CN105237694B - A kind of acrylate block copolymer and its preparation method and application - Google Patents
A kind of acrylate block copolymer and its preparation method and application Download PDFInfo
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- CN105237694B CN105237694B CN201510791084.XA CN201510791084A CN105237694B CN 105237694 B CN105237694 B CN 105237694B CN 201510791084 A CN201510791084 A CN 201510791084A CN 105237694 B CN105237694 B CN 105237694B
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- block copolymer
- acrylate
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 86
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 61
- 239000011248 coating agent Substances 0.000 claims abstract description 60
- 239000002270 dispersing agent Substances 0.000 claims abstract description 34
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims description 37
- 239000003999 initiator Substances 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 239000000049 pigment Substances 0.000 claims description 21
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 8
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 6
- 238000012661 block copolymerization Methods 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 22
- 239000002245 particle Substances 0.000 abstract description 12
- 125000000753 cycloalkyl group Chemical group 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 33
- 150000002148 esters Chemical class 0.000 description 31
- 239000002253 acid Substances 0.000 description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 26
- -1 acrylic ester Chemical class 0.000 description 26
- 239000003973 paint Substances 0.000 description 18
- 239000003960 organic solvent Substances 0.000 description 16
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 238000005227 gel permeation chromatography Methods 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 11
- 229920000178 Acrylic resin Polymers 0.000 description 10
- 239000004925 Acrylic resin Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 description 9
- 239000004342 Benzoyl peroxide Substances 0.000 description 8
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 7
- JCCIFDCPHCKATH-UHFFFAOYSA-N 2-methylbutan-2-yl acetate Chemical compound CCC(C)(C)OC(C)=O JCCIFDCPHCKATH-UHFFFAOYSA-N 0.000 description 7
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ADLSGJNAHUYEQS-UHFFFAOYSA-N [Cl-].[NH4+].CC(CC(C(=O)O)=C)(C)C Chemical compound [Cl-].[NH4+].CC(CC(C(=O)O)=C)(C)C ADLSGJNAHUYEQS-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- RXGUIWHIADMCFC-UHFFFAOYSA-N 2-Methylpropyl 2-methylpropionate Chemical compound CC(C)COC(=O)C(C)C RXGUIWHIADMCFC-UHFFFAOYSA-N 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 4
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 4
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 0 CC(NCC*)=O Chemical compound CC(NCC*)=O 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000004815 dispersion polymer Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 235000010215 titanium dioxide Nutrition 0.000 description 3
- IDQBJILTOGBZCR-UHFFFAOYSA-N 1-butoxypropan-1-ol Chemical compound CCCCOC(O)CC IDQBJILTOGBZCR-UHFFFAOYSA-N 0.000 description 2
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-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
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical class CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- WOYWLLHHWAMFCB-UHFFFAOYSA-N 2-ethylhexyl acetate Chemical compound CCCCC(CC)COC(C)=O WOYWLLHHWAMFCB-UHFFFAOYSA-N 0.000 description 2
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- BTMVHUNTONAYDX-UHFFFAOYSA-N butyl propionate Chemical compound CCCCOC(=O)CC BTMVHUNTONAYDX-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical class CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 2
- 229940011051 isopropyl acetate Drugs 0.000 description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 229940090181 propyl acetate Drugs 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- OZFIGURLAJSLIR-UHFFFAOYSA-N 1-ethenyl-2h-pyridine Chemical class C=CN1CC=CC=C1 OZFIGURLAJSLIR-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical class C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-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
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-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
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical class C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- WFLRYNLDQFMIMS-UHFFFAOYSA-N CC(C)(CC(C)(C)OC([O]=C)=O)[N+](C)(C)C Chemical compound CC(C)(CC(C)(C)OC([O]=C)=O)[N+](C)(C)C WFLRYNLDQFMIMS-UHFFFAOYSA-N 0.000 description 1
- VIETUFSZPCIVQL-UHFFFAOYSA-N CN(C=CC1)C1=O Chemical compound CN(C=CC1)C1=O VIETUFSZPCIVQL-UHFFFAOYSA-N 0.000 description 1
- RABULBXBXKMRMC-UHFFFAOYSA-N C[n](cc1)c[n]1(C)=C Chemical compound C[n](cc1)c[n]1(C)=C RABULBXBXKMRMC-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- PRTXHLNVNLADCY-UHFFFAOYSA-N azanium;prop-2-enoic acid;chloride Chemical compound [NH4+].[Cl-].OC(=O)C=C PRTXHLNVNLADCY-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 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
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 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
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- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Graft Or Block Polymers (AREA)
Abstract
The invention belongs to the field of chemical synthesis more particularly to a kind of acrylate block copolymer and its preparation method and application.Acrylate block copolymer provided by the invention includes formula (I) building block and formula (II) building block；Wherein, a and b represents the degree of polymerization, X1And X2Independent is selected from H or alkyl, Y1For alkyl or cycloalkyl, Y2For with formula (Y21)~formula (Y28) any one in the group of structure；M1 and m2 is the integer more than 0.The present invention is by rationally designing the structures of two blocks in block copolymer, so as to be obviously improved dispersion performance of the block copolymer when being used as dispersant.The experimental results showed that：The coating surface that coating added with block copolymer provided by the invention is formed is smooth, without apparent particle, and is not layered after coating long-time standing.
