MXPA01005873A - Method for producing a polymer reaction product - Google Patents
Method for producing a polymer reaction productInfo
- Publication number
- MXPA01005873A MXPA01005873A MXPA/A/2001/005873A MXPA01005873A MXPA01005873A MX PA01005873 A MXPA01005873 A MX PA01005873A MX PA01005873 A MXPA01005873 A MX PA01005873A MX PA01005873 A MXPA01005873 A MX PA01005873A
- Authority
- MX
- Mexico
- Prior art keywords
- radical
- free radical
- monomer
- substituted
- reaction product
- Prior art date
Links
- 239000007795 chemical reaction product Substances 0.000 title claims abstract description 27
- 229920000642 polymer Polymers 0.000 title claims description 45
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 19
- 239000011541 reaction mixture Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000008346 aqueous phase Substances 0.000 claims description 7
- PJANXHGTPQOBST-VAWYXSNFSA-N (E)-Stilbene Chemical compound C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 229960002887 Deanol Drugs 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Tris Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- PJANXHGTPQOBST-QXMHVHEDSA-N (Z)-Stilbene Chemical compound C=1C=CC=CC=1/C=C\C1=CC=CC=C1 PJANXHGTPQOBST-QXMHVHEDSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N Diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N Dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 230000002209 hydrophobic Effects 0.000 claims description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N Diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N ethyl amine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims 1
- 229940086542 triethylamine Drugs 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 45
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 34
- -1 thiocarbonylthio compound Chemical class 0.000 description 28
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000002194 synthesizing Effects 0.000 description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 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 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinylpyrrolidone Chemical class C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N N-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229960004418 Trolamine Drugs 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 238000011068 load Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000002763 monocarboxylic acids Chemical class 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 229940029612 triethanolamine Drugs 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N (E)-but-2-enedioate;hydron Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N 2-cyanopropene-1 Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N 2-hydroxyethyl 2-methylacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-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
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-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
- ALXUOLQRSSGTMU-UHFFFAOYSA-N 6-(diethylamino)-2-methylhex-2-enamide Chemical compound CCN(CC)CCCC=C(C)C(N)=O ALXUOLQRSSGTMU-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N Ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N Itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- XFHJDMUEHUHAJW-UHFFFAOYSA-N N-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L Sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N butyl 2-methylprop-2-enoate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000004815 dispersion polymerization Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
- 238000007342 radical addition reaction Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920000638 styrene acrylonitrile Polymers 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N α-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- IAXXETNIOYFMLW-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) 2-methylprop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C(=C)C)CC1C2(C)C IAXXETNIOYFMLW-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- FSRCPKKQDVVIQS-UHFFFAOYSA-N 1-(prop-2-enoylamino)pentan-3-ylphosphonic acid Chemical compound CCC(P(O)(O)=O)CCNC(=O)C=C FSRCPKKQDVVIQS-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 1-ethenyl-4-methylbenzene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-O 1-ethenylimidazole;hydron Chemical class C=CN1C=C[NH+]=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-O 0.000 description 1
- WDRZVZVXHZNSFG-UHFFFAOYSA-N 1-ethenylpyridin-1-ium Chemical class C=C[N+]1=CC=CC=C1 WDRZVZVXHZNSFG-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
- 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 1
- SSZXAJUPVKMUJH-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate;hydrochloride Chemical compound Cl.CN(C)CCOC(=O)C=C SSZXAJUPVKMUJH-UHFFFAOYSA-N 0.000 description 1
- BDKSYBXVYUGXIG-UHFFFAOYSA-N 2-(ethylamino)ethyl prop-2-enoate Chemical compound CCNCCOC(=O)C=C BDKSYBXVYUGXIG-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Acrylamido-2-methylpropane sulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 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
- MZGMQAMKOBOIDR-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCO MZGMQAMKOBOIDR-UHFFFAOYSA-N 0.000 description 1
- VETIYACESIPJSO-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound OCCOCCOCCOC(=O)C=C VETIYACESIPJSO-UHFFFAOYSA-N 0.000 description 1
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- NEYTXADIGVEHQD-UHFFFAOYSA-N 2-hydroxy-2-(prop-2-enoylamino)acetic acid Chemical compound OC(=O)C(O)NC(=O)C=C NEYTXADIGVEHQD-UHFFFAOYSA-N 0.000 description 1
- UIERETOOQGIECD-UHFFFAOYSA-N 2-methylbut-2-enoic acid Chemical compound CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- PSZAEHPBBUYICS-UHFFFAOYSA-N 2-methylidenepropanedioic acid Chemical compound OC(=O)C(=C)C(O)=O PSZAEHPBBUYICS-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- KFNGWPXYNSJXOP-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)OCCCS(O)(=O)=O KFNGWPXYNSJXOP-UHFFFAOYSA-N 0.000 description 1
- BQQGVSONEPNPAB-UHFFFAOYSA-N 3-(diethoxymethylsilyl)propyl 2-methylprop-2-enoate Chemical compound CCOC(OCC)[SiH2]CCCOC(=O)C(C)=C BQQGVSONEPNPAB-UHFFFAOYSA-N 0.000 description 1
- SLDXSSRFNABVCN-UHFFFAOYSA-N 3-diethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[SiH](OCC)CCCOC(=O)C(C)=C SLDXSSRFNABVCN-UHFFFAOYSA-N 0.000 description 1
