NO168252B - LOOSE, CARBOXYL GROUP-CONTAINED ACRYLATE COPY POLYMERIZATE, PROCEDURE WITH PREPARATION THEREOF, AND USE OF THE ACRYLATE COPOLYMERIZATE IN A COATING AGENT. - Google Patents
LOOSE, CARBOXYL GROUP-CONTAINED ACRYLATE COPY POLYMERIZATE, PROCEDURE WITH PREPARATION THEREOF, AND USE OF THE ACRYLATE COPOLYMERIZATE IN A COATING AGENT. Download PDFInfo
- Publication number
- NO168252B NO168252B NO872278A NO872278A NO168252B NO 168252 B NO168252 B NO 168252B NO 872278 A NO872278 A NO 872278A NO 872278 A NO872278 A NO 872278A NO 168252 B NO168252 B NO 168252B
- Authority
- NO
- Norway
- Prior art keywords
- weight
- monomers
- acrylate copolymer
- olefinically unsaturated
- unsaturated double
- Prior art date
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims description 17
- -1 CARBOXYL Chemical group 0.000 title claims description 14
- 239000011248 coating agent Substances 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title description 2
- 239000000178 monomer Substances 0.000 claims description 111
- 229920001577 copolymer Polymers 0.000 claims description 64
- 239000007787 solid Substances 0.000 claims description 31
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 28
- 125000001302 tertiary amino group Chemical group 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000004132 cross linking Methods 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000007334 copolymerization reaction Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000003505 polymerization initiator Substances 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 6
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 6
- 150000003512 tertiary amines Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004018 acid anhydride group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000003972 cyclic carboxylic anhydrides Chemical class 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 claims 1
- 239000004925 Acrylic resin Substances 0.000 description 25
- 239000000203 mixture Substances 0.000 description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 8
- 150000002118 epoxides Chemical class 0.000 description 8
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000007792 addition Methods 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- 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 6
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229940014800 succinic anhydride Drugs 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 150000003335 secondary amines Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 4
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 4
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 4
- OGBWMWKMTUSNKE-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CCCCCC(OC(=O)C(C)=C)OC(=O)C(C)=C OGBWMWKMTUSNKE-UHFFFAOYSA-N 0.000 description 3
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 235000015927 pasta Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- 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 2
- HSOOIVBINKDISP-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(CCC)OC(=O)C(C)=C HSOOIVBINKDISP-UHFFFAOYSA-N 0.000 description 2
- MIYFFZILCMZNRY-UHFFFAOYSA-N 1-hydroxypentyl prop-2-enoate Chemical compound CCCCC(O)OC(=O)C=C MIYFFZILCMZNRY-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 2
- OCIFJWVZZUDMRL-UHFFFAOYSA-N 6-hydroxyhexyl prop-2-enoate Chemical compound OCCCCCCOC(=O)C=C OCIFJWVZZUDMRL-UHFFFAOYSA-N 0.000 description 2
- JSCDRVVVGGYHSN-UHFFFAOYSA-N 8-hydroxyoctyl prop-2-enoate Chemical compound OCCCCCCCCOC(=O)C=C JSCDRVVVGGYHSN-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 235000011087 fumaric acid Nutrition 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 125000000466 oxiranyl group Chemical group 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- ZWAJLVLEBYIOTI-OLQVQODUSA-N (1s,6r)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCC[C@@H]2O[C@@H]21 ZWAJLVLEBYIOTI-OLQVQODUSA-N 0.000 description 1
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-UHFFFAOYSA-N 0.000 description 1
- WLXGHTAWTRXFTI-UHFFFAOYSA-N 1-(dibutylamino)ethanol Chemical compound CCCCN(C(C)O)CCCC WLXGHTAWTRXFTI-UHFFFAOYSA-N 0.000 description 1
- NCXUNZWLEYGQAH-UHFFFAOYSA-N 1-(dimethylamino)propan-2-ol Chemical compound CC(O)CN(C)C NCXUNZWLEYGQAH-UHFFFAOYSA-N 0.000 description 1
- COKMLVOGWBEPNX-UHFFFAOYSA-N 1-(dipropylamino)ethanol Chemical compound CCCN(C(C)O)CCC COKMLVOGWBEPNX-UHFFFAOYSA-N 0.000 description 1
- SVZXPYMXOAPDNI-UHFFFAOYSA-N 1-[di(propan-2-yl)amino]ethanol Chemical compound CC(C)N(C(C)C)C(C)O SVZXPYMXOAPDNI-UHFFFAOYSA-N 0.000 description 1
- NLNUDODFFAWTHQ-UHFFFAOYSA-N 1-ethenyl-2,3-dihydropyrrole Chemical compound C=CN1CCC=C1 NLNUDODFFAWTHQ-UHFFFAOYSA-N 0.000 description 1
- ZCYXFITUYVYSJW-UHFFFAOYSA-N 1-ethenylisoquinoline Chemical compound C1=CC=C2C(C=C)=NC=CC2=C1 ZCYXFITUYVYSJW-UHFFFAOYSA-N 0.000 description 1
- WGCYRFWNGRMRJA-UHFFFAOYSA-N 1-ethylpiperazine Chemical compound CCN1CCNCC1 WGCYRFWNGRMRJA-UHFFFAOYSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- LQJPFRZLZSLIIO-UHFFFAOYSA-N 2,11-dimethyldodeca-2,10-dienediamide Chemical compound NC(=O)C(C)=CCCCCCCC=C(C)C(N)=O LQJPFRZLZSLIIO-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-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
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- JOKWWCUTHYSVSG-UHFFFAOYSA-N 2-(dimethylaminooxy)benzoic acid Chemical compound CN(C)OC1=CC=CC=C1C(O)=O JOKWWCUTHYSVSG-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- KKFDCBRMNNSAAW-UHFFFAOYSA-N 2-(morpholin-4-yl)ethanol Chemical compound OCCN1CCOCC1 KKFDCBRMNNSAAW-UHFFFAOYSA-N 0.000 description 1
- KZTWONRVIPPDKH-UHFFFAOYSA-N 2-(piperidin-1-yl)ethanol Chemical compound OCCN1CCCCC1 KZTWONRVIPPDKH-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
- DJKKWVGWYCKUFC-UHFFFAOYSA-N 2-butoxyethyl 2-methylprop-2-enoate Chemical compound CCCCOCCOC(=O)C(C)=C DJKKWVGWYCKUFC-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- XUGNJOCQALIQFG-UHFFFAOYSA-N 2-ethenylquinoline Chemical compound C1=CC=CC2=NC(C=C)=CC=C21 XUGNJOCQALIQFG-UHFFFAOYSA-N 0.000 description 1
- CHNGPLVDGWOPMD-UHFFFAOYSA-N 2-ethylbutyl 2-methylprop-2-enoate Chemical compound CCC(CC)COC(=O)C(C)=C CHNGPLVDGWOPMD-UHFFFAOYSA-N 0.000 description 1
- NJRHMGPRPPEGQL-UHFFFAOYSA-N 2-hydroxybutyl prop-2-enoate Chemical compound CCC(O)COC(=O)C=C NJRHMGPRPPEGQL-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- LFDKSGOXWIDWPO-UHFFFAOYSA-N 2-o-ethenyl 1-o-(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=COC(=O)C1=CC=CC=C1C(=O)OCC1OC1 LFDKSGOXWIDWPO-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BBPSWYWJFWHIHC-UHFFFAOYSA-N 3,5,5-trimethylhexyl 2-methylprop-2-enoate Chemical compound CC(C)(C)CC(C)CCOC(=O)C(C)=C BBPSWYWJFWHIHC-UHFFFAOYSA-N 0.000 description 1
- FIXKCCRANLATRP-UHFFFAOYSA-N 3,5,5-trimethylhexyl prop-2-enoate Chemical compound CC(C)(C)CC(C)CCOC(=O)C=C FIXKCCRANLATRP-UHFFFAOYSA-N 0.000 description 1
- JRCGLALFKDKSAN-UHFFFAOYSA-N 3-hydroxybutyl prop-2-enoate Chemical compound CC(O)CCOC(=O)C=C JRCGLALFKDKSAN-UHFFFAOYSA-N 0.000 description 1
- ULYIFEQRRINMJQ-UHFFFAOYSA-N 3-methylbutyl 2-methylprop-2-enoate Chemical compound CC(C)CCOC(=O)C(C)=C ULYIFEQRRINMJQ-UHFFFAOYSA-N 0.000 description 1
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- VJOWMORERYNYON-UHFFFAOYSA-N 5-ethenyl-2-methylpyridine Chemical compound CC1=CC=C(C=C)C=N1 VJOWMORERYNYON-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
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- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
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- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-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
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- VEPKQEUBKLEPRA-UHFFFAOYSA-N VX-745 Chemical compound FC1=CC(F)=CC=C1SC1=NN2C=NC(=O)C(C=3C(=CC=CC=3Cl)Cl)=C2C=C1 VEPKQEUBKLEPRA-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 compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000003927 aminopyridines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 229920005605 branched copolymer Polymers 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960004979 fampridine Drugs 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 150000002238 fumaric acids Chemical class 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 1
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 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
- 150000002689 maleic acids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 238000002156 mixing Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- UQUPIHHYKUEXQD-UHFFFAOYSA-N n,n′-dimethyl-1,3-propanediamine Chemical compound CNCCCNC UQUPIHHYKUEXQD-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 125000002743 phosphorus functional group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229940081066 picolinic acid Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- RVEZZJVBDQCTEF-UHFFFAOYSA-N sulfenic acid Chemical class SO RVEZZJVBDQCTEF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Description
Oppfinnelsen vedrører et oppløselig akrylatkopolymerisat, som kan fremstilles ved kopolymerisering av monomere med minst to polymeriserbare, olefinisk umettede dobbeltbindinger, monomere som bærer funksjonelle grupper og andre polymeriserbare monomere med en olefinisk umettet dobbeltbinding, hvorved akrylatkopolymerisatet inneholder karbok-syl-grupper. The invention relates to a soluble acrylate copolymer, which can be produced by copolymerizing monomers with at least two polymerizable, olefinically unsaturated double bonds, monomers carrying functional groups and other polymerizable monomers with an olefinically unsaturated double bond, whereby the acrylate copolymer contains carboxyl groups.
Det er kjent et artsdannede akrylatkopolymerisat fra EP-A-103 199 som er fremstilt ved kopolymerisering fra 10 til 95 vekt-% av t-butylakrylat, 0,1 til 3 vekt-% av polyfunk-sjonelle monomere, som eksempelvis trimetylolpropantriakrylat, 1 til 3 0 vekt-% comonomere med en funksjonell fornettbar gruppe og 0 til 80 vekt-% av andre polymeriserbare, etylenisk umettede monomere. Som comonomere med en funksjonell fornettbar gruppe skal det nevnes blant annet karboksylgruppe-holdige monomere som acrylsyre og metakrylsyre. Fra EP-A-103 199 er det videre kjent en overtrekks-sammensetning som inneholder et karboksylgruppeholdig akrylatkopolymerisat som er fornettet ved innpolymerisering av flere ganger etylenisk umettede monomere og et polyepok-syd som fornetter. De beskrevne forgrenede akrylatkopolymerisater fører til overtrykk med god værbestandighet, særlig god fuktighetsbestandighet, hvilket på den ene side kan tilbakeføres til innholdet av innpolymerisert t-butylakrylat og på den annen side til innholdet av innpolymeriserte flere ganger olefinisk umettede monomere. A species-formed acrylate copolymer is known from EP-A-103 199 which is produced by copolymerizing from 10 to 95% by weight of t-butyl acrylate, 0.1 to 3% by weight of polyfunctional monomers, such as for example trimethylolpropane triacrylate, 1 to 30% by weight of comonomers with a functional crosslinkable group and 0 to 80% by weight of other polymerizable, ethylenically unsaturated monomers. Comonomers with a functional crosslinkable group include carboxyl group-containing monomers such as acrylic acid and methacrylic acid. From EP-A-103 199, a coating composition is also known which contains a carboxyl group-containing acrylate copolymer which is cross-linked by the polymerization of several times ethylenically unsaturated monomers and a polyepoxy which cross-links. The described branched acrylate copolymers lead to overpressure with good weather resistance, particularly good moisture resistance, which can be attributed on the one hand to the content of polymerized t-butyl acrylate and on the other hand to the content of polymerized several times olefinically unsaturated monomers.