Description
Technical field
The invention belongs to the field of chemical synthesis more particularly to a kind of acrylate block copolymer and preparation method thereof and answer
With.
Background technology
Dispersant is the interface active agent that can improve coating monodisperse system stability.Dispersant is in chemical constitution
Containing hydrophilic radical and lipophilic group.Hydrophilic segment or oleophilic moiety absorption are in pigment particle when it is added in coating
On surface, and the unadsorbed part of the other end is just aligned except particle surface.If particle surface is hydrophobic, inhale
The oleophilic moiety of Fufen powder, it is on the contrary then adsorb hydrophilic segment.In the adsorption process of dispersant, the moisture on particle surface is gentle
Body etc. is substituted, and therefore, with the help of dispersant, wetting action of the pigment in base-material is improved, so as to promote pigment
Dispersibility in base-material.
At present, application dispersant the most universal is high polymer dispersion, typical high molecular polymer dispersion
Agent is that the substance for having compatibility respectively with pigment and base-material is aggregated into living polymer by the way of block copolymerization.Due to this
Kind dispersant had not only had the chain link of close pigment, but also the chain link with close base-material, therefore can be obviously improved pigment in base-material
Dispersibility.
As one kind of high polymer dispersion, the application of acrylic polymer dispersant is more and more extensive,
But since the segmented structure design in existing acrylic polymer dispersant is unreasonable, existing esters of acrylic acid is caused to polymerize
The dispersion performance of object dispersant is difficult to meet requirement.
Invention content
In view of this, the purpose of the present invention is to provide a kind of acrylate block copolymer and preparation method thereof and should
With with excellent dispersion performance when acrylate block copolymer provided by the invention is used as dispersant.
The present invention provides a kind of acrylate block copolymer, including formula (I) building block and formula (II) building block；
Wherein, a and b represents the degree of polymerization, X1And X2Independent is selected from H or alkyl, Y1For alkyl or cycloalkyl, Y2To have
Formula (Y2- 1)~formula (Y2- 8) any one in the group of structure：
Formula (Y2- 7) and formula (Y2- 8) in, m1 and m2 are the integer more than 0.
Preferably, the X1And X2Independent is selected from C1~C5Alkyl.
Preferably, the Y1For C1~C25Alkyl or C3~C25Cycloalkyl.
Preferably, the Y1For with formula (Y1- 1)~formula (Y1- 7) any one in the group of structure：
Formula (Y1- 1) in, 0≤n≤24.
Preferably, 0 ＜ m1≤10,0 ＜ m2≤10.
Preferably, 5≤a≤300；5≤b≤100.
Preferably, formula (I) building block is any one in the block with formula (I-1)~formula (I-3) structure：
Formula (II) building block is any one in the block with formula (II-1)~formula (II-3) structure：
The present invention provides a kind of preparation method of the acrylate block copolymer described in above-mentioned technical proposal, including with
Lower step：
A), formula (III) structural compounds carry out polymerisation in the presence of chain-transferring agent and initiator, obtain prepolymer；
B), the prepolymer and formula (IV) structural compounds carry out polymerisation in the presence of initiator, obtain acrylic acid
Ester block copolymer；
Wherein, X1And X2Independent is selected from H or alkyl, Y1For alkyl or cycloalkyl, Y2For with formula (Y2- 1)~formula (Y2-
8) any one in the group of structure：
Formula (Y2- 7) and formula (Y2- 8) in, m1 and m2 are the integer more than 0.
The present invention provides the block copolymer described in a kind of above-mentioned technical proposal or above-mentioned technical proposal the method systems
Application of the block copolymer obtained as dispersant in coating.
Preferably, the acrylic resin of the coating including 10~100 parts by weight, the pigment of 10~100 parts by weight and 1~
The block copolymer of 10 parts by weight.
Compared with prior art, the present invention provides a kind of acrylate block copolymers and its preparation method and application.
Acrylate block copolymer provided by the invention includes formula (I) building block and formula (II) building block；Wherein, a and b is represented
The degree of polymerization, X1And X2Independent is selected from H or alkyl, Y1For alkyl or cycloalkyl, Y2For with formula (Y2- 1)~formula (Y2- 8) structure
Group in any one；M1 and m2 is the integer more than 0.The present invention is by rationally designing two blocks in block copolymer
Structure, so as to be obviously improved dispersion performance of the block copolymer when being used as dispersant.The experimental results showed that：Addition
The coating surface that the coating for having block copolymer provided by the invention is formed is smooth, and without apparent particle, and the coating is quiet for a long time
It postpones and is not layered.So as to have when proving that acrylate block copolymer provided by the invention is used as coating dispersant
Excellent dispersion performance can effectively facilitate dispersion of the pigment in coating.