- BZCWFJMZVXHYQA-UHFFFAOYSA-N 3-dimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[SiH](OC)CCCOC(=O)C(C)=C BZCWFJMZVXHYQA-UHFFFAOYSA-N 0.000 description 1
- SDYYWRBMQSZLOC-UHFFFAOYSA-N 3-methyloxetane-2,4-dione Chemical compound CC1C(=O)OC1=O SDYYWRBMQSZLOC-UHFFFAOYSA-N 0.000 description 1
- NYUTUWAFOUJLKI-UHFFFAOYSA-N 3-prop-2-enoyloxypropane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCOC(=O)C=C NYUTUWAFOUJLKI-UHFFFAOYSA-N 0.000 description 1
- YFISHOAHNLGUEL-UHFFFAOYSA-N 3-tributoxysilylpropyl prop-2-enoate Chemical compound CCCCO[Si](OCCCC)(OCCCC)CCCOC(=O)C=C YFISHOAHNLGUEL-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 1
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 description 1
- JDCCCHBBXRQRGU-UHFFFAOYSA-N 5-phenylpenta-2,4-dienenitrile Chemical compound N#CC=CC=CC1=CC=CC=C1 JDCCCHBBXRQRGU-UHFFFAOYSA-N 0.000 description 1
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N Benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- AYFZTTMHGQGYLE-UHFFFAOYSA-N C(C(=C)C)(=O)OCCC([SiH2]C)(OC(C)C)OC(C)C Chemical compound C(C(=C)C)(=O)OCCC([SiH2]C)(OC(C)C)OC(C)C AYFZTTMHGQGYLE-UHFFFAOYSA-N 0.000 description 1
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 description 1
- PAOULKYBFBZLBP-UHFFFAOYSA-N CC(C)OC(OC(C)C)[SiH2]CCCOC(=O)C=C Chemical compound CC(C)OC(OC(C)C)[SiH2]CCCOC(=O)C=C PAOULKYBFBZLBP-UHFFFAOYSA-N 0.000 description 1
- KIUQKRVLTQTVDR-UHFFFAOYSA-N CC(C)O[SiH](OC(C)C)CCCOC(=O)C=C Chemical compound CC(C)O[SiH](OC(C)C)CCCOC(=O)C=C KIUQKRVLTQTVDR-UHFFFAOYSA-N 0.000 description 1
- SWNRQFURMFHRNC-HJWRWDBZSA-N CCCCCC\C(=C\C(N)=O)C(=O)NC Chemical compound CCCCCC\C(=C\C(N)=O)C(=O)NC SWNRQFURMFHRNC-HJWRWDBZSA-N 0.000 description 1
- DACWUGOLTNQROR-UHFFFAOYSA-N CCO[SiH](OCC)CCCOC(=O)C=C Chemical compound CCO[SiH](OCC)CCCOC(=O)C=C DACWUGOLTNQROR-UHFFFAOYSA-N 0.000 description 1
- HHHPYRGQUSPESB-UHFFFAOYSA-N COC(OC)[SiH2]CCCOC(=O)C=C Chemical compound COC(OC)[SiH2]CCCOC(=O)C=C HHHPYRGQUSPESB-UHFFFAOYSA-N 0.000 description 1
- HNVMCAHOYIOFAQ-UHFFFAOYSA-N CO[SiH](OC)CCCOC(=O)C=C Chemical compound CO[SiH](OC)CCCOC(=O)C=C HNVMCAHOYIOFAQ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N Chloroethane Chemical group CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N Citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Diethyl maleate Chemical compound CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N Diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N Dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N Glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N Indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- 229940119545 Isobornyl methacrylate Drugs 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N Mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N Methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- DPLUMPJQXVYXBH-UHFFFAOYSA-N N,N-diethyl-2-phenylethenamine Chemical compound CCN(CC)C=CC1=CC=CC=C1 DPLUMPJQXVYXBH-UHFFFAOYSA-N 0.000 description 1
- UTKONZMCFKGKAR-UHFFFAOYSA-N N,N-diethyl-2-phenylprop-1-en-1-amine Chemical compound CCN(CC)C=C(C)C1=CC=CC=C1 UTKONZMCFKGKAR-UHFFFAOYSA-N 0.000 description 1
- 229940088644 N,N-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N N,N-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N N-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- VQGWOOIHSXNRPW-UHFFFAOYSA-N N-butyl-2-methylprop-2-enamide Chemical compound CCCCNC(=O)C(C)=C VQGWOOIHSXNRPW-UHFFFAOYSA-N 0.000 description 1
- YRVUCYWJQFRCOB-UHFFFAOYSA-N N-butylprop-2-enamide Chemical compound CCCCNC(=O)C=C YRVUCYWJQFRCOB-UHFFFAOYSA-N 0.000 description 1
- OFESGEKAXKKFQT-UHFFFAOYSA-N N-ethenyl-N-methylformamide Chemical compound C=CN(C)C=O OFESGEKAXKKFQT-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N N-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N N-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- CNWVYEGPPMQTKA-UHFFFAOYSA-N N-octadecylprop-2-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)C=C CNWVYEGPPMQTKA-UHFFFAOYSA-N 0.000 description 1
- QQZXAODFGRZKJT-UHFFFAOYSA-N N-tert-butyl-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC(C)(C)C QQZXAODFGRZKJT-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 229920001748 Polybutylene Polymers 0.000 description 1
- 229920001451 Polypropylene glycol Polymers 0.000 description 1
- 229920001567 Vinyl ester Polymers 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N Vinyl fluoride Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N Vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N Vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-BREBYQMCSA-N [(1R,3R,4R)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C=C)C[C@@H]1C2(C)C PSGCQDPCAWOCSH-BREBYQMCSA-N 0.000 description 1
- VUQBZRUPQCOFGI-UHFFFAOYSA-N [1-[(2-methylpropan-2-yl)oxy]-2-phenylethenyl]benzene Chemical group C=1C=CC=CC=1C(OC(C)(C)C)=CC1=CC=CC=C1 VUQBZRUPQCOFGI-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atoms Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WQHCGPGATAYRLN-UHFFFAOYSA-N chloromethane;2-(dimethylamino)ethyl prop-2-enoate Chemical compound ClC.CN(C)CCOC(=O)C=C WQHCGPGATAYRLN-UHFFFAOYSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 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
- 229960003750 ethyl chloride Drugs 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229920000578 graft polymer Polymers 0.000 description 1
- 239000003630 growth substance Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- KCAMXZBMXVIIQN-UHFFFAOYSA-N octan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C(C)=C KCAMXZBMXVIIQN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative Effects 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HETCEOQFVDFGSY-UHFFFAOYSA-N prop-1-en-2-yl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229960002668 sodium chloride Drugs 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Abstract
A method for producing a reaction product (A) comprising the following step (i):(iv) a reaction mixture comprising at least one radically reactable monomer (a) is reacted in radical conditions in the presence of at least one radical initiator and a compound of formula (I), wherein R1-R4 represent independently from each other hydrogen, a respectively unsubstituted or substituted alkyl radical, a cycloalkyl radical, an aralkyl radical, an unsubstituted or substituted aromatic hydrocarbon radical, under the proviso that at least two from R1-R4 represent an unsubstituted or substituted aromatic hydrocarbon radical.