Fra EP-B-51 275 er kjent en reaktiv herdbar bindemiddelblanding på basis av spesielle polykarboksylsyreenheter, basert på polymerisasjons- og/eller kondensasjonsprodukter, hvorved karboksylgrupper eksempelvis dannes ved addisjon av sykliske karbonsyreanhydrider på OH-akrylater, og på basis av alifatiske eller sykloalifatiske epoksid-forbindelser. Fordelen med den herdbare bindemiddelblanding består i at det foreligger en katalysator for karboksyepoksy-fornet-ningen i form av metallsalter ved siden av bindemiddelet, slik at en ekstern katalysator kan unngås. From EP-B-51 275 a reactive curable binder mixture is known on the basis of special polycarboxylic acid units, based on polymerization and/or condensation products, whereby carboxyl groups are for example formed by the addition of cyclic carboxylic anhydrides on OH-acrylates, and on the basis of aliphatic or cycloaliphatic epoxide -connections. The advantage of the curable binder mixture is that there is a catalyst for the carboxy-epoxy cross-linking in the form of metal salts next to the binder, so that an external catalyst can be avoided.
Fra EP-A-123 793 er kjent en sammensetning som allerede herder ved romtemperatur, bestående av polyepoksider og polymere, hvilket inneholder karboksylgrupper og tertiære aminogrupper og fremstilles ved omsetning av vinylpolymere som inneholder syreanhydrid- og karboksylgrupper med forbindelser som inneholder minst et aktivt hydrogen, som kan inngå i reaksjon med syreanhydridet, og minst en tertiær aminogruppe som eksempelvis tertiære aminoalkoholer. Den beskrevne sammensetning har den fordel at den herder allerede ved romtemperatur, utviser god bensin-, vann- og alkalibestandighet og at det ikke opptrer uønskede farge-forandringer som kan tilbakeføres på tertiære aminofor-bindelser. From EP-A-123 793 is known a composition which already hardens at room temperature, consisting of polyepoxides and polymers, which contains carboxyl groups and tertiary amino groups and is produced by reacting vinyl polymers containing acid anhydride and carboxyl groups with compounds containing at least one active hydrogen, which can react with the acid anhydride, and at least one tertiary amino group such as tertiary amino alcohols. The described composition has the advantage that it hardens already at room temperature, exhibits good petrol, water and alkali resistance and that no unwanted color changes occur which can be attributed to tertiary amino compounds.
Det japanske utlegningsskrift 53 145/79 beskriver sammensetninger på basis av kopolymerisater med tertiære aminogrupper, karboksylgrupper og fosforgrupper, samt alifatiske polyepoksider. Sammensetningen herder ved relativ lav temperatur og fører til filmer med god løsningsmiddelbestan dighet og værbestandighet. Japanese specification 53 145/79 describes compositions based on copolymers with tertiary amino groups, carboxyl groups and phosphorus groups, as well as aliphatic polyepoxides. The composition hardens at a relatively low temperature and leads to films with good solvent resistance and weather resistance.
Fra DE-OS 2 6 3 5 177 er det kjent sammensetninger av akrylat harpikser og di- og polyepoxider. I akrylatharpiksene er de innpolymerisert cx, e -etylenisk umettede karboksylsyrer, og harpiksene har et syretall fra 70 til 250. Sammensetningen utviser et høyt faststoffinnhold og har gode resultater når det gjelder mekaniske egenskaper, kjemikalie- og løsnings-middelbestandighet samt korrosjonsbestandighet. From DE-OS 2 6 3 5 177 compositions of acrylate resins and di- and polyepoxides are known. Cx, e -ethylenically unsaturated carboxylic acids are polymerized in the acrylate resins, and the resins have an acid number from 70 to 250. The composition exhibits a high solids content and has good results in terms of mechanical properties, chemical and solvent resistance as well as corrosion resistance.
Fra JP-OS 76 338/77 er det kjent en overtrekksammensetning som kan fremstilles ved blanding av akrylat-kopolymerisater fra akrylsyreestere, karboksylgruppeholdige monomerer og akrylmonomerer, som inneholder tertiær nitrogen, som eksempelvis dietylaminoetylakrylat, med polyepoksider. Overtrekkssammensetningen kan herdes ved lav temperatur og har et høyt faststoffinnhold. From JP-OS 76 338/77, a coating composition is known which can be produced by mixing acrylate copolymers from acrylic acid esters, carboxyl group-containing monomers and acrylic monomers, which contain tertiary nitrogen, such as diethylaminoethyl acrylate, for example, with polyepoxides. The coating composition can be cured at a low temperature and has a high solids content.
Fra JP-OS 21 92 67/83 er det kjent en fremgangsmåte ved fremstilling av et overtrekk, ved hvilken et akrylatkopolymerisat som er fremstilt ved kopolymerisering av akrylmonomere med en tertiær aminogruppe, akryl- eller metakrylsyreestere og eventuelt andre monomere, en poly-epoksidkomponent og en karboksylsyregruppe som er aktivert ved en dobbeltbinding og/eller hydroksylgrupper blandes og blandingen påføres substratet. Blandingen herder ved romtemperatur eller noe høyere temperatur, og den slik dannede film har gode fysikalske egenskaper, en god bensinfasthet og god værbestandighet. En fordel med fremgangsmåten beskrevet i JP-OS 21 92 67/83 består i at det ikke opptrer grunnfar-ging av akrylat-oppløsningen ved de tertiære aminogruppene etter lengre lagringstid, hvilket oppnås ved tilsetningen av den aktiverte karboksylsyre. From JP-OS 21 92 67/83, a method for the production of a coating is known, in which an acrylate copolymer which is produced by the copolymerization of acrylic monomers with a tertiary amino group, acrylic or methacrylic acid esters and possibly other monomers, a poly-epoxide component and a carboxylic acid group which is activated by a double bond and/or hydroxyl groups are mixed and the mixture is applied to the substrate. The mixture hardens at room temperature or a slightly higher temperature, and the film thus formed has good physical properties, a good resistance to petrol and good weather resistance. An advantage of the method described in JP-OS 21 92 67/83 is that no basic coloring of the acrylate solution occurs at the tertiary amino groups after a longer storage time, which is achieved by the addition of the activated carboxylic acid.
Fra EP-B-13 439 er det kjent fremstillingen av en tertiær aminogruppe i et akrylatkopolymerisat. Den tertiære aminogruppe erholdes ved omsetningen i akrylatkopolymerisatet innebygde glycerylgrupper med aminer, hvilke inneholder en sekundær aminogruppe og minst en sekundær hydroksylgruppe. From EP-B-13 439 it is known the production of a tertiary amino group in an acrylate copolymer. The tertiary amino group is obtained by reacting glyceryl groups embedded in the acrylate copolymer with amines, which contain a secondary amino group and at least one secondary hydroxyl group.
Hensikten med foreliggende oppfinnelse består i å forbedre egenskapene til overtrekksmiddelet og/eller overtrekket på basis av en epoksy-karboksy-fornetning når det gjelder bestandighet ovenfor langtidsbelastning ved kjemikalier, oppløsningsmidler, når det gjelder bensinfasthet, elasti-siteten av overtrekkene som dannes på basis av overtrekksmidlene, glansen, korrisjonsbestandigheten og når det gjelder bestandighet ovenfor vann og vanndamp. Foruten dette stilles det krav til sammensetningen at den eventuelt herder ved romtemperatur eller noe høyere temperatur og derved for eksempel kan anvendes ved bilreparasjons-lakkeringer. Videre skal det av økonomiske grunner kunne oppnås et høyt faststoffinnhold i det herdbare overtrekksmiddelet ved relativ lav viskositet. The purpose of the present invention is to improve the properties of the coating agent and/or the coating based on an epoxy-carboxy crosslinking in terms of resistance to long-term exposure to chemicals, solvents, in terms of petrol resistance, the elasticity of the coatings which are formed on the basis of the coating agents, the gloss, the corrosion resistance and when it comes to resistance to water and water vapour. In addition to this, there is a requirement for the composition that it possibly hardens at room temperature or a slightly higher temperature and thereby can, for example, be used for car repair paintwork. Furthermore, for economic reasons, it must be possible to achieve a high solids content in the curable coating agent at a relatively low viscosity.
Denne oppgave løses overraskende ved et oppløselig akrylatkopolymerisat, hvilket utviser en høyere andel av innpolymerisert flere ganger etylenisk umettede monomerer enn akrylatharpiksene beskrevet i EP-A-103 199. Sammenlignet med lineære akrylatharpikser og akrylatharpiksene fra EP-A-103 199 kan det ved akrylatkopolymerisatet i henhold til oppfinnelsen oppnås en lavere viskositet ved relativt høyt faststoffinnhold. Først ved reaksjonsbetingelsene i henhold til oppfinnelsen for kopolymerisasjonen kan det innføres andeler på mer enn 3 vekt-% av flere ganger umettede monomerer i akrylatharpiksen. Ved kopolymerisatets sterkt fornettede struktur blir akrylatharpiksens funksjonelle grupper mer reaktive, noe som medfører en stor fordel. This task is surprisingly solved by a soluble acrylate copolymer, which exhibits a higher proportion of polymerized several times ethylenically unsaturated monomers than the acrylate resins described in EP-A-103 199. Compared to linear acrylate resins and the acrylate resins from EP-A-103 199, the acrylate copolymer in according to the invention, a lower viscosity is achieved with a relatively high solids content. Only at the reaction conditions according to the invention for the copolymerization can proportions of more than 3% by weight of polyunsaturated monomers be introduced into the acrylate resin. With the highly cross-linked structure of the copolymer, the acrylate resin's functional groups become more reactive, which entails a major advantage.