Description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention, for those of ordinary skill in the art, without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the GPC figures that the embodiment of the present invention 1 provides；
Fig. 2 is the paint film for the coating added with acrylic acid block copolymerization provided by the invention that the embodiment of the present invention 1 provides
Observation figure；
Fig. 3 is the paint film observation figure of the coating for the addition commercial dispersants that the embodiment of the present invention 1 provides；
Fig. 4 is the GPC figures that the embodiment of the present invention 2 provides；
Fig. 5 is the paint film for the coating added with acrylic acid block copolymerization provided by the invention that the embodiment of the present invention 2 provides
Observation figure；
Fig. 6 is the paint film observation figure of the coating for the addition commercial dispersants that the embodiment of the present invention 2 provides；
Fig. 7 is the GPC figures that the embodiment of the present invention 3 provides；
Fig. 8 is the coating observation figure that the embodiment of the present invention 3 provides；
Fig. 9 is the observation figure after the coating that the embodiment of the present invention 3 provides is stood 60 days.
Specific embodiment
The technical solution in the embodiment of the present invention is clearly and completely described below, it is clear that described embodiment
Only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel all other embodiments obtained without making creative work belong to the model that the present invention protects
It encloses.
The present invention provides a kind of acrylate block copolymer, including formula (I) building block and formula (II) building block；
Wherein, a and b represents the degree of polymerization, X1And X2Independent is selected from H or alkyl, Y1For alkyl or cycloalkyl, Y2To have
Formula (Y2- 1)~formula (Y2- 8) any one in the group of structure：
Formula (Y2- 7) and formula (Y2- 8) in, m1 and m2 are the integer more than 0.
Acrylate block copolymer provided by the invention includes formula (I) building block and formula (II) building block.Wherein,
The concrete structure of the block of formula (I) structure is as follows：
In formula (I), X1For H or alkyl, Y1For alkyl or cycloalkyl, a represents the degree of polymerization.In a reality provided by the invention
It applies in example, X1For C1~C5Alkyl；In another embodiment provided by the invention, X1For methyl, ethyl or propyl.At this
It invents in the one embodiment provided, Y1For C1~C25Alkyl or C3~C25Cycloalkyl；It is provided by the invention another
In embodiment, Y1For C1~C22Alkyl or C3~C22Cycloalkyl；In other embodiment provided by the invention, the Y1For
With formula (Y1- 1)~formula (Y1- 7) any one in the group of structure：
Formula (Y1- 1) in, 0≤n≤24.In one embodiment provided by the invention, 0≤n≤21.
In the present invention, in formula (I), a represents the degree of polymerization；In one embodiment provided by the invention, 5≤a≤300；
In another embodiment provided by the invention, 5≤a≤200.
In one embodiment provided by the invention, formula (I) building block is with formula (I-1)~formula (I-3) knot
Any one in the block of structure：
In the present invention, the concrete structure of the block of formula (II) structure is as follows：
In formula (II), X2For H or alkyl, Y2For nitrogen-containing group, b represents the degree of polymerization.In one embodiment provided by the invention
In, X2For C1~C5Alkyl；In another embodiment provided by the invention, X2For methyl, ethyl or propyl.In the present invention
In one embodiment of offer, Y2For with formula (Y2- 1)~formula (Y2- 8) any one in the group of structure：
Formula (Y2- 7) and formula (Y2- 8) in, m1 and m2 are the integer more than 0.In one embodiment provided by the invention, 0
＜ m1≤10,0 ＜ m2≤10；In another embodiment provided by the invention, 0 ＜ m1≤5,0 ＜ m2≤5；It is carried in the present invention
In the other embodiment of confession, m1=1,2 or 3, m2=1,2 or 3.
In the present invention, in formula (II), b represents the degree of polymerization；In one embodiment provided by the invention, 5≤b≤100；
In another embodiment provided by the invention, 5≤b≤50.
In one embodiment provided by the invention, formula (II) building block is with formula (II-1)~formula (II-3)
Any one in the block of structure：
In one embodiment provided by the invention, the acrylate block copolymer is by formula (I) building block and formula
(II) building block is formed, and structure can use formula (V) general structure to represent：
In the present invention, the range of choice of each substituent group in formula (V) is identical with formula (I) and formula (II) building block,
This is repeated no more.
The present invention has been obviously improved block copolymer and has made by rationally designing the structures of two blocks in block copolymer
Dispersion performance when being used for dispersant, acrylate block copolymer provided by the invention specifically have the following advantages that：
1), the acrylate solvent segment of acrylate block copolymer provided by the invention, that is, formula (I) building block tool
There is very prominent compatibility, can be compatible with most of resin such as acrylic resin, alkyd resin, so as to ensure that the present invention
The acrylate block copolymer of offer can use in most cold coatings as dispersant, including furniture lacquer, industrial paint, vapour
Vehicle paint etc.；Particularly when the formula (I) building block is butyl polyacrylate, compatibility is especially prominent.
