体（３
）を得た。Example 3 A reaction vessel similar to that in Example 1 was charged with 60 parts of an aqueous solution in which 100 parts of the aqueous dispersion (2) prepared in Example 2 and 0.4 parts of sodium dodecylbenzenesulfonate were dissolved, and the vessel was purged with nitrogen. The stomach was warmed to 60°C. Next, 40 parts of a monomer mixture for grafting consisting of 24 parts of styrene, 8 parts of acrylonitrile, and 8 parts of methyl acrylate, concentrations of 0 and 51
25 parts of ffi% ammonium persulfate aqueous solution and 10 parts of 0.5 wt% sodium hydrogen sulfite aqueous solution were each continuously added dropwise over 1.5 hours with stirring, until the solid content was 3.
Graft copolymer aqueous dispersion (3
) was obtained.
なお、グラフト用単聞体混合物の手合率は９９６１重間
％、グラフト率は７０重澁％であった。The monomer mixture for grafting had a hand yield of 9961% by weight and a grafting ratio of 70% by weight.
このことから明らかなように、本発明の重合体はグラフ
トポリマーのベースポリマーとして使用できることがわ
かる。As is clear from this, it can be seen that the polymer of the present invention can be used as a base polymer for graft polymers.
第１図は実施例１で得たヒドロキシル基含有メタクリレ
ート重合体の赤外吸収スペクトルである。FIG. 1 is an infrared absorption spectrum of the hydroxyl group-containing methacrylate polymer obtained in Example 1.
Claims (1)
範囲にある新規ヒドロキシル基含有（メタ）アクリレー
ト重合体。 （記） ▲数式、化学式、表等があります▼（II） 〔ただし式中、Ｒ＾１は水素原子または炭素数２０以下
の（ハロ置換）炭化水素基であ り、Ｒ＾２は炭素数２０以下のアルケニル基である。〕 ２、アルケニルグリシジルエーテル類がアリルグリシジ
ルエーテルである特許請求の範囲第１項記載の新規ヒド
ロキシル基含有（メタ）アクリレート重合体。 ３、アルケニルグリシジルエーテル類を除く環状化合物
がアルキレンオキシド、ε−カプロラクトン類、テトラ
ヒドロフラン、アルキルグリシジルエーテル、アリール
グリシジルエーテルおよびエピハロヒドリンからなる群
から選ばれた１種または２種以上の化合物である特許請
求の範囲第１項または第２項記載の新規ヒドロキシル基
含有（メタ）アクリレート重合体。 ４、ｍ／（ｍ＋ｎ）が０．０１〜１．０である特許請求
の範囲第１項、第２項または第３項記載の新規ヒドロキ
シル基含有（メタ）アクリレート重合体。[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R is a hydrogen atom or a methyl group, and Z is a divalent organic compound having 2 to 8 carbon atoms. (A) is a ring-opening group of alkenyl glycidyl ethers represented by the following general formula (II), and (B) is a ring-opening group of alkenyl glycidyl ethers represented by the following general formula (II). represents a ring-opening group, k is an integer of 1 to 20, l is 0 or an integer of 1 to 20, and the arrangement of the ring-opening group of the alkenyl glycidyl ethers or cyclic compounds represented by (A) and (B); is arbitrary; A novel hydroxyl group-containing (meth)acrylate polymer having a hydroxyl group in the range of 10^3 to 10^6. (Note) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [In the formula, R^1 is a hydrogen atom or a (halo-substituted) hydrocarbon group having 20 or less carbon atoms, and R^2 is a hydrogen atom with a carbon number of 20 or less. The following alkenyl groups. 2. The novel hydroxyl group-containing (meth)acrylate polymer according to claim 1, wherein the alkenyl glycidyl ether is allyl glycidyl ether. 3. A patent claim in which the cyclic compound other than alkenyl glycidyl ethers is one or more compounds selected from the group consisting of alkylene oxide, ε-caprolactones, tetrahydrofuran, alkyl glycidyl ether, aryl glycidyl ether, and epihalohydrin. A novel hydroxyl group-containing (meth)acrylate polymer according to item 1 or 2. 4. The novel hydroxyl group-containing (meth)acrylate polymer according to claim 1, 2 or 3, wherein m/(m+n) is 0.01 to 1.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10778186A JPS62265315A (en) | 1986-05-13 | 1986-05-13 | Novel hydroxyl group-containing (meth)acrylate polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10778186A JPS62265315A (en) | 1986-05-13 | 1986-05-13 | Novel hydroxyl group-containing (meth)acrylate polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62265315A true JPS62265315A (en) | 1987-11-18 |
Family
ID=14467857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10778186A Pending JPS62265315A (en) | 1986-05-13 | 1986-05-13 | Novel hydroxyl group-containing (meth)acrylate polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62265315A (en) |
-
1986
- 1986-05-13 JP JP10778186A patent/JPS62265315A/en active Pending
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