Description
METHOD TO PRODUCE A POLYMER REACTION PRODUCT
The present invention relates to a method for preparing a reaction product (A) by the reaction, under free radical conditions, of at least one monomer that can react as free radical (a) in the presence of less a free radical initiator and a compound (I), as defined below, in aqueous phase, to said reaction product per se, to a method for preparing a
polymer, which uses said reaction product, and its use in the dispersions of the polymer. The present invention is placed within the technical field of free radical addition polymerization, which has typical characteristics of a
In the case of active polymerization, the method of the invention is capable, in principle, of supplying reaction products or polymers, which can have a narrow molecular weight distribution (Mw / Mn). Also, through the proper selection of the monomers and, if desired, the
By successively adding various monomers, it is possible to produce homopolymers and copolymers, both branched and unbranched, and also block copolymers. In this context, the present invention relates not only to the polymer itself, but also to a reaction product obtained in a first stage. Over a number of years, there has been great interest in methods and process concepts that are suitable for preparing a large number of polymers and making possible the preparation of polymers of this kind, having a predetermined structure, molecular weight and molecular weight distribution. . For example, WO 98/01478 describes a method for preparing polymers, in which the monomer to be reacted, which is selected, in particular, from vinyl monomers and acid derivatives, having unsaturated groups, such as anhydrides, esters and imides of (meth) acrylic acid, for example, reacts in the presence of a free radical initiator and a thiocarbonylthio compound, as a chain transfer agent. WO 92/13903 describes a method for prepolishing polymers having a low molecular weight, by free radical chain polymerization of one or more monomers in the presence of a chain transfer agent, as defined herein, which has a double CS link. As is clear from that document, the compounds described herein, which have a double C- bond, do not act as chain transfer agents, but also as growth regulators, so, according to that document, it is only possible to prepare polymers of low molecular weight in the presence of this compound. A method for the chain polymerization of
The free radical of unsaturated monomers in an aqueous medium and in the presence of a macromonomer, having an end group of -CH2C (X) = CH2, is defined in WO 93/22351, which also defines X In evidence of the examples of that application, various (meth) acrylates or (meth) acrylic acid, if desired, monomers, such as styrene,
are reacted in each case under the conditions of emulsion or suspension polymerization. WO 93/22355 relates to a process for preparing crosslinkable polymers, which use a macromonomer, as described in WO 93/22351. WO 96/15157 describes, similarly, a method for preparing polymers having a comparatively narrow molecular weight distribution, in which a vinyl monomer, as defined herein, is reacted with a similar vinyl-terminated macromonomer , in the
presence of a free radical initiator. Likewise, WO 98/37104 relates to the preparation of polymers of controlled molecular weight, including acrylate-based polymers, by the polymerization of free radial of corresponding monomers, which use a
Chain transfer agent, which is defined more closely here, and a double bond of C-C, and radicals that activate that double bond in terms of the free radical addition reaction of the monomers. < - A polymerization or chain copolymerization of
free radical with an oligo (methyl methacrylate) - unsaturated with ethyl acrylate, styrene, methyl methacrylate, acrylonitrile and vinyl acetate as comonomers, described in a scientific article in J. Macromol. Sci. -Chem., A 23 (7), 839-851 (1986). It is an object of the present invention to provide a novel method for preparing a reaction product, which can be used, inter alia, as a macroinitiator and which can first be used by itself, as an emulsifying or dispersing agent and with the
It is also possible to react with free radical monomers, homopolymerizable or copolymerizable, in order to obtain further polymers that possibly differ in composition. It is a further object of the present invention to provide the specific adjustment
of the properties of the polymer and thus allow the diverse use of polymers thus adjusted, which can be obtained by the simple polymerization of free radical, in particular by the preparation of block structures by means of free radical polymerization.
We have found that these objects can be achieved by the method of the invention to prepare a reaction product (A), which comprises the next step
(i): (i) reacting, under free radical conditions, a reaction mixture, comprising at least one monomer (a) that can react as a free radical, in the presence of at least one free radical initiator and a compound (I) of the formula:
R3 Ri \ / C - c / \ R2
wherein R_ to R4, independently of one another, are hydrogen, an alkyl radical, substituted or unsubstituted, a cycloalkyl radical or an aralkyl radical, or an aromatic hydrocarbon radical, unsubstituted or substituted, with the proviso that at least two of Ri to R4 are radicals of aromatic hydrocarbons, unsubstituted or substituted. in aqueous phase.
The invention further provides a reaction product (A), which can be prepared by a method comprising the following step (i): f¿
(i) reacting, under free radical conditions, a reaction mixture, comprising at least one monomer (a) which can react in free radical, in the presence of at least one free radical initiator and a compound (I) ) of the formula: 10
C C / \ 15 R4 R2
wherein R_ to R4, independently of one another, are hydrogen, an alkyl radical, substituted or unsubstituted, a cycloalkyl radical or a radical
aralkyl, or aromatic hydrocarbon radical, unsubstituted or substituted, with the proviso that at least two of R to R4 are aromatic hydrocarbon radicals, unsubstituted or substituted, in aqueous phase.