2), the anchoring group (nitrogen-containing group) in acrylate block copolymer provided by the invention is all in a block
In (formula (II) building block), therefore the pigment that the block copolymer can be preferably and in coating combines, and then it is embedding to improve this
Section copolymer is to the dispersibility of pigment.
3) the segments component such as polyethers, polystyrene, is not contained in acrylate block copolymer provided by the invention, this is common
Polymers is more simple in structure, and each structural unit effect is clear and definite, therefore performance is more superior.
The experimental results showed that：The coating surface that coating added with block copolymer provided by the invention is formed is smooth, nothing
Apparent particle, and be not layered after coating long-time standing, so as to prove acrylic ester block provided by the invention
With excellent dispersion performance when object is used as coating dispersant, dispersion of the pigment in coating can be effectively facilitated.
The present invention provides a kind of preparation methods of above-mentioned acrylate block copolymer, include the following steps：
A), formula (III) structural compounds carry out polymerisation in the presence of chain-transferring agent and initiator, obtain prepolymer；
B), the prepolymer and formula (IV) structural compounds carry out polymerisation in the presence of initiator, obtain acrylic acid
Ester block copolymer；
Wherein, X1And X2Independent is selected from H or alkyl, Y1For alkyl or cycloalkyl, Y2For with formula (Y2- 1)~formula (Y2-
8) any one in the group of structure：
Formula (Y2- 7) and formula (Y2- 8) in, m1 and m2 are the integer more than 0.
In preparation method provided by the invention, formula (III) structural compounds are subjected to polymerisation first.In the present invention
In, formula (III) structural compounds carry out polymerisation in the presence of chain-transferring agent and initiator, which is specially：
Formula (III) structural compounds, chain-transferring agent and initiator are mixed in organic solvent, carry out polymerisation.Its
In, formula (III) the structural compounds structure is as follows：
In formula (III), X1For H or alkyl, Y1For alkyl or cycloalkyl.In one embodiment provided by the invention, X1For
C1~C5Alkyl；In another embodiment provided by the invention, X1For methyl, ethyl or propyl.Provided by the invention one
In a embodiment, Y1For C1~C25Alkyl or C3~C25Cycloalkyl；In another embodiment provided by the invention, Y1For
C1~C22Alkyl or C3~C22Cycloalkyl；In other embodiment provided by the invention, the Y2For with formula (Y1- 1)~
Formula (Y1- 7) any one in the group of structure：
Formula (Y1- 1) in, 0≤n≤24.In one embodiment provided by the invention, 0≤n≤21.
In one embodiment provided by the invention, formula (III) structural compounds are specially methyl acrylate, propylene
Acetoacetic ester, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, lauryl acrylate, acrylic acid 2- ethylhexyls
Ester, stearyl acrylate acid esters, cyclohexyl acrylate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate,
N-BMA, Isobutyl methacrylate, Tert-butyl Methacrylate, lauryl methacrylate, metering system
Sour 2- ethylhexyls, stearyl methacrylate, cyclohexyl methacrylate or isobornyl methacrylate.
In the present invention, formula (III) structural compounds, chain-transferring agent and initiator mix progress in organic solvent
During polymerisation, the chain-transferring agent includes but not limited to the chain-transferring agent with formula (K-1)~formula (K-14) structure
In it is one or more：
In the present invention, formula (III) structural compounds, chain-transferring agent and initiator mix progress in organic solvent
During polymerisation, the initiator includes but not limited to azodiisobutyronitrile, two isobutyl heptonitrile of azo, benzoyl peroxide first
Acyl, benzoyl peroxide, peroxidating 2- ethyl acids tert-pentyl ester, the peroxidating 2- ethyl acids tert-butyl ester, bis- (the tertiary pentyl mistakes of 1,1-
Oxidation) ring group alkane, bis- (the t-amyl peroxy) -3,3,5- trimethyls thiacyclohexanes of 1,1-, peroxidating acetic acid tert-pentyl ester, benzoyl peroxide first
Sour tert-pentyl ester, 3,5,5 trimethyl of peroxidating bis- (t-amyl peroxy) fourths of tert-butyl acrylate, peroxidized t-butyl perbenzoate, 3,3-
Bis- (t-butyl peroxy) ethyl butyrates of acetoacetic ester, 3,3-, cumyl peroxide, di t-amyl peroxide, two tertiary fourth of peroxidating
Base, t-amyl peroxy hydrogen and tert-butyl hydroperoxide it is one or more.
In the present invention, formula (III) structural compounds, chain-transferring agent and initiator mix progress in organic solvent
During polymerisation, the organic solvent includes but not limited to toluene, dimethylbenzene, ethyl acetate, butanone, isopropyl acetate
Ester, 2 pentanone, propyl acetate, hexone, isobutyl acetate, n-butyl acetate, methyl isoamyl ketone, acetic acid are different
Ester, n-butyl propionate, propylene glycol methyl ether acetate, pentyl acetate, methyl-n-amyl ketone, isobutyl isobutyrate, ethylene glycol
Ether, cyclohexanone, glycol monobutyl ether, Propylene glycol n-propyl ether, propylene glycol methyl ether acetate, ethyl cellosolve acetate, two
Isobutyl ketone, diacetone alcohol, butyl glycol ether, propandiol butyl ether, 2-ethyl hexyl ethanoate, butyl glycol ether acetic acid esters, two
Propylene glycol monomethyl ether, ethylene acetate, diethylene glycol dimethyl ether, diethylene glycol ether, glycol hexyl ether, diethylene glycol ether second
One kind in acid esters, butyl, ethylene glycol -2- ethyls hexyl ether, butyl acetic acid esters and propylene glycol phenylate is more
Kind.