Oppgaven som ligger til grunn for oppfinnelsen løses ved det innledningsvis nevnte oppløselige akrylatkopolymerisat som er kjennetegnet ved at det inneholder 3 til 10 vekt-% i forhold til monomerenes samlede vekt av en monomer med minst to polymeriserbare, olefinisk umettede dobbeltbindinger er innpolymerisert i akrylatkopolymerisatet, at monomerene er kopolymerisert i et organisk løsningsmiddel ved 70-130°C, fortrinnsvis ved 80-120°C, under anvendelse av minst 0,5 vekt%, fortrinnsvis minst 2,5% vekt%, beregnet på monomerenes samlede vekt, av en polymerisasjonsregulator og under anvendelse av polymerisasjonsinitiatorer, til et forfornettet, ikke gelatinisert produkt, at polymerisasjonen er utført slik at den resulterer i en løsning av polymerisatet med et faststoffinnhold på 40-65 vekt%, og at syretallet for akrylatkopolymerisatet utgjør 15 til 200, fortrinnsvis 30 til 120. The problem underlying the invention is solved by the initially mentioned soluble acrylate copolymer which is characterized by the fact that it contains 3 to 10% by weight in relation to the total weight of the monomers of a monomer with at least two polymerisable, olefinically unsaturated double bonds polymerized into the acrylate copolymer, that the monomers are copolymerized in an organic solvent at 70-130°C, preferably at 80-120°C, using at least 0.5% by weight, preferably at least 2.5% by weight, calculated on the total weight of the monomers, of a polymerization regulator and using polymerization initiators, to a pre-crosslinked, non-gelatinized product, that the polymerization is carried out so that it results in a solution of the polymer with a solids content of 40-65% by weight, and that the acid number of the acrylate copolymer amounts to 15 to 200, preferably 30 to 120.
En foretrukket gjenstand for oppfinnelsen er et oppløselig akrylatkopolymerisat som er kjennetegnet ved at det kan fremstilles fra A preferred object of the invention is a soluble acrylate copolymer which is characterized by the fact that it can be produced from
al) 3 til 30 vekt-%, fortrinnsvis 5 til 25 vekt-% av en monomer med minst 2 polymeriserbare olefinisk umettede dobbeltbindinger, al) 3 to 30% by weight, preferably 5 to 25% by weight of a monomer with at least 2 polymerizable olefinically unsaturated double bonds,
a2) 3 til 30 vekt-%, fortrinnsvis 5 til 20 vekt-% av en a2) 3 to 30% by weight, preferably 5 to 20% by weight of a
karboksylgruppeholdig monomer og carboxyl group-containing monomer and
a3) 40 til 93 vekt-% av et annet monomer med et polymeriserbar umettet dobbeltbinding, a3) 40 to 93% by weight of another monomer with a polymerizable unsaturated double bond,
hvorved summen av al, a2 og a3 utgjor 100 vekt-%. whereby the sum of al, a2 and a3 amounts to 100% by weight.
Som komponent al kan det med fordel anvendes forbindelser med den generelle formel Compounds with the general formula can advantageously be used as component al
hvori de følgende betydninger gjelder: in which the following meanings apply:
R = H eller CH3R = H or CH 3
X = O, S, NR' hvor R' = H, alkyl, akryl X = O, S, NR' where R' = H, alkyl, acrylic
n = 2 til 8 n = 2 to 8
Eksempler på slike forbindelser er heksandioldiakrylat, heksandioldimetakrylat, glykoldiakrylat, glykoldimetakrylat, butandioldiakrylat, butandioldimetakrylat, heksa-metylenbismetakrylamid, trimetylolpropantriakrylat, trimetylolpropantrimetakrylat og lignende forbindelser. Examples of such compounds are hexanediol diacrylate, hexanediol dimethacrylate, glycol diacrylate, glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, hexamethylenebismethacrylamide, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate and similar compounds.
Naturligvis kan det også anvendes kombinasjoner av de flere ganger umettede monomere. Andre mulige komponenter al er omsetningsprodukter av en karboksylsyre med en polymeriserbar, olefinisk umettet dobbeltbinding og glycidylakrylat og/eller glycidylmetakrylat. Som komponent al kan det også anvendes en polykarboksylsyre som er forestret med en umettet alkohol som inneholder en polymeriserbar dobbeltbinding eller en umettet monokarboksylsyre. Videre kan også diolefiner, som divinylbenzen anvendes. Som monomere med minst to polymeriserbare, olefinisk umettede dobbeltbindinger anvendes også omsetningsprodukter av et poly-isocyanat med umettede alkoholer eller aminer som inneholder polymeriserbare dobbeltbindinger. Som eksempel skal det nevnes omsetningsproduktet av et mol heksametylendiisocyanat med to mol allylalkohol. De flere ganger etyleniske umettede monomere kan med fordel være diestere av polyetylenglykol og/eller polypropylenglykol med en gjennomsnittlig molvekt på mindre enn 1500, fortrinnsvis mindre enn 1000, og akrylsyre og/eller metakrylsyre. Naturally, combinations of the polyunsaturated monomers can also be used. Other possible components al are reaction products of a carboxylic acid with a polymerizable, olefinically unsaturated double bond and glycidyl acrylate and/or glycidyl methacrylate. As component al, a polycarboxylic acid esterified with an unsaturated alcohol containing a polymerizable double bond or an unsaturated monocarboxylic acid can also be used. Furthermore, diolefins such as divinylbenzene can also be used. As monomers with at least two polymerizable, olefinically unsaturated double bonds, reaction products of a polyisocyanate with unsaturated alcohols or amines containing polymerizable double bonds are also used. As an example, mention should be made of the reaction product of one mole of hexamethylene diisocyanate with two moles of allyl alcohol. The polyethylenically unsaturated monomers can advantageously be diesters of polyethylene glycol and/or polypropylene glycol with an average molecular weight of less than 1500, preferably less than 1000, and acrylic acid and/or methacrylic acid.
Som komponent a2) regner særlig P-karboksyetylakrylat seg, og videre kommer akrylsyre, metakrylsyre, itakonsyre, krotonsyre, akonitsyre, maleinsyre og fumarsyre eller deres halv estere på tale. As component a2), P-carboxyethyl acrylate is especially important, and acrylic acid, methacrylic acid, itaconic acid, crotonic acid, aconitic acid, maleic acid and fumaric acid or their half esters are also mentioned.
Utvalget av komponenten a3) retter seg vidtgående etter de ønskede egenskaper til akrylatkopolymerisatet når det gjelder elastisitet, hardhet, fordragelighet og polaritet. Disse egenskaper lar seg tildels styre ved hjelp av de kjente glassovergangstemperaturer til monomerene. Monomerene kan velges fra gruppen bestående av styren, vinyltolu-en, alkylester av akrylsyren og metakrylsyren, alkoksyety-lakrylater og aryloksyetylakrylater og de tilsvarende metakrylater samt estere av malein- og fumarsyren. The selection of component a3) largely depends on the desired properties of the acrylate copolymer in terms of elasticity, hardness, tolerability and polarity. These properties can partly be controlled using the known glass transition temperatures of the monomers. The monomers can be selected from the group consisting of styrene, vinyltoluene, alkyl esters of acrylic acid and methacrylic acid, alkoxyethyl acrylates and aryloxyethyl acrylates and the corresponding methacrylates as well as esters of maleic and fumaric acids.
Det skal også nevnes metylakrylat, etylakrylat, propyl-akrylat, butylakrylat, isopropylakrylat, isobutylakrylat, pentylakrylat, isoamylakrylat, heksylakrylat, 2-etylheksyl-akrylat, octylakrylat, 3,5,5-trimetylheksylakrylat, decylakrylat, dodecylakrylat, heksadecylakrylat, octadecyl-akrylat, octadecenylakrylat, pentylmetakrylat, isoamylmet-akrylat, heksylmetakrylat, 2-etylbutylmetakrylat, octyl-metakrylat, 3,5,5-trimetylheksylmetakrylat, decylmetakrylat, dodecylmetakrylat, heksadecylmetakrylat, octadecylmetakrylat butoksyetylakrylat, butoksyetylmetakrylat, metylmetakrylat, etylmetakrylat, propylmetakrylat, isopropylmetakrylat, butylmetakrylat, cykloheksylakrylat, cykloheksylmetakrylat, akrylnitril, metacrylnitril, vinylacetat, vinylklorid og fenoksyetylacrylat. Mention should also be made of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isopropyl acrylate, isobutyl acrylate, pentyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, 3,5,5-trimethylhexyl acrylate, decyl acrylate, dodecyl acrylate, hexadecyl acrylate, octadecyl acrylate, octadecenyl acrylate, pentyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-ethylbutyl methacrylate, octyl methacrylate, 3,5,5-trimethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate butoxyethyl acrylate, butoxyethyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, cyclohexyl methacrylate , acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride and phenoxyethyl acrylate.
Andre monomerer kan anvendes såfremt det ikke fører til uønskede egenskaper i kopolymerisatet. Foruten dette kan det som komponent a3) også anvendes hydroksylgruppeholdige monomere, eksempelvis hydroksy-alkylestere til akrylsyren og/eller metakrylsyren. Det er mulig å anvende som en ytterligere monomer med en polymeriserbar olefinisk umettet dobbeltbinding 0,1 vekt-% i forhold til den samlede vekt av alle monomere, monomere med fosforsyre-grupper, altså for eksempel fosforsyreestere med polymeriserbare dobbeltbindinger. Other monomers can be used as long as it does not lead to undesirable properties in the copolymer. In addition to this, monomers containing hydroxyl groups can also be used as component a3), for example hydroxy-alkyl esters of acrylic acid and/or methacrylic acid. It is possible to use as an additional monomer with a polymerizable olefinic unsaturated double bond 0.1% by weight in relation to the total weight of all monomers, monomers with phosphoric acid groups, i.e. for example phosphoric acid esters with polymerizable double bonds.
Særlig fordelaktig er det når det bygges inn monomere i akrylatkopolymerisatet som utviser et syretall på 15 til 200, fortrinnsvis 30 til 120, hvilke monomere inneholder grupper som katalyserer en etterfølgende fornetning av det karboksylgruppeholdige akrylatkopolymerisatet med epoksidgrupper, altså eksempelvis tertiære aminogrupper. It is particularly advantageous when monomers are incorporated into the acrylate copolymer which exhibit an acid number of 15 to 200, preferably 30 to 120, which monomers contain groups which catalyze a subsequent cross-linking of the carboxyl group-containing acrylate copolymer with epoxide groups, i.e. for example tertiary amino groups.
En foretrukket gjenstand for oppfinnelsen er også et løselig akrylatkopolymerisat som er kjennetegnet ved at det kan fremstilles fra A preferred object of the invention is also a soluble acrylate copolymer which is characterized by the fact that it can be produced from
al) 3 til 30 vekt-%, fortrinnsvis 5 til 25 vekt-% av al) 3 to 30% by weight, preferably 5 to 25% by weight of
en monomer med minst to polymeriserbare, olefinisk umettede dobbeltbindinger, hvorved di- og polyestere av di- og polyoler med akrylsyre er uttatt. a monomer with at least two polymerisable, olefinically unsaturated double bonds, whereby di- and polyesters of di- and polyols with acrylic acid have been removed.
a2) 3 til 30 vekt-%, fortrinnsvis 5 til 2 0 vekt-% av en a2) 3 to 30% by weight, preferably 5 to 20% by weight of a
karboksylgruppeholdig monomer, carboxyl group-containing monomer,
a3) 0,1 til 20 vekt-%, fortrinnsvis 1 til 14 vekt-% av en tertiært amin med en polymeriserbar, olefinisk umettet dobbeltbinding, a3) 0.1 to 20% by weight, preferably 1 to 14% by weight of a tertiary amine with a polymerizable, olefinically unsaturated double bond,
a4) 0 til 40 vekt-%, fortrinnsvis 5 til 25 vekt% av en hydroksylgruppeholdig monomer og a4) 0 to 40% by weight, preferably 5 to 25% by weight of a monomer containing a hydroxyl group and
a5) 0 til 80 vekt-% av et annet monomer med en polymeriserbar, olefinisk umettet dobbeltbinding, a5) 0 to 80% by weight of another monomer with a polymerizable, olefinically unsaturated double bond,
hvorved summen av komponentene al, a2, a3, a4 og a5 utgjor 100 vekt-%. whereby the sum of the components a1, a2, a3, a4 and a5 amounts to 100% by weight.