Within the scope of the above method of the invention, it is possible to use all the monomers (a) which can react in free radical. As the monomer (a) is preferred, it uses those homopolymerizable or copolymerizable, free radical compounds, which include a hydrophilic group, such as, for example, a carboxyl group. More preferably, the monomers (a) comprise homopolymerizable or copolymerizable monomers, free radical, hydrophilic, that is monomers whose solubility in water is greater than that of styrene. Of course, it is also possible to make mixtures of different hydrophilic monomers and mixtures of at least one hydrophilic monomer and at least one hydrophobic monomer, which is present in the reaction mixture of step (i). Representative examples of the monomers (a) are methyl methacrylate, ethyl methacrylate, propyl methacrylate (all isomers), methacrylate butiio (all isomers) acrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, methacrylic acid, benzyl methacrylate, phenyl methacrylate, methacrylonitrile, alpha-methyl styrene, methyl acrylate, ethyl acrylate, propyl acrylate (all isomers), butyl acrylate
(All isomers), 2-ethylhexyl acrylate, isobornyl acrylate, acrylic acid, benzyl acrylate, phenyl acrylate, acrylonitrile, styrene, methacrylates func: .onalizados; acrylic acids and styrenes, selected from glycidyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate (all isomers), hydroxybutyl methacrylate (all isomers), diethylaminoethyl methacrylate, triethylene glycol methacrylate, itaconic anhydride, itaconic acid , glycol acrylate: .dyl, 2-hydroxyethyl acrylate, hydroxypropyl acrylate (all isomers), hydroxybutyl acrylate (all isomers), diethylaminoethyl acrylate, triethylene glycol acrylate, methacrylamide, N-tert-butyl methacrylamide , N-butyl-methacrylamide, N-methylolmethacrylamide, N-ethylolmethacrylamide, N-tert.-butylacrylamide, N-butylacrylamide, N-methylol-acrylamide, N-ethylol acrylamide, vinylbenzoic acid (all isomers), diethylaminostyrene (all isomers), alpha-methylvinylbenzoic acid (all isomers), diethylamino-alpha-methylstyrene (all isomers), para-methylstyrene, p-vinylbenzenesulfonic acid, trimethyl methacrylate etixisililpropilo methacrylate, triethoxysilylpropyl methacrylate tributoxisililpropilo methacrylate, diethoxymethylsilyl-propyl methacrylate, dibutoximetilsililpropilo, diisopropoxy-methylsilylpropyl methacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropyl methacrylate, dibutoxysilylpropyl methacrylate, propyl methacrylate diisopropoxisilil- acrylate, trimethoxysilylpropyl acrylate, triethoxysilylpropyl, tributoxysilylpropyl acrylate, dimethoxymethylsilylpropyl acrylate, acrylate
£ * diethoxymethylsilylpropyl, dibutoxymethyl-5-silylpropyl acrylate, diisopropoxymethylsilylpropyl acrylate, dimethoxysilylpropyl acrylate, diethoxysilylpropyl acrylate, dibutoxysilylpropyl acrylate, diisopropoxysilylpropyl acrylate, vinyl acetate and vinyl butyrate, vinyl chloride, vinyl fluoride, bromide from
vinyl, and mixtures of the aforementioned monomers. Preferably used as a first monomer (a ') are acrylic or methacrylic acid, a C 1 -C 4 alkyl acrylate or methacrylate or C 1 -C 4 hydroxyalkyl, a substituted or unsubstituted vinyl pyrrolidone, a mixture of
Two or more thereof, or a mixture of said first monomer (a) with at least one monomer (a) homopolymerizable or copolymerizable free radical more. Also used, according to the invention, in relation to the preparation of the reaction product (A), is
a compound (I) of the formula:
R3 Ri \ / c C * - * 25 / R2 where Ri to R4, independently of one another, are hydrogen, an alkyl radical, substituted or unsubstituted, a cycloalkyl radical or a radical
I? Aralkyl, or an unsubstituted or substituted aromatic hydrocarbon radical, the invention requires that at least two of Ri to R4 be an aromatic, unsubstituted or substituted hydrocarbon radical.
Again, it is possible, in principle, to use all
compounds of the above formula, according to the invention. Preference is given as the compound (I) to the use of diphenylethylene, dinaphthalethylene, 4,4-vinylidene-bis (N, N'-dimethylaniline), 4,4-vinylidene-bis (aminobenzene), cis- and trans-stilbene or a mixture of two or more of them,
Furthermore, preference is given to the use of diphenylethylene. It is also possible to use the substituted diphenylethylenes, which are substituted on either or both aromatic hydrocarbon radicals, with removal of electrons or electron donating substituents, such as, for example,
Tertiary butyl, benzyl or CN groups, or an alkoxydiphenyl ethylene, such as, for example, methoxy-, ethoxy- or tert-butoxy-diphenylethylene,. or thio or amino analogs compounds. In addition, the method of the invention is conducted in the
In the presence of at least one free radical initiator, preference is given here to oxidation-free radical initiators. The initiator should preferably be soluble in water. In general, however, it is possible to use the all azo and / or peroxo compounds, which are conventionally used in the free radical chain polymerization. Suitable initiators are described in WO 98/01478 on page 10, lines 17-34, which, in this aspect, is incorporated in its entirety in the present specification. Preference is given to the use of oxidation-free radical initiators, such as potassium, sodium and ammonium peroxodisulfates, for example, or in combination with, a conventional, i.e., non-oxidizing, initiator with H202. In a preferred embodiment of the method of the invention, a comparatively large amount of the free radical initiator is added, this free radical initiator, as a proportion of the reaction mixture, is preferably 0.5 to 50% by weight, more preferably from 1 to 20% by weight, with base, in each case, in the general amount of the monomer (a) and the initiator. The ratio of the initiator to the compound (I) is preferably from 3: 1 to 1: 3, more preferably from 2: 1 to 1: 2 and, in particular, from 1.5: 1 to 1: 1.5. The reaction, described above, of according to step (i), it is conducted in an aqueous phase, in this case preference is given here to water or mixtures of water with miscible solvents therein, such as THF and ethanol, for example. It is, however, also possible to conduct the reaction in the presence of a mixture of water and a water-immiscible solvent, such as, for example, an aromatic solvent, such as toluene, for example. In a further embodiment, the above reaction, according to step (i) is conducted in the presence of at least one base. In this context, all bases with low molecular mass can be used in principle, preferably given to NaOH, KOH, ammonia, diethanolamine, triethanolamine, mono-, di- and triethanolamine, dimethylethanolamine or a mixture of two or more of them, and with reference particular to ammonia and di- and tri-ethanolamine. The reaction, conducted at temperatures according to step (i), is generally above room temperature and below the decomposition temperature of the monomers, the temperature range chosen is preferably 50 to 150 ° C, more preferably 70 to 120 ° C and, in particular, 80 to 110 ° C. Although there are no restrictions of any kind with respect to molecular weight distribution, it is possible in the reaction, according to (i), to obtain a reaction product having a molecular weight distribution, Mw / Mn, as measured by chromatography gel permeation, which uses polystyrene as a standard, from <; 4, preferably < 3, more preferably < 2, in particular < 1.5 and, in certain cases, < _1.3. The molecular weights of the reaction product (A) can be controlled within wide limits by selecting the ratio of monomers (a) to compounds (I), to the free radical initiator. In this context, the molecular weight is determined, in particular, by the amount of the compound (I), specifically so that the greater proportion of the compound (1), the lower the resulting molecular weight. The reaction, according to step (i), can also be conducted in the presence of a surfactant. The reaction product obtained in the reaction, according to (i), which is generally produced in the form of an aqueous mixture, can, in that case, be further processed directly as a dispersion. or also used as a macroinitiator for the subsequent reaction, according to step (ii), as defined below below. It is also possible to isolate the reaction product from step (i) as a solid and then react it further or send it for use.