In the present invention, formula (III) structural compounds, chain-transferring agent and initiator mix progress in organic solvent
During polymerisation, formula (III) structural compounds, chain-transferring agent, the molar ratio of initiator and organic solvent are preferred
For (5~300)：1：(0.1~0.5)：(10~1000), more preferably (5~200)：1：(0.1~0.5)：(10~1000).
The mode that formula (III) structural compounds, chain-transferring agent and initiator mix in organic solvent is preferably first by formula (III)
Structural compounds are mixed with chain-transferring agent, later again by the organic solvent containing initiator be added drop-wise to formula (III) binding compounds with
In the mixed system of chain-transferring agent composition.In the present invention, the temperature of the polymerisation is preferably 50~160 DEG C.The present invention
The time of the polymerisation is not particularly limited, preferably reaches more than 80% in the conversion ratio of formula (III) structural compounds
Stop reaction afterwards.In one embodiment provided by the invention, the time of the polymerisation is 6~7.5h.
In the present invention, after formula (III) structural compounds carry out polymerisation, prepolymer is obtained.It obtains described pre-
After polymers, the prepolymer and formula (IV) structural compounds carry out polymerisation.In the present invention, the prepolymer and formula (IV)
Structural compounds carry out polymerisation in the presence of initiator, which is specially：
The prepolymer, formula (IV) structural compounds and initiator are mixed in organic solvent, carry out polymerisation.Its
In, formula (IV) the structural compounds structure is as follows：
In formula (IV), X2For H or alkyl, Y2For nitrogen-containing group.In one embodiment provided by the invention, X2For C1~C5
Alkyl；In another embodiment provided by the invention, X2For methyl, ethyl or propyl.In a reality provided by the invention
It applies in example, Y2For with formula (Y2- 1)~formula (Y2- 8) any one in the group of structure：
Formula (Y2- 7) and formula (Y2- 8) in, m1 and m2 are the integer more than 0.In one embodiment provided by the invention, 0
＜ m1≤10,0 ＜ m2≤10；In another embodiment provided by the invention, 0 ＜ m1≤5,0 ＜ m2≤5；It is carried in the present invention
In the other embodiment of confession, m1=1,2 or 3, m2=1,2 or 3.
In one embodiment provided by the invention, formula (IV) structural compounds are specially N, N- dimethylaminoethyls
Base acrylate, 2- trimethylethyl acrylic acid ammonium chloride, N, N- dimethylaminopropylacryls acid esters, 4-vinylpridine,
2- vinylpyridines, vinyl imidazole, N- caprolactams, n-vinyl pyrrolidone, 4- acryloyl morpholines, N, N- bis-
Methylaminoethyl methacrylate, 2- trimethylethyl methacrylic acid ammonium chlorides or N, N- dimethylaminopropyl methyl
Acrylate.
In the present invention, the prepolymer, formula (IV) structural compounds and initiator mix gathered in organic solvent
During closing reaction, the initiator includes but not limited to azodiisobutyronitrile, two isobutyl heptonitrile of azo, benzoyl peroxide first
Acyl, benzoyl peroxide, peroxidating 2- ethyl acids tert-pentyl ester, the peroxidating 2- ethyl acids tert-butyl ester, bis- (the tertiary pentyl mistakes of 1,1-
Oxidation) ring group alkane, bis- (the t-amyl peroxy) -3,3,5- trimethyls thiacyclohexanes of 1,1-, peroxidating acetic acid tert-pentyl ester, benzoyl peroxide first
Sour tert-pentyl ester, 3,5,5 trimethyl of peroxidating bis- (t-amyl peroxy) fourths of tert-butyl acrylate, peroxidized t-butyl perbenzoate, 3,3-
Bis- (t-butyl peroxy) ethyl butyrates of acetoacetic ester, 3,3-, cumyl peroxide, di t-amyl peroxide, two tertiary fourth of peroxidating
Base, t-amyl peroxy hydrogen and tert-butyl hydroperoxide it is one or more.