Som komponent al kan det med fordel anvendes forbindelser med den generelle formel Compounds with the general formula can advantageously be used as component al
hvori de følgende betydninger gjelder: in which the following meanings apply:
X = 0, S, NR hvor R = H, alkyl, aryl X = 0, S, NR where R = H, alkyl, aryl
n = 2 til 8 n = 2 to 8
Komponenten al kan være et omsetningsprodukt fra karboksylsyre med en polymeriserbar, olefinisk umettet dobbeltbinding, hvorved akrylsyre er unntatt, og glycidylmetakrylat. Videre kommer polykarboksylsyrer eller umettede monokar-boksylsyrer som er forestret med en umettet alkohol som inneholder en polymeriserbar dobbeltbinding i betraktning, bortsett fra akrylsyrens derivater. Gunstig er også anvendelsen av polyolefiner som for eksempel divinylbenzen. Med fordel velges komponenten al fra produkter som fremstilles av polyisocyanater med umettede alkoholer eller aminer som inneholder polymeriser-bare dobbeltbindinger. Videre kommer diestere av polyetylenglykol og/eller polypropylenglykol med en gjennomsnittlig molvekt på mindre enn 1500, fortrinnsvis mindre enn 1000, og metakrylsyre i betraktning. The component al can be a reaction product from carboxylic acid with a polymerizable, olefinically unsaturated double bond, whereby acrylic acid is excluded, and glycidyl methacrylate. Furthermore, polycarboxylic acids or unsaturated monocarboxylic acids which are esterified with an unsaturated alcohol containing a polymerizable double bond come into consideration, apart from the acrylic acid derivatives. The use of polyolefins such as divinylbenzene is also advantageous. Advantageously, the component al is selected from products which are produced from polyisocyanates with unsaturated alcohols or amines which contain polymerisable double bonds. Furthermore, diesters of polyethylene glycol and/or polypropylene glycol with an average molecular weight of less than 1500, preferably less than 1000, and methacrylic acid come into consideration.
Eksempler på etylenisk umettede forbindelser med en tertiær aminogruppe, altså for komponenten a3, er Examples of ethylenically unsaturated compounds with a tertiary amino group, i.e. for the component a3, are
N, N<*->dimetylaminoetylmetakrylat, N,N', dietylaminoetyl-metakrylat, 2-vinylpyridin og 4-vinylpyridin, vinylpyrrolin, vinylkinolin, vinylisokinolin, N,N'-Dimetyl-aminoetyl- ;vinyleter og 2-metyl-5-vinylpyridin. ;Eventuelt kan det også anvendes hydroksylgruppeholdige monomerer. Som eksempel skal det nevnes hydroksyalkylestere av akryl- og metakrylsyren, som for eksempel hydroksyetylakrylat, hydroksypropylakrylat, hydroksybutylakrylat, hydroksyamylakrylat, hydroksyheksylakrylat, hydroksyoctylakrylat og de tilsvarende metakrylater. Utvalget av andre monomerer med en polymeriserbar, olefinisk umettet dobbeltbinding skjer fra den allerede ovenfornevnte gruppe. Det er også i dette tilfelle fordelaktig at de andre monomerer med polymeriserbare dobbeltbindinger som innsettes i 0,1 til 5 vekt-% i forhold til den samlede vekt av alle monomerer, er monomerer med fosforsyregrupper. ;I henhold til oppfinnelsen er oppløselige akrylatkopolymerisater som utviser et syretall på 15 til 200, fortrinnsvis 30 til 120, fremstillbart fra ;al) 3 til 30 vekt-%, fortrinnsvis 5 til 25 vekt-% av en monomer med minst to polymeriserbare olefiniske umettede dobbeltbindinger, hvorved di- og polyestere av di- og polyoler med akrylsyre er unntatt, ;a2) 0,1 til 20 vekt-%, fortrinnsvis 1 til 14 vekt-% av et tertiært amin med en polymeriserbar, olefinisk umettet dobbeltbinding, ;a3) 5 til 4 0 vekt-%, fortrinnsvis 10 til 3 0 vekt-% av hydroksylgruppeholdige monomerer, ;a4) o til 80 vekt-% av andre polymeriserbare monomerer ;med en olefinisk umettet dobbeltbinding, og ;a5) cykliske karboksylsyreanhydrider, ;hvorved summen av al, a2, a3 og a4 utgjør 100 vekt-%. ;Som komponenter al kan det med fordel anvendes forbindelser med den generelle formel ;;hvori de følgende betydninger gjelder: ;X = 0, S, NR' hvor R = H, alkyl, aryl ;n = 2 til 8. ;Eksempler på flere ganger etylenisk umettede forbindelser er heksandioldimetakrylat, glykoldimetakrylat, butandioldimetakrylat, trimetylolpropantrimetakrylat, divinylbenzen og lignende forbindelser. Det kan med fordel også anvendes de allerede nevnte etylenisk umettede forbindelser med den forutsetning at det ikke dreier seg om di- og polyestere av di- og polyoler med akrylsyre. ;Som polymeriserbare tertiære aminer kommer de allerede ovenfor nevnte i betraktning. ;Som komponent a3 egner seg hydroksyalkylestere av akryl og/eller metakrylsyre med en primær hydroksylgruppe, for eksempel hydroksyetylakrylat, hydroksypropylakrylat, hydroksybutylakrylat, hydroksyamylakrylat, hydroksyheksylakrylat, hydroksyoctylakrylat og de tilsvarende metakrylater, samt hydroksyalkylester med en sekundær 0H-gruppe, som 2-hydroksypropylakrylat, 2-hydroksybutylakrylat, 3-hydroksybutylakrylat og de tilsvarende metakrylater. ;Foruten dette kommer som komponent a3 i betraktning omsetningsprodukter av akrylsyre og/eller metakrylsyre med glycidylesteren av en karbonsyre med et tertiært a-karbon-atom. ;Utvalget av komponenten a4 er ikke særlig kritisk og retter seg etter de ønskede egenskaper hos akrylatkopolymerisatet. Det skal nevnes at det som komponent a4 også kan anvendes karboksylgruppeholdige monomerer. ;Eksempler på komponenten a5 er ftalsyreanhydrid, tetrahydroftalsyreanhydrid, heksahydroftalsyreanhydrid, ravsyreanhydrid samt deres halogenerte derivater. Som komponent a5 kan det også anvendes maleinsyreanhydrid, og det må passes på at det ikke anvendes løsningsmiddel som under katalyse med tertiære nitrogengrupper reagerer med maleinsyreanhydrid. Ikke anvendbare er for eksempel aceton, metyletylketon, butylakrylat samt andre acetyliserende løsningsmid-ler. Det kan anvendes hydrokarboner og polare løsningsmidler som dietylformamid, dimetylacetamid, N-metylpyrrolidon etc. ;En foretrukket gjenstand for foreliggende oppfinnelse er også et oppløselig akrylatkopolymerisat med et syretall på 15 til 200, som kan fremstilles av ;al) mer enn 3 til 30 vekt-%, fortrinnsvis 5 til 25 vekt-% ;av monomere med minst to polymeriserbare, olefinisk umettede dobbeltbindinger ;a2) 1 til 25 vekt-%, fortrinnsvis 3 til 15 vekt-% av ;monomerer med cykliske karboksylsyreanhydridgrupper ;a3) 45 til 80 vekt-% av andre polymeriserbare monomerer ;med en olefinisk umettet dobbeltbinding, ;hvorved summen av al, a2 og a3 utgjør 100 vekt-%, og av ;a4 forbindelser som både inneholder minst et hydrogen som kan reagere med syreanhydridgrupper og minst en tertiær aminogruppe, ;hvorved endel av karboksylsyreanhydridgruppene også kan være omsatt med en monofunksjonell forbindelse med aktivt hydro- ;gen. ;Som komponent al egner seg de allerede nevnte flere ganger etylenisk umettede monomere omfattende di- og polyestere av di- og polyoler med akrylsyre. ;Eksempler på monomere med cykliske karboksylsyreanhydridgrupper er maleinsyreanhydrid eller itaconsyreanhydrid. ;Valget av komponenten a3 retter seg etter de ønskede egenskaper for akrylatkopolymerisatet. Det skal være nevnt at det i foreliggende tilfelle egner seg monomere med karboksylgrupper, altså for eksempel akrylsyre eller metakrylsyre. ;Med fordel anvendes som komponent a4 alkoholer som inneholder en tertiær aminogruppe, samt primære eller sekundære aminer med en tertiær aminogruppe. Det reaktive hydrogen i komponenten a4 kan stamme fra en hydroksylgruppe, en primær eller sekundær aminogruppe eller en tiolgruppe. ;Eksempler på alkoholer med tertiære aminogrupper er addukter av sekundære aminer og epoksyforbindelser. Eksempler på sekundære aminer er dimetylamin, dietylamin, dipropylamin, dibutylamin, morfolin og pyrrolidin. ;Eksempler på egnede epoksyforbindelser er etylenoksyd, propylenoksyd, butylenoksyd, styroloksyd og cykloheksan-oksyd. ;Egnede alkoholer med tertiære aminogrupper, som fremstilles ved omsetning av sekundære aminer med epoksyforbindelser er dimetylaminoetanol, dietylaminoetanol, di-n-propylaminoetanol, diisopropylaminoetanol, di-n-butyl-aminoetanol, N-(2-hydroksyety1)morfolin, N-(2-hydroksyety1) piperidin, N-(2-hydroksyety1) pyrrolidon, N-(2-hydroksyet-yl)azeridin, N,N•-dimetyl-2-hydroksypropylamin, N,N<»->dietyl-2-hydroksypropylamin, trietanolamin og tripropanolamin. Andre eksempler på alkoholer som inneholder tertiære aminogrupper er vinylpolymere som inneholder både en tertiær aminogruppe og en hydroksylgruppe i sidekjeden og som kan fremstilles ved kopolymerisering av de nevnte (met)akrylatmonomerer som inneholder tertiære aminogrupper med monomerer som inneholder OH-grupper, som eksempelvis 3-hydroksyetyl(met)akrylat. ;Eksempler på de primære eller sekundære aminer som inneholder en tertiær aminogruppe er N,N'-dialkyl-1,3-propylen-diaminer som for eksempel N,N'-dimetyl-l,3-propylendiamin, N,N<1->dietyl-1,3-propylendiamin og N,N<1->dialkyl-1,4-tetra-metylendiaminer, som for eksempel N,N'-dimetyl-1,4-tetra-metylendiamin og N,N'-dietyl-1,4-tetrametylen-diamin. Videre kommer N,N'-dialkyl-1,6-heksametylendiaminer og N-alkyl-piperaziner samt 2-aminopyridin, 4-aminopyridin og N-alkylaminopyridin i betraktning. ;Det skal nevnes at endel av karboksylsyreanhydridgruppene også kan være omsatt med en monfunksjonell forbindelse med aktivt hydrogen, som for eksempel alkoholer. ;En foretrukket gjenstand for foreliggende oppfinnelse er videre et akrylatkopolymerisat som utviser et syretall på 15 til 200, fortrinnsvis 30 til 120, og kan fremstilles fra ;al) 3 til 30 vekt-%, fortrinnsvis 5 til 25 vekt-% av monomerer med minst to polymeriserbare, olefinisk umettede dobbeltbindinger, ;a2) 1 til 30 vekt-% av glycidylestere av etylenisk umettede karboksylsyrer og/eller glycidyletere av olefinisk umettede forbindelser, ;a3) 40 til 95 vekt-% av andre polymeriserbare monomerer med en olefinisk umettet dobbeltbinding, ;hvorved summen av alle monomerer utgjør 100 vekt-%, og av ;a4) aminer med en sekundær aminogruppe eller di- eller polyaminer med minst en tertiær aminogruppe og en primær eller sekundær aminogruppe og/eller ;a5) karboksylsyrer som inneholder et tertiært nitrogen-atom, og av ;a6) cykliske karboksylsyreanhydrider. ;Som komponent al kommer de allerede nevnte flere ganger etylenisk umettede monomerer i betraktning. ;Eksempler på komponentene a2) er glycidylesteret til akrylsyren eller metakrylsyren samt allyl- og vinylglycidyl-eter, glycidylvinylester eller glycidylallylester, som glycidylvinylftalat, glycidylallylftalat. Utvalget av komponenten a3 retter seg etter de ønskede egenskaper hos akrylatkopolymerisatet og kan skje fra den allerede ovenfornevnte gruppe. Det skal dog som komponent a3 ikke anvendes karboksylgruppeholdige