In the reaction, according to step (ii), it is possible to react at least one monomer (b) homopolymerizable or copolymerizable, free radical, freely selected. This monomer (b) can be identical or different from monomer (a), used in step (i). The selection of the monomer (b) is made in principle, according to the desired structure of the polymer prepared in step (ii) and thus, depending on the intended use of this polymer. The following specific monomers preferred for use as the monomers (b) can be mentioned: The monomers (b) are preferably selected from C3-C_0 monocarboxylic acids, monoethylenically unsaturated, their alkali metal salts and / or ammonium salts, examples are acrylic acid, methacrylic acid, dimethylacrylic acid, ethylacrylic acid, allylacetic acid and vinylacetic acid, - and also C4-C_ dicarboxylic acids, monoethylenically unsaturated, their anhydrides, monoesters, alkali metal salts and / or ammonium salts, examples being maieic acid, fumaric acid, itaconic acid, mesaconic acid, methylenemalonic acid, citraconic acid, maieic anhydride, itaconic anhydride and methylmalonic anhydride; and also monoethylenically unsaturated monomers containing sulfonic acid groups, examples being allylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methallylsulfonic and vinylsulphonic acid, 3-sulfo-propyl acrylate and 3-sulfopropyl methacrylate. , and also monoethylenically unsaturated monomers containing phosphonic acid groups, examples being vinylphosphonic acid, allyl-osophonic acid, and acrylamidoethylpropane-phosphonic acid, C_-C20 hydroxyalkyl alkyl esters, of C3-C monocarboxylic acids. , monoethylenically unsaturated or C4-C8 dicarboxylic acids, examples being methyl acrylate, ethyl acrylate, n-butyl acrylate, stearyl acrylate, diethyl maleate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate , and hydroxypropyl methacrylate, and also the (meth) acrylic esters of C alcohols .-C.e alkoxylates, which have reacted with from 2 to 50 moles of ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof; and also N-substituted amides and amides of C3-C_0 monoethylenically unsaturated monocarboxylic acids or C4-C8 dicarboxylic acids, examples being the acrylamide, N-alkyl acrylamides and N, N-dialkyl acrylamides, in this case with 1 to 18 atoms carbon in the alkyl group, such as N-methylacrylamide, N, N-dimethylacrylamide, N-tert.-butylacrylamide and N-octadecyl acrylamide, N-methylhexylmaleamide, N-decamaleamide, diethylaminopropylmethacrylamide and acrylamidoglycolic acid; and also the alkylamidoalkyl (meth) acrylates, examples being dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethyl aminopropyl acrylate and dimethyl methacrylate inopropyl; and also vinyl esters, such as vinyl acetate, vinyl acetate and vinyl propionate, which may also be in hydrolyzed form following polymerization; and also
N-vinyl compounds, examples being N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinyl-N-methylformamide, 1-vinylimidazole and l-vinyl-2-methylimidazole; and also the vinyl ethers of C? -C? 8 alcohols, vinyl ethers of alkoxylated C.-Ciß alcohols and vinyl ethers of
polyalkylene oxides, such as polyethylene oxide, polypropylene oxide or polybutylene oxide, styrene or its derivatives, such as alpha-methylstyrene, indene and dicyclopentadiene; monomers containing amino or imino groups,
such as, for example, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, diethylaminopropylmethacrylamide and allylamine, monomers bearing quaternary ammonium groups, in the form, for example, of salts, as obtained by the reaction of the basic functions of
amino with acids, such as hydrochloric acid, sulfuric acid, nitric acid, formic acid or acetic acid, or in quaternized form (examples of suitable quaternizing agents being dimethyl sulfate, diethyl sulfate, methyl tt chloride, sodium chloride, ethyl and benzyl chloride), such as, for example, dimethylaminoethyl acrylate hydrochloride, diallyldimethylammonium chloride, dimethylaminoethyl acrylate methyl chloride, dimethylaminoethylamino-propylmethacrylamide methosulfate, vinylpyridinium salt and 1-vinylimidazolium salts; and monomers in which amino groups and / or ammonium groups are released only after polymerization and subsequent hydrolysis, such as, for example, N-vinylformamide and N-vinylacetamide. The present invention also provides a method for preparing a polymer (B), which comprises: reacting the reaction product (A) obtained in it. step (1), under free radical conditions, in the presence of at least one monomer (b) homopolymerizable or copolymerizable, free radical. The reaction, according to step (ii), is conducted, in principle, in accordance with the usual conditions, for the polymerization of free radical, it being possible that suitable solvents are present.
Steps (i) and (ii) of the process of the invention can be conducted separately, both spatially and temporally, in each case, of course step (i) tt is conducted first and then step (ii). However, in addition, steps (i) and (ii) can be carried out in succession in a reactor, that is to say, first of all, the compound of formula (I) is reacted, partially or totally, as a function of the desired use and / or the desired properties, with at least the monomer (a) and then
At least one monomer (b) is added and the free radical polymerization is carried out, or also directly from starting with a monomer mixture comprising at least one monomer (a) and at least one monomer (b), the which are used and react with the compound (I). In this context,
assumes that the compound (I) is reacted first of all with at least one monomer (a) and then the reaction product (A) thus formed also reacts, above a certain molecular weight, with the monomer (b). Depending on the reaction regime, it is possible,
according to the invention, in this case, prepare functionalized polymers of the end group,
(c) polymers of gradient of blocks or multiple blocks, star polymers, graft copolymers and branched (co) polymers.