In the present invention, the prepolymer, formula (IV) structural compounds and initiator mix gathered in organic solvent
Close reaction during, the organic solvent include but not limited to toluene, dimethylbenzene, ethyl acetate, butanone, isopropyl acetate,
2 pentanone, propyl acetate, hexone, isobutyl acetate, n-butyl acetate, methyl isoamyl ketone, acetic acid dissident
Ester, n-butyl propionate, propylene glycol methyl ether acetate, pentyl acetate, methyl-n-amyl ketone, isobutyl isobutyrate, ethylene glycol ethyl ethers
It is ether, cyclohexanone, glycol monobutyl ether, Propylene glycol n-propyl ether, propylene glycol methyl ether acetate, ethyl cellosolve acetate, two different
Butyl ketone, diacetone alcohol, butyl glycol ether, propandiol butyl ether, 2-ethyl hexyl ethanoate, butyl glycol ether acetic acid esters, dipropyl
Glycol methyl ether, ethylene acetate, diethylene glycol dimethyl ether, diethylene glycol ether, glycol hexyl ether, diethylene glycol ether acetic acid
It is one kind of multiple in ester, butyl, ethylene glycol -2- ethyls hexyl ether, butyl acetic acid esters and propylene glycol phenylate.
In the present invention, the prepolymer, formula (IV) structural compounds and initiator mix gathered in organic solvent
During closing reaction, raw material i.e. formula (III) structural compounds, formula (IV) structural compounds, initiation of the prepolymer are prepared
The molar ratio of agent and organic solvent is preferably (5~300)：(5~100)：(0.1~0.5)：(10~1000), more preferably (5
~200)：(5~50)：(0.1~0.5)：(10~1000).The prepolymer, formula (IV) structural compounds and initiator are having
The mode mixed in solvent preferably first mixes the prepolymer and formula (IV) structural compounds, will contain initiator again later
Organic solvent be added drop-wise to prepolymer and formula (IV) structural compounds composition mixed system in.In the present invention, the polymerization
The temperature of reaction is preferably 50~160 DEG C.The time of the polymerisation is not particularly limited in the present invention, preferably at formula (IV)
The conversion ratio of structural compounds stops reaction after reaching 100%.In one embodiment provided by the invention, the polymerisation
Time be 7~8h.
In the present invention, after prepolymer and formula (IV) structural compounds carry out polymerisation, offer of the present invention is obtained
Acrylate block copolymer.
Method provided by the invention is used using formula (III) structural compounds and formula (IV) structural compounds as comonomer
Acrylate block copolymer is prepared in the mode of step-by-step polymerization, the block copolymer used as dispersant show it is excellent
Different dispersion performance.Preparation method provided by the invention specifically has the following advantages that：
1), preparation method provided by the invention is for environmental requirement milder, monomer selection face more tolerant to reaction unit
Wider, adaptability is stronger；Meanwhile, molecular weight point controllable using block polymer molecules amount prepared by method provided by the invention
Cloth is relatively narrow.
2), in preferred embodiment provided by the invention, using the chain tra nsfer with formula (K-1)~formula (K-14) structure
Agent, the transfer agent preparation process is simple, is suitble to industrializing implementation.
The experimental results showed that：The coating surface that coating added with block copolymer made from the method provided by the present invention is formed
It is smooth, it without apparent particle, and is not layered after coating long-time standing, so as to prove third made from the method provided by the present invention
With excellent dispersion performance when olefin(e) acid ester block copolymer is used as coating dispersant, pigment can be effectively facilitated in coating
In dispersion.
A kind of block copolymer or above-mentioned technical proposal the method by described in above-mentioned technical proposal provided by the invention
Application of the block copolymer obtained as dispersant in coating.
In application provided by the invention, used, be added in coating as coating dispersant using the block copolymer
Excellent dispersion performance is shown afterwards.In one embodiment provided by the invention, the coating includes 10~100 parts by weight
The block copolymer of acrylic resin, the pigment of 10~100 parts by weight and 1~10 parts by weight；Provided by the invention another
In one embodiment, the acrylic resin of the coating including 10~60 parts by weight, the pigment and 1~7 weight of 10~60 parts by weight
Measure the block copolymer of part.In the present invention, the pigment includes but not limited to one in titanium dioxide, carbon black and phthalocyanine blue
Kind is a variety of.In one embodiment provided by the invention, the coating further includes solvent, and the solvent is preferably dimethylbenzene
(enumerating other solvents), additive amount of the solvent in coating are preferably 2~60 parts by weight.
For the sake of becoming apparent from, it is described in detail below by following embodiment.
Embodiment 1
1) acrylate block copolymer, is prepared：
1-1), the preparation of prepolymer：
Chain-transferring agent, 5mol methyl acrylates that 1mol has formula (K-1) structure are added in reaction kettle, are passed through nitrogen
10min, temperature for be slowly added dropwise at 50 DEG C containing 0.1mol azodiisobutyronitriles xylene solution (azodiisobutyronitrile with
The molar ratio of dimethylbenzene is 0.1:10) after the xylene solution containing azodiisobutyronitrile, is added dropwise, methyl acrylate proceeds by poly-
Reaction is closed, after 6h is reacted, stops reaction, obtains prepolymer.
The content of methyl acrylate in the prepolymer is detected, and according to methyl acrylate using gas-chromatography
The conversion ratio of content calculation methyl acrylate, result are：The conversion ratio of methyl acrylate reaches 80%.