og aminogruppeholdige monomerer, da disse reagerer med oksirangruppen i komponenten a2. Andelen av hydroksylgruppeholdige monomerer bør holdes så lav som mulig. Er det nødvendig med hydroksylgrupper for å oppnå en bestemt polaritet for kopolymerisatet, så skal monomerer med sekundære OH-grupper være foretrukket . ;Eksempler på komponenten a4 er imidazol, aminopyridin, N-alkylaminopyridin, etylpiperazin, dibutylamin. ;Eksempler på komponenten a5 er 3- og 4-dimetylaminobenzen-syre, picolinsyre og dimetylaminosalicylsyre. ;Som eksempel på komponenten a6 skal det nevnes ftalsyreanhydrid, tetrahydroftalsyreanhydrid, heksahydroftalsyreanhydrid, ravsyreanhydrid samt deres halogenerte derivater. Oppfinnelsen vedrører også en fremgangsmåte ved fremstilling av de oppløselige akrylatkopolymerisater i henhold til krav 1-12, hvilke er kjennetegnet ved at til deres fremstilling kopolymeriseres de monomere i et organisk løsningsmiddel ved 70"C til 130"C, fortrinnsvis 80°C til 12 0°C under anvendelse av minst 0,5 vekt-%, fortrinnsvis minst 2,5 vekt-% beregnet på monomerenes samlede vekt, av en polymerisasjonsregulator og av polymerisasjonsinitiatorer til et forfornettet, ikke gelatinisert produkt, at polymerisasjonen utføres slik at en løsning av polymerisatet med et faststoffinnhold på 40-65 vektprosent resulterer, og at etter kopolymerisasjonen følger eventuelt omsetning med ytterligere komponenter. ;Gjenstand for oppfinnelsen er også en fremgangsmåte ved fremstilling av det oppløselige akrylatkopolymerisat i henhold til krav 6 som er kjennetegnet ved at til dennes fremstilling monomerene først kopolymeriseres i et organisk løsningsmiddel ved 70°C til 130"C, fortrinnsvis ved 80°C til 12 0°C under anvendelse av minst 0,5 vekt-%, fortrinnsvis minst 2,5 vekt-% relativt til den samlede vekt av de monomere, av en polymerisasjonsregulator og under anvendelse av polymerisasjonsinitiatorer til et forfornettet, ikke gelert produkt og etter avsluttet kopolymerisering gjennom-føres omsetningen med det cykliske syreanhydrid. ;Oppfinnelsen vedrører videre en fremgangsmåte ved fremstilling av det oppløselige akrylatkopolymerisat i henhold til krav 7, som er kjennetegnet ved at for fremstilling av denne kopolymeriseres først de monomere i et organisk løsningsmid-del ved 70°C til 130°C, fortrinnsvis ved 80oC til 120°C under anvendelse av minst 0,5 vekt-%, fortrinnsvis minst 2,5 vekt-% relativt til det samlede vekt, av de monomere, av en polymerisasjonsregulator og under anvendelse av polymerisasjonsinitiatorer til et forfornettet ikke gelert produkt og etter avsluttet kopolymerisasjonsreaksjon gjennomføres omsetningen av kopolymerisatet med de forbindelser som inneholder både minst et hydrogen som kan reagere med syreanhydridgrupper og også minst en tertiær aminogruppe og eventuelt med mono-funksjonelle forbindelser med aktivt hydrogen. ;Det skal legges merke til at det fremstilles et forfornettet, men ikke gelert kopolymerisat. Ved egnede polymerisa-sjonsbetingelser lar det seg overraskende fremstille en klar, transparent, ikke gelert oppløsning av et forgrenet kopolymerisat. Ved anvendelse av monomerer med minst to etylenisk umettede grupper fremkalles en forfornetning av kopolymerisatmolekylene, hvilket grunnet de spesielle reaksjonsbetingelser i henhold til oppfinnelsen likevel ikke fører til gelerte produkter. ;Polymerisasjonen gjennomføres slik at den resulterer i en oppløsning av polymerisatet med en faststoffinnhold på 40 til 65 vekt-%. Faststoffinnholdet er avhengig av andelen av innpolymeriserte, flere ganger etylenisk umettede monomere. Er denne andel lav, så kan det polymeriseres ved høyere faststoffinnhold. ;Videre er det nødvendig å anvende egnede initiatorer og alt etter andelen av flerfunksjonene monomere, minst 0,5 vekt-%, fortrinnsvis dog minst 2,5 vekt-% av en polymerisasjonsregulator. Utvalget av initiatoren retter seg etter andelen av de anvendte flerfunksjonene monomere. Ved lav andel, ;anvendes de initiatorer som vanligvis anvendes ved slike ;temperaturer, som for eksempel peroksiestere. Ved høy andel av flerfunksjonene monomerer anvendes fortrinnsvis initiatorer som for eksempel azo-forbindelser. Etter polymerisasjonen konsentreres polymerisatoppløsningen ved avdestil-lering av løsningsmiddel til det ønskede faststoffinnhold, fortrinnsvis til faststoffinnhold på 60 vekt-%. De slik dannede klare kopolymerisasjonsoppløsninger har en viskositet på 0,4 til 10 dPa.s. når de er innstilt på et faststoffinnhold på 50 vekt-%. ;Polymerisasjonen gjennomføres i nærvær av et organisk løsningsmiddel. Eksempler er etanol, isopropanol, n-propanol, n-butanol, isobutanol, t-butanol, metyl-, etyl-, propyl- og butylester av eddiksyre, aceton, metyletylketon, xylen, toluen. ;Som polymerisasjonsregulatorer egner seg fortrinnsvis mercaptogruppeholdige forbindelser, hvorved det særlig foretrukket anvendes mercaptetanol. Andre mulige regulato-rer er eksempelvis t-dodecylmercaptan, fenylmercaptan, octyldecylmercaptan, butylmercaptan og tiokarboksylsyrer, som for eksempel tiomelkesyre. ;Det skal bemerkes at ved fremstillingen av akrylatkopolymerisatet i henhold til krav 7, 8 eller 9 må det ikke anvendes hydroksymercaptaner, henholdsvis mercaptaner med primære SH-grupper som polymerisasjonsregulator. Ved valget av polymerisasjonsregulatoren ved fremstillingen av akrylatet i henhold til krav 10 må det passes på at det ikke anvendes tiokarboksylsyrer. ;Oppfinnelsen vedrører også anvendelse av akrylatkopolymerisatet ifølge krav 1-12 som overtrekksmiddel sammen med en forbindelse som inneholder minst to epoksydgrupper pr. molekyl, hvorved forholdet mellom syregruppene i akrylatkopolymerisatet og epoksydgruppene i overtrekksmiddelet ligger i området 0,5:3 og 2:0,5, og eventuelt anvendes en fornetningskatalysator. ;Eksempler på forbindelser på minst to epoksidgrupper per molekyl er kondensasjonsprodukter av epiklorhydrin og bisfenol A, cykloalifatiske bisepoksider, som tilsvarer formel I og II: ;samt epoksyderte polybutadiener, hvilke fremstilles ved omsetning av polybutadioler som er kommersielt tilgjenge-lige med persyrer, henholdsvis organiske syre-H202-blan-dinger, epoksidgruppeholdige novolaker, glycidyleter av en merverdig alkohol, for eksempel etylenglykoldi-glycidyleter, glycerinpolyglycidyleter, sorbitolpolygly-cidyleter, trimetylolpropanpolyglycidyleter og pentaery-tritpolyglycidyleter og lavmolekylære akrylatharpikser med oksirangrupper i sidekjedene. ;Eventuelt kan det anvendes en fornetningskatalysator. Herved egner det seg særlig tertiære aminer, kvaternære ammoniumforbindelser som for eksempel benzyltrimetylammo-niumhydroksid og benzyltrimetylammoniumklorid, spesielle kromforbindelser samt tinnforbindelser. Naturligvis er det ikke nødvendig å anvende fornetningskatalysator i de fleste tilfeller ved hvilke det allerede er bygget inn tertiære aminogrupper i akrylatkopolymerisatet. Ved anvendelsen av en intern eller extern fornetningskatalysator oppnås lavere innbrenningstemperaturer og kortere innbrenningstider. Fortrinnsvis anvendes fornetningskatalysatoren i en mengde på 0,5 til 10 vekt-%, relativt til vekten av di-, henholdsvis polyepoksidkomponenten. ;Overtrekksmidlene fremragende egenskaper når det gjelder bestandighet ovenfor langvarig belastning av kjemikalier, løsningsmidler og når det gjelder bensinfasthet, elastisitet, glans, korrosjons-bestandighet og bestandighet ovenfor vann og vanndamp. Overtrekksmidlene herder eventuelt ved lav temperatur og er derved anvendbare eksempelvis ved bilreparasjonslakkeringer. Videre kan det oppnås et høyt faststoffinnhold i det herdbare overtrekksmiddel ved relativt lav viskositet, sammenlignet med lineære akrylat-kopolymerisater og med akrylatharpikser med lav andel av innpolymeriserte flere ganger etylenisk umettede monomerer. ;I det følgende skal oppfinnelsen belyses ved hjelp av utførelseseksempler: A) Fremstilling av kopolymerisater i henhold til oppfinnelsen (Bindemiddel A) ;I de følgende eksempler skal alle prosentangivelser stå for vektprosent og alle andeler betyr vektandeler når det ikke er oppført annet. Faststoffverdiene ble bestemt i en omluftovn etter 1 time ved 130°C. Viskositeten ble bestemt på et kjegle-plate-viskosimeter. ;Akrylatharpiks I ;I en 3-liters edelstålkjele fylles ;212 deler Solvenon PM (l-metoksypropanol-2) ;212 deler butylacetat 98/100 ;0,16 deler fosfinsyre (50 % i H20) ;Blandingen oppvarmes til 110°C, i løpet av 3 timer tilsettes jevnt fra to tilførselsbeholdere: ;Tilførsel 1 ;160 deler styren ;160 deler heksandioldimetakrylat ;80 deler B-karboksyetylakrylat ;120 deler n-butylakrylat ;100 deler t-butylakrylat ;52 deler tiomelkesyre ;Tilførsel 2 ;80 deler 4-vinylpyridin ;I løpet av 4 timer tilsettes jevnt fra tilløpsbeholder 3 ;Tilførsel 3 ;3 2 deler azobisisobutyronitril ;230 deler Solvenon PM (l-metoksypropanol-2) ;230 deler butylakrylat 98/100 ;Alle 3 tilløp startes samtidig. Etter avsluttet initiator-tilløp etterpolymeriseres det videre i 2 timer. Akrylat-harpiksoppløsning I har et faststoff (2 t 100°C) på 50,7%, viskositet (23'C, orginal) på 6,1 dPa.s og et syretall på 67 (mg KOH/g fastharpiks). ;Akrylatharpiks II ;Fremgangsmåte og tilførselstider som ved akrylatharpiks I, ;;Tilløp 1+2 3 t, tilløp 3 4 t, deretter 3 t ytter- ;ligere polymerisering ved 110°C. ;Til akrylatharpiksoppløsningen tilsettes 90,8 deler ravsyreanhydrid og røres i 6 timer ved 12 0*C. Oppløsningen av addisjonsproduktet av ravsyreanhydrid på OH-akrylatet har et syretall på 71, viskositet 6 dPa.s og faststoff 52,2%. N, N<*->dimethylaminoethyl methacrylate, N,N', diethylaminoethyl methacrylate, 2-vinylpyridine and 4-vinylpyridine, vinylpyrroline, vinylquinoline, vinylisoquinoline, N,N'-Dimethylaminoethyl-;vinyl ether and 2-methyl-5- vinylpyridine. ; Optionally, monomers containing hydroxyl groups can also be used. As an example, mention should be made of hydroxyalkyl esters of acrylic and methacrylic acid, such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyamyl acrylate, hydroxyhexyl acrylate, hydroxyoctyl acrylate and the corresponding methacrylates. The selection of other monomers with a polymerisable, olefinically unsaturated double bond takes place from the group already mentioned above. It is also advantageous in this case that the other monomers with polymerizable double bonds which are inserted in 0.1 to 5% by weight in relation to the combined weight of all monomers, are monomers with phosphoric acid groups. According to the invention, soluble acrylate copolymers exhibiting an acid number of 15 to 200, preferably 30 to 120, can be prepared from ;al) 3 to 30% by weight, preferably 5 to 25% by weight of a monomer with at least two polymerizable olefinic unsaturated double bonds, whereby di- and polyesters of di- and polyols with acrylic acid are excluded, ;a2) 0.1 to 20% by weight, preferably 1 to 14% by weight of a tertiary amine with a polymerizable, olefinically unsaturated double bond, ;a3 ) 5 to 40% by weight, preferably 10 to 30% by weight of monomers containing hydroxyl groups, ;a4) o to 80% by weight of other polymerizable monomers ;with an olefinically unsaturated double bond, and ;a5) cyclic carboxylic acid anhydrides, ;whereby the sum of a1, a2, a3 and a4 amounts to 100% by weight. ;As components al, compounds with the general formula ;;in which the following meanings apply: ;X = 0, S, NR' where R = H, alkyl, aryl ;n = 2 to 8 can be advantageously used. ;Examples of several times ethylenically unsaturated compounds are hexanediol dimethacrylate, glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane trimethacrylate, divinylbenzene and similar compounds. The already mentioned ethylenically unsaturated compounds can also be advantageously used, provided that they are not di- and polyesters of di- and polyols with acrylic acid. As polymerizable tertiary amines, those already mentioned above come into consideration. ; As component a3, hydroxyalkyl esters of acrylic and/or methacrylic acid with a primary hydroxyl group, for example hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyamyl acrylate, hydroxyhexyl acrylate, hydroxyoctyl acrylate and the corresponding methacrylates, as well as hydroxyalkyl esters with a secondary OH group, such as 2-hydroxypropyl acrylate, are suitable. 