As is evident from the above, the present invention also provides the polymer (B), which can in itself be prepared by the process defined above. In this context, the reaction of the invention is conducted to thereby provide a polymer (B), which has a block structure. In this context, it is possible, according to the invention, for the first time to supply block copolymers in a simple manner, using the compound (I), readily available, these block copolymers having, for example, a
hydrophilic block, such as, for example, an acid
(meth) acrylic or a block of C? -4 alkyl (meth) acrylate, and in addition, a preferably hydrophobic polymer block, such as, for example, a block based on vinylaromatic monomers, such as, for example, styrene or
substituted styrenes, and also non-aromatic vinyl compounds, such as, for example, vinyl acetate and also alkyl (meth) acrylates (> C4). Also, it is also possible, according to the invention, to prepare polymers of the following structure: poly (meth) acrylic acid - (meth) acrylate-b- (styrene - (meth) acrylate)). The term "(meth) acrylate" denotes alkyl esters of methacrylic acid and acrylic acid. Specifically, mention may be made of the
following new block polymers: poly (acrylic acid-b-styrene), poly (methyl-methacrylate-b-styrene), poly (methacrylic acid-b-hydroxyethyl acrylate), poly (methyl methacrylate-bN-vinyl-pyrrolidone), poly (methyl methacrylate-bN-vinyl-formamide), poly (methyl methacrylate-b-hydroxyethyl acrylate), poly (methyl methacrylate-b-styrene-acrylonitrile)), poly (n-butyl-b-styrene-b-styrene-b-acrylate n-butyl acrylate), poly ( methyl methacrylate-b-styrene-b-methyl methacrylate-b-styrene), and poly (n-butyl-b-styrene-b-styrene-b-acrylate n-butyl-b-styrene acrylate). Also, the present invention also provides an aqueous mixture comprising the reaction product (A) of the invention, the polymer (B) of the invention or a combination of two or more of them. The aqueous mixture, which comprises the reaction product (A), can be used, in particular, as a primary dispersion. The reaction product (A) and / or the polymer (B), or a mixture of two or more of them, can be used according to the field of application, in a form suitable for the purpose, especially in polymer dispersions . The intention of the following text is to illustrate the present invention with reference to a number of examples.
Example 1 Synthesis of poly (acrylic acid-b-styrene) 224 g of water and 15.4 g of 25% ammonia were heated to 90 ° C. 3 g of 1, 1-diphenylethylene, dissolved in 45 μl of acrylic acid and 4.73 g of ammonium peroxodisulfate, dissolved in 22.4 g of water, then added in droplets in parallel, through 2 drip funnels in the course 30 minutes. The batch was maintained at 90 ° C for a total of 4 hours. 101 g of this batch were mixed with 25 g of water,
40 ml of a 25% ammonia solution and 38 g of styrene, and then kept at 90 ° C for 13 hours. This provided a white polymer, which can be swollen with water.
Example 2 Synthesis of poly (methyl methacrylate-b-styrene) 125 g of a 25% ammonia solution in 125 g of acfua, were initially introduced and the oil bath kept at 90 ° C. 6 g of 1,1-diphenylethylene, dissolved in 125 g of methyl methacrylate and 4.73 g of ammonium peroxodisulfate, dissolved in 22.4 g of water, then added in droplets in parallel through 2 dropping funnels in the course of 60 minutes. Then, 4.73 g more of ammonium peroxodisulfate, dissolved in 22.4 g of water, were added in drops in the course of one hour. The batch was then kept at 90 ° C for one more hour. 65 g of styrene were added to this batch and the temperature of the oil bath was raised to 100 ° C. After 4 hours, a white polymer was obtained, which can be swollen in air, with an Mw of 15,000 g / mol and a polydispersity of 1.5. The structure of the block was detected by means of electron microscopy.
Example 3 Synthesis of poly (methacrylic acid-hydroxyethyl b-acrylate 112 g of water and 112 g of a 25% ammonia solution, were initially introduced and heated to 90 ° C. Then 9.46 g of ammonium peroxodisulfate, dissolved in 45 g of water were added in drops, in the course of 30 minutes, and 6 g of 1,1-diphenylethylene, dissolved in 107.5 g of methacrylic acid were added in droplets quickly, then 9.46 g more were added dropwise. of ammonium peroxydisulfate, dissolved in 45 g of water, over the course of 30 minutes, after this addition, the batch was kept at 90 ° C for 5 hours, then 1 mole of hydroxyethyl acrylate was added to the batch and kept at 85 ° C for 5 hours.
A water-soluble polymer was obtained.
Example 4 Synthesis of poly (methyl methacrylate-b-N-vinyl-pyrrolidone) 360 g of water were initially introduced and kept at 90 ° C. Then, in parallel, 10 g of 1,1-diphenylethylene, dissolved in 200 g of methyl methacrylate and 10.3 g of ammonium peroxodisulfate, dissolved in 100 g of water, were added in drops in the course of 60 minutes and 9.2 g of a 25% ammonia solution, dissolved in 100 g of water, were added in drops over the course of 90 minutes. The batch was then kept at 90 ° C for 3 hours. Then, 20.4 g of the N-vinylpyrrolidone was added to 100 g of the dispersion described above and the batch was maintained at 75 ° C for 5 hours.
Example 5 Synthesis of poly (methyl methacrylate-b-N-vinyl-formamide) 360 g of water were initially introduced and maintained at 90 ° C. Then, in parallel, 10 g of 1,1-diphenylethylene, dissolved in 200 g of methyl methacrylate and 10.3 g of ammonium peroxodisulfate, dissolved in 100 g of water, were added in drops in the course of 60 minutes and 9.2 g of a 25% ammonia solution, dissolved in 100 g of water were added in drops over the course of 90 minutes. The batch was maintained at 90 ° C for 3 hrs. Then, 25 g of N-vinylformamide was added to 100 cf of the above-described dispersion, and the batch was kept at 75 ° C for 6 hours.