1-2), the preparation of block polymer：
The prepolymer of preparation is added in reaction kettle, and adds in N, N- dimethyl amino ethyl acrylate 5mol,
Temperature is that xylene solution (benzoyl peroxide and dimethylbenzene containing 0.1mol benzoyl peroxides are slowly added dropwise at 50 DEG C
Molar ratio is 0.1:10) after the xylene solution containing benzoyl peroxide, is added dropwise, prepolymer and N, N- dimethyl aminoethyl third
Olefin(e) acid ester proceeds by polymerisation, after 7.5h is reacted, stops reaction, obtains acrylate block copolymer.
Using gas-chromatography to N in the acrylate block copolymer, N- dimethyl amino ethyl acrylates contain
Amount is detected, and according to N, content calculation N, N- the dimethylaminoethylacryl acid of N- dimethyl amino ethyl acrylates
The conversion ratio of ester, result are：The conversion ratio of N, N- dimethyl amino ethyl acrylate reaches 100%.
Gel permeation chromatography (Gel Permeation are carried out to acrylate block copolymer obtained
Chromatography, GPC) analysis, the results are shown in Figure 1, and Fig. 1 is the GPC figures that the embodiment of the present invention 1 provides, can by Fig. 1
To find out, the number-average molecular weight of the acrylate block copolymer is 1620g/mol, and molecular weight distribution index (PDI) is 1.21.
The acrylic acid according to made from raw material type, raw material rate of charge and gpc analysis result can extrapolate the present embodiment
The block copolymer that ester block copolymer is formed for formula (I-1) building block and formula (II-1) building block：
Wherein, a=5, b=5.
2), application of the acrylate block copolymer prepared in coating：
By 35 grams of acrylic resin (producers：Fine horse nation, model：32221), 60 grams of titanium dioxides, 1 gram of acrylic acid obtained above
Ester block copolymer and 4 grams of dimethylbenzene are added in dispersion cylinder together, are stirred 20min in 1200rpm/min, are obtained white coating
1。
By 35 grams of acrylic resin (producers：Fine horse nation, model：32221), 60 grams of titanium dioxides, 1 gram of certain commercial dispersants and 4
Gram dimethylbenzene is added in dispersion cylinder together, is stirred 20min in 1200rpm/min, is obtained white coating 2.
The film on tinplate by above-mentioned white coating 1 and white coating 2, observe paint film, paint film observation result such as Fig. 2 and
Shown in Fig. 3, Fig. 2 is the paint film for the coating added with acrylic acid block copolymerization provided by the invention that the embodiment of the present invention 1 provides
Observation figure；Fig. 3 is the paint film observation figure of the coating for the addition commercial dispersants that the embodiment of the present invention 1 provides.Pass through Fig. 2 and Fig. 3
The coating surface that can be seen that in Fig. 2 of comparison it is smooth, without apparent particle, the paint film in Fig. 3 has apparent particle.So as to demonstrate,prove
It, can with excellent dispersion performance when bright acrylate block copolymer provided in this embodiment is used as coating dispersant
Effectively facilitate dispersion of the pigment in cold coating.
Embodiment 2
1) acrylate block copolymer, is prepared：
1-1), the preparation of solvation segment：
Chain-transferring agent, 100mol stearyl acrylate acid esters that 1mol has formula (K-5) structure are added in reaction kettle, led to
Enter nitrogen 30min, the ethylene glycol ethyl ethers containing the 0.3mol peroxidating 2- ethyl acid tert-butyl esters are slowly added dropwise at being 100 DEG C in temperature
(molar ratio of the peroxidating 2- ethyl acids tert-butyl ester and ethyl cellosolve acetate is 0.3 to ether acetic acid ester solution:500) it, is added dropwise
After the ethyl cellosolve acetate solution of the ethyl acid tert-butyl esters of 2- containing peroxidating, it is anti-that stearyl acrylate acid esters proceeds by polymerization
Should, after 6.5h is reacted, stop reaction, obtain prepolymer.
The amount of stearyl acrylate acid esters in the prepolymer is detected, and according to stearyl acrylate using gas-chromatography
The conversion ratio of the content calculation stearyl acrylate acid esters of acid esters, result are：The conversion ratio of stearyl acrylate acid esters reaches 90%.
1-2), the preparation of block polymer：
The prepolymer of preparation is added in reaction kettle, and adds in 2- trimethylethyl acrylic acid ammonium chloride 20mol, in temperature
It spends at 100 DEG C and to be slowly added dropwise the ethyl cellosolve acetate solution containing the 0.3mol peroxidating 2- ethyl acid tert-butyl esters
(molar ratio of the peroxidating 2- ethyl acids tert-butyl ester and ethyl cellosolve acetate is 0.3:500) second of 2- containing peroxidating, is added dropwise
After the ethyl cellosolve acetate solution of tert-butyl acrylate, prepolymer and 2- trimethylethyl acrylic acid ammonium chlorides proceed by base
Polymerisation after 7.5h is reacted, stops reaction, obtains acrylate block copolymer.