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate and the corresponding methacrylates. In addition to this, reaction products of acrylic acid and/or methacrylic acid with the glycidyl ester of a carboxylic acid with a tertiary α-carbon atom come into consideration as component a3. The selection of component a4 is not particularly critical and is based on the desired properties of the acrylate copolymer. It should be mentioned that monomers containing carboxyl groups can also be used as component a4. Examples of component a5 are phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic anhydride and their halogenated derivatives. Maleic anhydride can also be used as component a5, and care must be taken that no solvent is used which during catalysis with tertiary nitrogen groups reacts with maleic anhydride. Not applicable are, for example, acetone, methyl ethyl ketone, butyl acrylate and other acetylating solvents. Hydrocarbons and polar solvents such as diethylformamide, dimethylacetamide, N-methylpyrrolidone etc. can be used. A preferred object of the present invention is also a soluble acrylate copolymer with an acid number of 15 to 200, which can be prepared from ;al) more than 3 to 30 weight -%, preferably 5 to 25% by weight of monomers with at least two polymerizable, olefinically unsaturated double bonds; a2) 1 to 25% by weight, preferably 3 to 15% by weight of monomers with cyclic carboxylic acid anhydride groups; a3) 45 to 80 % by weight of other polymerizable monomers ;with an olefinic unsaturated double bond, ;wherein the sum of al, a2 and a3 amounts to 100% by weight, and of ;a4 compounds which both contain at least one hydrogen that can react with acid anhydride groups and at least one tertiary amino group , whereby part of the carboxylic acid anhydride groups can also be reacted with a monofunctional compound with active hydrogen. As component al, the already mentioned several times ethylenically unsaturated monomers comprising di- and polyesters of di- and polyols with acrylic acid are suitable. Examples of monomers with cyclic carboxylic acid anhydride groups are maleic anhydride or itaconic anhydride. The choice of component a3 is based on the desired properties of the acrylate copolymer. It should be mentioned that in the present case monomers with carboxyl groups are suitable, i.e. for example acrylic acid or methacrylic acid. Alcohols containing a tertiary amino group, as well as primary or secondary amines with a tertiary amino group are advantageously used as component a4. The reactive hydrogen in component a4 can originate from a hydroxyl group, a primary or secondary amino group or a thiol group. ;Examples of alcohols with tertiary amino groups are adducts of secondary amines and epoxy compounds. Examples of secondary amines are dimethylamine, diethylamine, dipropylamine, dibutylamine, morpholine and pyrrolidine. Examples of suitable epoxy compounds are ethylene oxide, propylene oxide, butylene oxide, styrene oxide and cyclohexane oxide. Suitable alcohols with tertiary amino groups, which are produced by reacting secondary amines with epoxy compounds, are dimethylaminoethanol, diethylaminoethanol, di-n-propylaminoethanol, diisopropylaminoethanol, di-n-butylaminoethanol, N-(2-hydroxyethyl)morpholine, N-(2 -hydroxyethyl)piperidine, N-(2-hydroxyethyl)pyrrolidone, N-(2-hydroxyethyl)azeridine, N,N-dimethyl-2-hydroxypropylamine, N,N<»->diethyl-2-hydroxypropylamine, triethanolamine and tripropanolamine. Other examples of alcohols that contain tertiary amino groups are vinyl polymers that contain both a tertiary amino group and a hydroxyl group in the side chain and which can be produced by copolymerizing the aforementioned (meth)acrylate monomers that contain tertiary amino groups with monomers that contain OH groups, such as 3- hydroxyethyl (meth)acrylate. Examples of the primary or secondary amines containing a tertiary amino group are N,N'-dialkyl-1,3-propylene diamines such as N,N'-dimethyl-1,3-propylenediamine, N,N<1- >diethyl-1,3-propylenediamine and N,N<1->dialkyl-1,4-tetramethylenediamines, such as N,N'-dimethyl-1,4-tetramethylenediamine and N,N'-diethyl -1,4-tetramethylenediamine. Furthermore, N,N'-dialkyl-1,6-hexamethylenediamines and N-alkyl-piperazines as well as 2-aminopyridine, 4-aminopyridine and N-alkylaminopyridine come into consideration. It should be mentioned that some of the carboxylic acid anhydride groups can also be reacted with a monofunctional compound with active hydrogen, such as alcohols. A preferred object of the present invention is further an acrylate copolymer which exhibits an acid number of 15 to 200, preferably 30 to 120, and can be prepared from ;al) 3 to 30% by weight, preferably 5 to 25% by weight of monomers with at least two polymerizable, olefinically unsaturated double bonds, ;a2) 1 to 30% by weight of glycidyl esters of ethylenically unsaturated carboxylic acids and/or glycidyl ethers of olefinically unsaturated compounds, ;a3) 40 to 95% by weight of other polymerizable monomers with an olefinically unsaturated double bond, ;whereby the sum of all monomers amounts to 100% by weight, and of ;a4) amines with a secondary amino group or di- or polyamines with at least one tertiary amino group and a primary or secondary amino group and/or ;a5) carboxylic acids containing a tertiary nitrogen -atom, and of ;a6) cyclic carboxylic anhydrides. As component al, the already mentioned several times ethylenically unsaturated monomers come into consideration. Examples of components a2) are the glycidyl ester of acrylic acid or methacrylic acid as well as allyl and vinyl glycidyl ether, glycidyl vinyl ester or glycidyl allyl ester, such as glycidyl vinyl phthalate, glycidyl allyl phthalate. The selection of component a3 is based on the desired properties of the acrylate copolymer and can be made from the group already mentioned above. However, monomers containing carboxyl groups and amino groups must not be used as component a3, as these react with the oxirane group in component a2. The proportion of monomers containing hydroxyl groups should be kept as low as possible. If hydroxyl groups are required to achieve a specific polarity for the copolymer, then monomers with secondary OH groups should be preferred. Examples of component a4 are imidazole, aminopyridine, N-alkylaminopyridine, ethylpiperazine, dibutylamine. Examples of component a5 are 3- and 4-dimethylaminobenzene acid, picolinic acid and dimethylaminosalicylic acid. As an example of the component a6, mention should be made of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic anhydride and their halogenated derivatives. The invention also relates to a method for the production of the soluble acrylate copolymers according to claims 1-12, which are characterized in that for their production the monomers are copolymerized in an organic solvent at 70°C to 130°C, preferably 80°C to 120 °C using at least 0.5% by weight, preferably at least 2.5% by weight, calculated on the total weight of the monomers, of a polymerization regulator and of polymerization initiators to a pre-crosslinked, non-gelatinized product, that the polymerization is carried out so that a solution of the polymer with a solids content of 40-65 percent by weight results, and that after the copolymerization any reaction with further components follows. The object of the invention is also a method for the production of the soluble acrylate copolymer according to claim 6, which is characterized in that for its production the monomers are first copolymerized in an organic solvent at 70°C to 130°C, preferably at 80°C to 12 0°C using at least 0.5% by weight, preferably at least 2.5% by weight relative to the total weight of the monomers, of a polymerization regulator and using polymerization initiators to a pre-crosslinked, non-gelled product and after completion of copolymerization the reaction is carried out with the cyclic acid anhydride. ;The invention further relates to a method for the production of the soluble acrylate copolymer according to claim 7, which is characterized in that, for the production of this, the monomers are first copolymerized in an organic solvent at 70°C to 130°C, preferably at 80°C to 120°C using at least 0.5% by weight, preferably at least 2.5% by weight relative to l the total weight, of the monomers, of a polymerization regulator and using polymerization initiators to a pre-crosslinked non-gelled product and after completion of the copolymerization reaction, the reaction of the copolymer is carried out with the compounds containing both at least one hydrogen that can react with acid anhydride groups and also at least one tertiary amino group and optionally with mono-functional compounds with active hydrogen. ;It should be noted that a pre-crosslinked but not gelled copolymer is produced. With suitable polymerization conditions, it is surprisingly possible to produce a clear, transparent, non-gelled solution of a branched copolymer. When using monomers with at least two ethylenically unsaturated groups, a pre-crosslinking of the copolymer