Ejemp > 6 Synthesis of poly (methyl methacrylate - b-hydroxyethyl acrylate) 360 g of water were initially introduced and kept at 90 ° C. Then, in parallel, 10 g of 1,1-diphenylethylene, dissolved in 200 g of methyl methacrylate, and 10.3 g of ammonium peroxodisulfate, dissolved in 100 g of water, were added in drops, in the course of 60 minutes, and 9.2 g of a 25% ammonia solution, dissolved in 100 g of water, were added in drops over the course of 90 minutes. The batch was then kept at 90 ° C for 3 hours. Then, 25 g of the hydroxyethyl acrylate was added to 100 g of the dispersion described above, and the batch was maintained at 75 ° C for 6 hours. Example 7 Synthesis of poly (methyl methacrylate - b - (styrene-acrylonitrile)) 360 g of water were initially introduced and maintained at 90 ° C. Then, in parallel, 10 g of 1,1-diphenylethylene, dissolved in 200 g of methyl methacrylate, and 10.3 g of ammonium peroxodisulfate, dissolved in 100 g of water, were added in drops, in the course of 60 minutes, and 9.2 f of a 25% ammonia solution, dissolved in 100 g of acfua, were added in drops over the course of 90 minutes. The batch was then kept at 90 ° C for 3 hours. Then, 17.2 g of styrene and 1 g of acrylonitrile were added to 100 g of the dispersion, described above, and the batch was kept at 75 ° C for 6 hours. A polymer having an Mw of 7,100 g / mol and a polydispersity of 2.7 was obtained.
Example 8 Synthesis of poly (n-butyl acrylate-b-styrene-b-n-butyl acrylate) 360 g of water were initially introduced and the oil bath was heated to 90 ° C. Then, through 3 dropping funnels, 11.1 g of 1,1-diphenylethylene, dissolved in 256 g of n-butyl acrylate and 10.7 g of sodium peroxodisulfate, dissolved in 100 g of water, were added in drops, in parallel, in the course of 180 minutes, and 2.3 g of sodium hydroxide dissolved in 100 g of water were added in drops, in the course of 120 minutes. The oil bath was maintained at 90 ° C for a total of 6 hours. Following removal of the aqueous phase, 138 g of styrene was added to the remaining polymer and the oil bath was maintained at 115 ° C for 6 hours. Subsequently, 169 g of n-butyl acrylate were added and the oil bath was maintained at 115 ° C for 6 hours. A polymer was obtained having an Mw of 366,000 g / mol, and a polydispersity of 2.6.
Example 9 Synthesis of poly (methyl methacrylate-b-styrene) 180 g of water were initially introduced and maintained at 90 ° C. Then, in parallel, from 3 drip funnels, 3 g of cis-stilbene, dissolved in 50 g of methyl methacrylate and 5 g of a 25% ammonia solution, dissolved in 50 g of water, were added in drops in 60 minutes, and 5.1 g of ammonium peroxodisulfate dissolved in 50 g of water, were added in drops in 90 minutes. The batch was then kept at 90 ° C for 4.5 hours more. A polymer having a Mw of 54,200 g / mol and a polydispersity of 2.4 was obtained.
70 g of the polymer dispersion, described above, were heated to 115 ° C and 50 g of styrene were metered into it. The batch was then kept at 115 ° C for 6 hours. ft A polymer was obtained having an Mw of 207,000 5 g / mol and a polydispersity of 3.1.
Example 10 Synthesis of poly (methyl methacrylate-b-styrene) 180 g of water were initially introduced and kept at 90 ° C. Then, in parallel, from 3 drip funnels, 3 g of the trans-stilbene, dissolved in 50 g of methyl methacrylate and 5 g of a 25% ammonia solution, dissolved in 50 g of water, were added in drops in 60 minutes, and 5.1 g of ammonium peroxodisulfate dissolved in 15 50 g of water, were added in drops in 90 minutes. The batch was then kept at 90 ° C for 4.5 hours more. A polymer having an Mw of 46,800 g / mol and a polydispersity of 2.9 was obtained. 70 g of the polymer dispersion, described above, were heated to 115 ° C and 50 g of styrene were dosed therein, The batch was then kept at 115 ° C for 6 hours. A polymer having a Mw of 207,000 g / mol and a polydispersity of 4.2 was obtained.
Example 11 Synthesis of polymethyl methacrylate (Only first stage)
180 g of water were initially introduced and kept at 90 ° C. Then, in parallel, from 3 dropping funnels, 5 g of 4,4-vinylidene-bis (N, N-dimethylaniline), dissolved in 100 g of methyl methacrylate and 4.6 g of a 25% solution of ammonia, dissolved in 100 g of water, they were added in drops in 60 minutes, and 5.1 g of ammonium peroxodisulfate dissolved in 510 g of water, were added in drops in the course of 90 minutes. The batch was then kept at 90 ° C for 4 more hours. A polymer having a Mw of 2150 g / mol and a polydispersity of 1.2 was obtained.
Example 12 A reaction vessel was charged with 52.56 g of deionized water and this initial charge was heated to 90 ° C. Subsequently, at a constant temperature of 90 ° C, three separate charging currents were dosed in parallel, at a uniform rate. The charge stream 1 consisted of 10.18 g of acrylic acid, 18.35 g of methyl methacrylate and 1.49 g of diphenylethylene. As the charging current 2, 9.9 g of a 25% by weight ammonia solution were added. Charge stream 3 consisted of a solution of 2.25 g of ammonium peroxodisulfate in 5.25 g of deionized water. The load currents I and II were dosed in the course of 1 hour, the load current II in the course of 1.25 hours. When the addition came to an end, the
< - post-polymerization phase of 4 hours, with cooling. The resulting micellar solution had a solids content of 33% by weight.
Example 13 First of all, 9.1 g of the product prepared in Example 1 were initially introduced into 51.62 g of deionized water and this initial charge was heated to 90 ° C, with stirring, in a reactor. Subsequently, a stream of ceirga, consisting of 16.19 g of n-butyl methacrylate, 14.21 g of styrene and 8.88 g of ethylhexyl methacrylate were metered in over the course of 6 hours, by means of stirring. The resulting dispersion had a solids content of 42% by weight.
Example 14 A 5 kg steel reactor was charged with 906.0 g of deionized water and this initial charge was heated to 90 ° C. Subsequently, at a constant temperature of 90 ° C, three separate charging currents were dosed in a regime
uniform in parallel, in the course of 4 hours. The charging stream I consisted of 457.6 g of ethyl acrylate, 215.3 g of acrylic acid and 20.2 g of diphenylethylene. Charge stream II was a solution of 40.4 g of ammonium peroxodisulfate in 94.2 g of deionized water. Charge stream III was composed of 133.2 g of dimethylethanolamine and 133.2 g of deionized water. When the addition was completed, a post-polymerization phase of 2 hours at 90 ° C resulted. This gave a clear, slightly orange solution, which had a pH of 5.2, a viscosity of 5.2 dPas, a solids content (60 minutes at 130 ° C) of 40.3% and an acid number, determined alcoholically, of 246 mg of KOH / g of solids.
Example 15 A 5 kg steel reactor was charged with 800.0 g of an aqueous solution, prepared in Example 14, and this initial charge was heated to 90 ° C. A solution consisting of 83.2 g of ethyl acrylate, 67.2 g of n-butyl acrylate, 80.0 g of styrene and 89.6 g of hydroxypropyl methacrylate was dosed in the course of 30 minutes, after which the batch was subjected to thermolysis at 90 ° C for 5 hours. This gave a slightly orange solution having a pH of 5.3, a viscosity of 8.4 dPas, a solids content (60 minutes at 130 ° C) of 39.7% and an acid number, determined alcoholically, of 133 mg KOH / g of solids.
Example 16 A 5 kg steel reactor was charged with 528.7 g of deionized water and this initial charge was heated to 90 ° C. tt Then, at a constant temperature of 90 ° C, three separate charging currents were dosed in a uniform regime, in parallel, over the course of 4 hours. The loading stream I consisted of 106.2 g of MA-13, 378.1 g of n-butyl methacrylate, 19.3 g of styrene, 54.5 g of acrylic acid, 332.4 g of methyl methacrylate and 31.9 g of
difetyethylene. Charge stream II was a solution of 42.5 g of ammonium peroxodisulfate in 170 g of desiccated water. The charging stream III contained 51.61 g of dimethylethanolamine. When the addition was complete, a post-polymerization phase of 2 hours at 90 ° C resulted. He
Cooling gave a white dispersion having a pH of 5.5, a solids content (60 minutes, 130 ° C) of 41%, an acid number, determined alcoholically, of 58 mg of KOH / g solids and a viscosity of 0.9 dPas (23 ° C, cone / plate). The molecular weight was determined by means of
GPC chromatography against polystyrene as standard and was Mn 4406 g / mol, Mw of 8603 g / mol and polydispersity of 1.95. The MA-13 is methacrylate ester 13.0 Rohm.
Claims (10)
- C C / \ R- R2 wherein R_ to R4, independently of one another, are hydrogen, an alkyl radical, substituted or unsubstituted, a cycloalkyl radical or an aralkyl radical, or an aromatic hydrocarbon radical, unsubstituted or substituted, with the proviso that at least two of Ri to R4 are radicals of aromatic hydrocarbons, unsubstituted or substituted. in aqueous phase.
- 2. A method, as claimed in claim 1, wherein the reaction is conducted in the presence of at least one base.
- 3. A method, as claimed in any of claims 1 or 2, wherein the compound (I) is the «Fc difer.ylethylene, an alkoxydiphenylethylene, dinaphthalethylene, 4, 4-vinylidene-bi (N, N-dimethylaniline), 4, 4-vinylidene-bis (1, 5-aminocbenzene), cis- or trans-stilbene, or a mixture of two or more of them.
- 4. A method, as claimed in any of claims 1 to 3, wherein the monomer (a) is a hydrophilic monomer, a mixture comprising at least two 10 hydrophilic monomers or a mixture comprising at least one hydrophilic monomer and at least one hydrophobic monomer.
- 5. A method, as claimed in any of claims 1 to 4, wherein the base with low molecular mass is NaOH, KOH, ammonia, diethanolamine, 15 Triethanolamine, mono, di-, or tri-ethylamine, dimethylethanolamine or a mixture of two or more of them.
- 6. A method for preparing a polymer (B), which comprises: (ii) reacting the reaction product, obtained in step (i), under free radial conditions, in the presence of at least one homopolymerizable monomer (b) or copolymerizable, free radical.
- 7. A reaction product (A), which can be prepared by means of a method, comprising the following step (i): (i) reacting, under free radical conditions, a reaction mixture, comprising at least one monomer (a) which can react as a free radical, in the presence of at least one free radical initiator and a compound (I) of the formula: R3 Ri \ / C C * - * / \ R4 R2 wherein R_ to R4, independently of one another, are hydrogen, an alkyl radical, substituted or substituted, a cycloalkyl radical or an aralkyl radical, or an aromatic hydrocarbon radical, substituted or substituted, with the proviso that less two of Ri to R4 are aromatic hydrocarbon radicals, unsubstituted or substituted. in aqueous phase.
- 8. A polymer B, which can be prepared by a method comprising step (ii): (ii) reacting the reaction product (A), obtained in step (i), under free radical conditions, in the presence of at least one monomer (b), homopolymerizable or copolymerizable, free radical.
- 9. An aqueous mixture, comprising a reaction product (A), as claimed in claim 7, or a polymer (B), as claimed in claim 8, or a combination of two or more of them.
- 10. The use of an aqueous mixture, comprising the reaction product (A) or the polymer (B), or a combination of two or more of them, as a dispersion.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19858708.2 | 1998-12-18 | ||
DE19909803.4 | 1999-03-05 |
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MXPA01005873A true MXPA01005873A (en) | 2001-12-13 |
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