molecules is induced, which, due to the special reaction conditions according to the invention, nevertheless does not lead to gelled products. The polymerization is carried out so that it results in a solution of the polymer with a solids content of 40 to 65% by weight. The solids content depends on the proportion of polymerized, several times ethylenically unsaturated monomers. If this proportion is low, it can be polymerized at a higher solids content. Furthermore, it is necessary to use suitable initiators and, depending on the proportion of the multifunctional monomers, at least 0.5% by weight, preferably at least 2.5% by weight of a polymerization regulator. The selection of the initiator is based on the proportion of the multifunctional monomers used. In the case of a low proportion, the initiators that are usually used at such temperatures, such as peroxyesters, are used. In the case of a high proportion of multifunctional monomers, initiators such as azo compounds are preferably used. After the polymerisation, the polymer solution is concentrated by distilling off the solvent to the desired solids content, preferably to a solids content of 60% by weight. The clear copolymerization solutions thus formed have a viscosity of 0.4 to 10 dPa.s. when they are set to a solids content of 50% by weight. ;The polymerization is carried out in the presence of an organic solvent. Examples are ethanol, isopropanol, n-propanol, n-butanol, isobutanol, t-butanol, methyl, ethyl, propyl and butyl esters of acetic acid, acetone, methyl ethyl ketone, xylene, toluene. Compounds containing mercapto groups are preferably suitable as polymerization regulators, whereby mercaptoethanol is particularly preferably used. Other possible regulators are, for example, t-dodecylmercaptan, phenylmercaptan, octyldecylmercaptan, butylmercaptan and thiocarboxylic acids, such as thiolactic acid. ;It should be noted that in the production of the acrylate copolymer according to claim 7, 8 or 9, hydroxy mercaptans, respectively mercaptans with primary SH groups must not be used as polymerization regulator. When choosing the polymerization regulator in the production of the acrylate according to claim 10, care must be taken that no thiocarboxylic acids are used. The invention also relates to the use of the acrylate copolymer according to claims 1-12 as a coating agent together with a compound containing at least two epoxide groups per molecule, whereby the ratio between the acid groups in the acrylate copolymer and the epoxy groups in the coating agent is in the range of 0.5:3 and 2:0.5, and a crosslinking catalyst is optionally used. ;Examples of compounds with at least two epoxide groups per molecule are condensation products of epichlorohydrin and bisphenol A, cycloaliphatic bisepoxides, which correspond to formulas I and II: ;as well as epoxidized polybutadienes, which are produced by reaction of commercially available polybutadiols with peracids, respectively organic acid H 2 O 2 mixtures, novolaks containing epoxide groups, glycidyl ethers of a higher alcohol, for example ethylene glycol diglycidyl ether, glycerin polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether and pentaerythritol polyglycidyl ether and low molecular weight acrylate resins with oxirane groups in the side chains. If necessary, a crosslinking catalyst can be used. Tertiary amines, quaternary ammonium compounds such as benzyltrimethylammonium hydroxide and benzyltrimethylammonium chloride, special chromium compounds and tin compounds are particularly suitable. Naturally, it is not necessary to use a crosslinking catalyst in most cases where tertiary amino groups have already been incorporated into the acrylate copolymer. When using an internal or external crosslinking catalyst, lower burn-in temperatures and shorter burn-in times are achieved. The crosslinking catalyst is preferably used in an amount of 0.5 to 10% by weight, relative to the weight of the di- or polyepoxide component. The coating agents have outstanding properties in terms of resistance to long-term exposure to chemicals, solvents and in terms of petrol resistance, elasticity, gloss, corrosion resistance and resistance to water and water vapour. The coating agents possibly harden at a low temperature and can therefore be used, for example, in car repair paintwork. Furthermore, a high solids content can be achieved in the curable coating agent at a relatively low viscosity, compared with linear acrylate copolymers and with acrylate resins with a low proportion of polymerized several times ethylenically unsaturated monomers. ;In the following, the invention shall be illustrated by means of examples: A) Production of copolymers according to the invention (Binder A) ;In the following examples, all percentages shall stand for percentage by weight and all proportions shall mean proportions by weight when not stated otherwise. The solids values were determined in a convection oven after 1 hour at 130°C. The viscosity was determined on a cone-plate viscometer. ;Acrylate resin I ;In a 3-litre stainless steel kettle, fill ;212 parts Solvenon PM (l-methoxypropanol-2) ;212 parts butyl acetate 98/100 ;0.16 parts phosphinic acid (50% in H20) ;The mixture is heated to 110°C, over the course of 3 hours, add evenly from two supply containers: ;Input 1 ;160 parts styrene ;160 parts hexanediol dimethacrylate ;80 parts B-carboxyethyl acrylate ;120 parts n-butyl acrylate ;100 parts t-butyl acrylate ;52 parts thiolactic acid ;Input 2 ;80 parts 4-vinylpyridine ; Over the course of 4 hours add evenly from feed container 3 ; Feed 3 ; 3 2 parts azobisisobutyronitrile ; 230 parts Solvenon PM (l-methoxypropanol-2) ; 230 parts butyl acrylate 98/100 ; All 3 feeds are started simultaneously. After finishing the initiator addition, it is further post-polymerised for 2 hours. Acrylate resin solution I has a solids (2 h 100°C) of 50.7%, viscosity (23°C, original) of 6.1 dPa.s and an acid number of 67 (mg KOH/g solid resin). ;Acrylate resin II ;Procedure and supply times as for acrylate resin I, ;;Inflow 1+2 3 h, flow 3 4 h, then 3 h further polymerization at 110°C. ; To the acrylate resin solution, 90.8 parts of succinic anhydride are added and stirred for 6 hours at 12 0*C. The solution of the addition product of succinic anhydride on the OH-acrylate has an acid number of 71, viscosity 6 dPa.s and solids 52.2%.
Akrylatharpiksoppløsning III Acrylate resin solution III
I en 3 1-edelstålkjele fylles: In a 3 1 stainless steel kettle fill:
195 deler butylacetat 98/100 195 parts butyl acetate 98/100
195 deler l-metoksypropylacetat-2 195 parts 1-methoxypropylacetate-2
Blandingen oppvarmes til 112°C og tilløp 1 og 2 tilføres i løpet av 3 timer jevnt: The mixture is heated to 112°C and inlets 1 and 2 are added evenly over the course of 3 hours:
Tilførsel 2: 70 deler 4-vinylpyridin Feed 2: 70 parts of 4-vinylpyridine
Tilførsel 3 tildoseres jevnt i løpet av 4,25 timer, tilløp fra 1, 2, 3 startes samtidig. Supply 3 is dosed evenly over 4.25 hours, supplies from 1, 2, 3 are started at the same time.
Tilførsel 3: 186,6 deler butylacetat 98/100 Feed 3: 186.6 parts butyl acetate 98/100
181,6 deler l-metoksypropylacetat-2 181.6 parts of 1-methoxypropylacetate-2
25,2 deler azobisisobutyronitril 25.2 parts azobisisobutyronitrile
Etter avsluttet tilløp 3 etterpolymeriseres videre i 2 timer ved 112°C, deretter tilsettes 81,4 deler ravsyreanhydrid og holdes under omrøring i 6 timer ved 12 0°C. Den dannede klare akrylatharpiksoppløsning har et faststoffinnhold på 52,5%, et syretall på 68 og en viskositet på 6,8 dPa.s. After addition 3 is finished, post-polymerisation continues for 2 hours at 112°C, then 81.4 parts of succinic anhydride are added and kept under stirring for 6 hours at 120°C. The resulting clear acrylate resin solution has a solids content of 52.5%, an acid number of 68 and a viscosity of 6.8 dPa.s.
Akrylatharpiksoppløsning IV Acrylate resin solution IV
I løpet av 3 timer tilsettes jevnt: Over the course of 3 hours, add evenly:
Tilførsel 2 70 deler 4-vinylpyridin Supply 2 70 parts 4-vinylpyridine
I løpet av 4 timer tilsettes jevnt: Over the course of 4 hours, add evenly:
Tilførsel 3 161,2 deler Solvenon PM Supply 3,161.2 parts Solvenon PM
161,2 deler butylacetat 98/100 161.2 parts butyl acetate 98/100
22,4 deler azobisisobutyronitril 22.4 parts azobisisobutyronitrile
Tilløp 1, 2 og 3 startes samtidig, mens polymeriseringen holdes på temperaturen 110°C, etterpolymeriseres i 2 timer etter avslutning av tilløp 3. Den dannede klare akrylat-harpiksoppløsningen har en viskositet på 2,1 dPa.s, et faststoff på 48,5% og et syretall på 52 %. Feeds 1, 2 and 3 are started simultaneously, while the polymerization is kept at the temperature of 110°C, post-polymerization for 2 hours after the end of feed 3. The clear acrylate resin solution formed has a viscosity of 2.1 dPa.s, a solids of 48, 5% and an acid number of 52%.
Akrylatharpiksoppløsning V Acrylate resin solution V
I en 3 1-edelstålkjele fylles: In a 3 1 stainless steel kettle fill:
Utgangsblanding: 266 deler butylacetat 98/100 Starting mixture: 266 parts butyl acetate 98/100
266 deler xylen 266 parts xylene
Utgangsblandingen oppvarmes til 112'C og tilløp 1 og 2 tilsettes jevnt i løpet av 3 timer ved 112 °C. The starting mixture is heated to 112 °C and inflows 1 and 2 are added evenly over 3 hours at 112 °C.
Tilførsel 1 Supply 1
Tilførsel 2 Supply 2
I løpet av 3,5 timer tilsettes tilløp 3 jevnt, alle tilløp settes igang samtidig. During 3.5 hours, inlet 3 is added evenly, all inlets are started at the same time.
Tilførsel 3 Supply 3
Etter avslutning av tilløp 3 etterpolymeriseres det i 2 timer ved 114'C. Akrylatharpiksoppløsningen har et faststoff på 49% og en viskositet på 3,1 dPa.s. After completion of flow 3, post-polymerisation is carried out for 2 hours at 114°C. The acrylate resin solution has a solids of 49% and a viscosity of 3.1 dPa.s.
Til denne akrylatharpiksoppløsning tilsettes To this acrylate resin solution is added
53,6 deler 2-aminopyridin 53.6 parts 2-aminopyridine
109 deler 2-metoksypropylacetat-2 109 parts 2-methoxypropylacetate-2
og ved 80"C tilsettes maleinsyreanhydrid-kopolymerisatet. Etter 3,5 timer ved 80"C er omsetningen avsluttet, den klare og fargeløse akrylatharpiksoppløsning har en viskositet på 9,5 dPa.s, et syretall på 57, en aminekvivalent-vekt på 1400 + 20 og et faststoff på 49,4%. and at 80"C the maleic anhydride copolymer is added. After 3.5 hours at 80"C the reaction is finished, the clear and colorless acrylate resin solution has a viscosity of 9.5 dPa.s, an acid number of 57, an amine equivalent weight of 1400 + 20 and a solids of 49.4%.
Akrylatharpiksoppløsning VI Acrylate resin solution VI
I en 3 1-edelstålkjele fylles: In a 3 1 stainless steel kettle fill:
Utgangsblanding: 197 deler l-metoksypropylacetat-2 Starting mixture: 197 parts of 1-methoxypropylacetate-2
197 deler butylacetat 197 parts butyl acetate
Utgangsblandingen oppvarmes til 110°C, og i løpet av 3 timer tilsettes tilløp 1 og 2 jevnt. The starting mixture is heated to 110°C, and over the course of 3 hours, inflows 1 and 2 are added evenly.
Tilførsel 1 Supply 1
Tilførsel 2 Tilførsel 3 Supply 2 Supply 3
I løpet av 4 timer tilsettes tilløp 3 jevnt. Tilløpene 1, 2 og 3 startes samtidig, under polymeriseringen holdes temperaturen på 110°C. Etter avslutning av tilløp 3 etterpolymeriseres det videre ved 110°C i 3 timer. Den slik dannede klare, fargeløse akrylatharpiksoppløsning omsettes deretter ved 120°C med 81 deler ravsyreanhydrid til C00H-akrylatet. Den slik dannede akrylatharpiksoppløsning har en viskositet på 7,2 dPa.s, et faststoff på 52,3% og et syretall på 68. In the course of 4 hours, addition 3 is added evenly. Feeds 1, 2 and 3 are started simultaneously, during the polymerization the temperature is kept at 110°C. After completion of batch 3, it is further post-polymerised at 110°C for 3 hours. The clear, colorless acrylate resin solution thus formed is then reacted at 120°C with 81 parts of succinic anhydride to the COOH acrylate. The acrylate resin solution thus formed has a viscosity of 7.2 dPa.s, a solids of 52.3% and an acid number of 68.
Akrylatharpiksoppløsning VII Acrylate resin solution VII
Utgangsblandingen oppvarmes til 110°C, i løpet av 3 timer tilsettes tilløp 1 og 2 jevnt. The starting mixture is heated to 110°C, during 3 hours additions 1 and 2 are added evenly.
Tilførsel 1 Supply 1
Tilførsel 2 Supply 2
80 deler vinylpyridin 80 parts vinylpyridine
I løpet av 4 timer tilsettes tilløp 3. Alle tilløp settes i gang samtidig, i løpet av polymeriseringen holdes temperaturen på 110°C. In the course of 4 hours, feed 3 is added. All feeds are started at the same time, during the polymerization the temperature is kept at 110°C.
Tilførsel 3 Supply 3
Etter avslutning av tilløp 3 etterpolymeriseres det videre i 2 timer ved 100"C. Den slik dannede klare akrylathar-piksoppløsning har et faststoff på 50,5%, et syretall på 64,2 og en viskositet på 12,0 dPa.s. After completion of feed 3, it is further post-polymerised for 2 hours at 100°C. The clear acrylate resin solution thus formed has a solids of 50.5%, an acid number of 64.2 and a viscosity of 12.0 dPa.s.
Akrylatharpiksoppløsning VIII Acrylate resin solution VIII
I en 3 1-edelstålkjele fylles: In a 3 1 stainless steel kettle fill:
479 deler xylen 479 parts xylene
439 deler dimetylformamid 439 parts dimethylformamide
Utgangsblandingen oppvarmes til 110°C og i løpet av 3 timer tilsettes jevnt tilløp 1 og 3. The starting mixture is heated to 110°C and, over the course of 3 hours, a steady stream of inputs 1 and 3 is added.
Tilførsel 1 Supply 1
80 deler dimetylaminoetylmetakrylat 80 parts dimethylaminoethyl methacrylate
Tilførsel 2 Supply 2
I løpet av 4 timer tilsettes tilløp 3. Tilløpene 1, 2 og 3 Inflow 3 is added during 4 hours. Inflows 1, 2 and 3
settes igang samtidig. are started at the same time.
Tilførsel 3 Supply 3
Under polymeriseringen holdes temperaturen på 110°C, etter avslutning av tilløp 3 etterpolymeriseres det i ytterligere 2 timer ved 110°C. Deretter tilsettes 101 deler maleinsyreanhydrid og ved 100'C tilsettes dette til kopolymerisatets hydrosylgrupper til det oppnås et syretall på 71 og en viskositet (original, 23°C) på 8,2 dPa.s. Deretter During the polymerization, the temperature is kept at 110°C, after completion of feed 3, it is post-polymerized for a further 2 hours at 110°C. Then 101 parts of maleic anhydride are added and at 100°C this is added to the copolymer's hydrosyl groups until an acid number of 71 and a viscosity (original, 23°C) of 8.2 dPa.s is achieved. Then
avdestilleres 340 deler løsningsmiddelblanding og løses med 270 deler butylacetat 98/100. Den slik dannede oppløsning av et forgrenet akrylat har et faststoff på 56,6%, en viskositet på 13,5 dPa.s og et syretall på 70,5. 340 parts of the solvent mixture are distilled off and dissolved with 270 parts of butyl acetate 98/100. The thus formed solution of a branched acrylate has a solids of 56.6%, a viscosity of 13.5 dPa.s and an acid number of 70.5.
Akrylatharpiks IV Acrylate resin IV
I en 3 1-edelstålkjele fylles: In a 3 1 stainless steel kettle fill:
480 deler xylen 480 parts xylene
240 deler dimetylformamid 240 parts dimethylformamide
Utgangsblandingen oppvarmes til 110°C og i løpet av 3 timer tilsettes tilløp 1: The starting mixture is heated to 110°C and, within 3 hours, feed 1 is added:
I løpet av 4 timer tilsettes tilløp 2. Startet av tilløp 1 og 2 skjer samtidig. In the course of 4 hours, inflow 2 is added. The start of inflows 1 and 2 occurs simultaneously.
Tilførsel 2 Supply 2
I løpet av polymeriseringen holdes temperaturen på 110"C. During the polymerization, the temperature is kept at 110°C.
Etter avslutning av tilløp 2 etterpolymeriseres det i 3 timer ved 110°C. Deretter tilsettes ved 100°C 101 del maleinsyreanhydrid og adderes til OH-akrylatet til syretallet 70 er oppnådd. Deretter avdestilleres 227 deler av løsningsmiddelblanding og 320 deler n-butanol tilsettes. Den slik dannede oppløsning av en forgrenet akrylatharpiks har et faststoff på 49,5%, et syretall på 68,3 og en viskositet på 18 dPa.s (orginal). After completion of flow 2, post-polymerisation is carried out for 3 hours at 110°C. Then, at 100°C, 101 parts of maleic anhydride are added and added to the OH acrylate until the acid number 70 is obtained. Then 227 parts of the solvent mixture are distilled off and 320 parts of n-butanol are added. The thus formed solution of a branched acrylate resin has a solids of 49.5%, an acid number of 68.3 and a viscosity of 18 dPa.s (original).
B) fremstilling av toningspastaer B) preparation of toning pastes
Pigmentpasta blir dispergert i respektive 40 minutter Pigment paste is dispersed for 40 minutes respectively
på en laboratoriesandmølle etter følgende sammensetning (kornfinhet 10 pm). on a laboratory sand mill according to the following composition (grain fineness 10 pm).
Pasta 25/2 Pasta 25/2
Pasta 25/3 Pasta 25/4 Pasta 25/3 Pasta 25/4
C) Fremstilling og utprøvning av lakker. C) Production and testing of varnishes.
Etter følgende sammensetning fremstilles dekklakker, påføres på glassplater ved hjelp av spatier (tørrsjikt-tykkelse 4 0 pm), tørkes ved romtemperatur eller forsert 3 0 minutter ved 60°C, lagres 6 dager ved romtemperatur og testes deretter. According to the following composition, topcoats are prepared, applied to glass plates using spacers (dry layer thickness 40 pm), dried at room temperature or forced for 30 minutes at 60°C, stored for 6 days at room temperature and then tested.
Pendelhardhet: I henhold til Konig Pendulum hardness: According to Konig
bensin (FAM forsøksbensin etter DIN 51604)-bestandighet og xylenbestandighet: 5 minutters belastning med en filtplate dekket med et av løsningsmidlene, tildekket. petrol (FAM test petrol according to DIN 51604) resistance and xylene resistance: 5 minute load with a felt plate covered with one of the solvents, covered.
Eksempel 1 Example 1
Resultater: Results:
Eksempel 2 Resultat Example 2 Result
Resultat: Result:
Eksempel 3 Epoxiharpiks av basis Example 3 Base epoxy resin
Resultat: Eksempel 4 Result: Example 4
Resultat: Result:
Eksempel 5 Example 5
Akrylatharpiks VII blandes med en polyglycidyleter på basis av sorbitol (epoksydekvivalentvekt 180) i forhold 82/18 (fast på fast), fortynnes med butylacetat til 25'' DIN 4 og påføres glasstavler med spatel (våtfilm tykkelse 200 pm). Acrylate resin VII is mixed with a polyglycidyl ether based on sorbitol (epoxide equivalent weight 180) in a ratio of 82/18 (solid on solid), diluted with butyl acetate to 25'' DIN 4 and applied to glass plates with a spatula (wet film thickness 200 pm).
Eksempel 6 Example 6
Akrylatharpiksen VIII blandes med en novolakk-polyglycidyleter (epoxidekvivalentvekt 178) i forhold 82/18 (fast på fast), fortynnes med xylen og spartles på glassplater (200 pm våtfilmtykkelse). Etter tørking i 6 dager ved romtemperatur oppnås en pendelhårdhet på 701'. Fornetningsforsøket med metyletylketon gir 155 dobbelslaglengde. The acrylate resin VIII is mixed with a novolak polyglycidyl ether (epoxide equivalent weight 178) in a ratio of 82/18 (solid on solid), diluted with xylene and spread on glass plates (200 µm wet film thickness). After drying for 6 days at room temperature, a pendulum hardness of 701' is achieved. The cross-linking experiment with methyl ethyl ketone gives 155 double stroke length.
Claims (16)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19853534858 DE3534858A1 (en) | 1985-09-30 | 1985-09-30 | SOLUBLE ACRYLATE COPOLYMERISATE CONTAINING CARBOXYL GROUPS, METHOD FOR THE PRODUCTION THEREOF AND COATING AGENTS BASED ON THE ACRYLATE COPOLYMERISATE |
PCT/EP1986/000488 WO1987002041A1 (en) | 1985-09-30 | 1986-08-20 | Soluble acrylic copolymer containing carboxyl groups, its production process and coating agent on the basis of this acrylic copolymer |
Publications (4)
Publication Number | Publication Date |
---|---|
NO872278D0 NO872278D0 (en) | 1987-05-29 |
NO872278L NO872278L (en) | 1987-07-14 |
NO168252B true NO168252B (en) | 1991-10-21 |
NO168252C NO168252C (en) | 1992-01-29 |
Family
ID=25836548
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO872278A NO168252C (en) | 1985-09-30 | 1987-05-29 | LOOSE, CARBOXYL GROUP-CONTAINED ACRYLATE COPY POLYMERIZATE, PROCEDURE WITH PREPARATION THEREOF, AND USE OF THE ACRYLATE COPOLYMERIZATE IN A COATING AGENT. |
Country Status (1)
Country | Link |
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NO (1) | NO168252C (en) |
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1987
- 1987-05-29 NO NO872278A patent/NO168252C/en not_active IP Right Cessation
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Publication number | Publication date |
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NO872278L (en) | 1987-07-14 |
NO872278D0 (en) | 1987-05-29 |
NO168252C (en) | 1992-01-29 |
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