Using gas-chromatography to the content of 2- trimethylethyls acrylic acid ammonium chloride in the acrylate block copolymer
It is detected, and turn of the content calculation 2- trimethylethyl acrylic acid ammonium chlorides according to 2- trimethylethyl acrylic acid ammonium chlorides
Rate, result are：The conversion ratio of 2- trimethylethyl acrylic acid ammonium chlorides reaches 100%.
Gel permeation chromatography (Gel Permeation are carried out to acrylate block copolymer obtained
Chromatography, GPC) analysis, the results are shown in Figure 4, and Fig. 4 is the GPC figures that the embodiment of the present invention 2 provides, can by Fig. 4
To find out, the number-average molecular weight of the acrylate block copolymer is 38000g/mol, and molecular weight distribution index (PDI) is
1.29。
The acrylic acid according to made from raw material type, raw material rate of charge and gpc analysis result can extrapolate the present embodiment
The block copolymer that ester block copolymer is formed for formula (I-2) building block and formula (II-2) building block：
Wherein, a=100, b=20.
2), application of the acrylate block copolymer prepared in coating：
By 60 grams of acrylic resin (producers：Fine horse nation, model：32221), 10 grams of high-carbon black pigment FW200,3 grams of above-mentioned systems
Acrylate block copolymer, 15 grams of transparent powders and the 12 grams of dimethylbenzene one obtained reinstate three-roll grinder grinding, obtain black painting
Material 1.
By 60 grams of acrylic resin (producers：Fine horse nation, model：32221), 10 grams of high-carbon black pigment FW200,3 grams certain are commercially available
Dispersant, 15 grams of transparent powders and 12 grams of dimethylbenzene one reinstate three-roll grinder grinding, obtain blacking 2.
The film on timber by above-mentioned aluminum-bronze paint 1 and aluminum-bronze paint 2 observes paint film, paint film observation result such as Fig. 5 and figure
Shown in 6, Fig. 5 is that the paint film for the coating added with acrylic acid block copolymerization provided by the invention that the embodiment of the present invention 2 provides is seen
Examine figure；Fig. 6 is the paint film observation figure of the coating for the addition commercial dispersants that the embodiment of the present invention 2 provides.Pass through Fig. 5's and Fig. 6
Compare as can be seen that the coating surface in Fig. 5 is smooth.Without apparent particle, the paint film in Fig. 6 has apparent particle.So as to prove
With excellent dispersion performance, Neng Gouyou when acrylate block copolymer provided in this embodiment is used as coating dispersant
Effect promotes dispersion of the pigment in cold coating.
Embodiment 3
1) acrylate block copolymer, is prepared：
1-1), the preparation of solvation segment：
Chain-transferring agent, 200mol isobornyl acrylates that 1mol has formula (K-14) structure are added in reaction kettle,
Nitrogen 60min is passed through, acetic acid dissident's ester containing 0.5mol peroxide acid tert-amyl acetates is slowly added dropwise at being 160 DEG C in temperature
(molar ratio of peroxide acid tert-amyl acetate and acetic acid dissident's ester is 0.5 to solution:1000) uncle containing perbenzoic acid penta, is added dropwise
After acetic acid dissident's ester solution of ester, isobornyl acrylate proceeds by polymerisation, after 7.5h is reacted, stops reaction, obtains
To prepolymer.
The content of isobornyl acrylate in the prepolymer is detected, and different according to acrylic acid using gas-chromatography
The conversion ratio of the content calculation isobornyl acrylate of norbornene ester, result are：The conversion ratio of isobornyl acrylate reaches
100%.
1-2), the preparation of block polymer：
The prepolymer of preparation is added in reaction kettle, and adds in n-vinyl pyrrolidone 50mol, and be slowly added dropwise and contain
Having the acetic acid dissident ester solutions of 0.5mol peroxide acid tert-amyl acetates, (peroxide acid tert-amyl acetate rubs with acetic acid dissident's ester
You are than being 0.5:1000) after acetic acid dissident's ester solution containing peroxide acid tert-amyl acetate, is added dropwise, prepolymer and N- vinylpyridines
Pyrrolidone proceeds by polymerisation, after 7.5h is reacted, stops reaction, obtains acrylate block copolymer.
The content of n-vinyl pyrrolidone in the acrylate block copolymer is detected using gas-chromatography,
And the conversion ratio of the content calculation n-vinyl pyrrolidone according to n-vinyl pyrrolidone, result are：N- vinyl pyrroles
The conversion ratio of alkanone reaches 100%.
Gel permeation chromatography (Gel Permeation are carried out to acrylate block copolymer obtained
Chromatography, GPC) analysis, the results are shown in Figure 7, and Fig. 7 is the GPC figures that the embodiment of the present invention 3 provides, can by Fig. 7
To find out, the number-average molecular weight of the acrylate block copolymer is 50000g/mol, and molecular weight distribution index (PDI) is
1.33。
The acrylic acid according to made from raw material type, raw material rate of charge and gpc analysis result can extrapolate the present embodiment
The block copolymer that ester block copolymer is formed for formula (I-3) building block and formula (II-3) building block：
Wherein, a=200, b=50.
2), application of the acrylate block copolymer prepared in coating：
By 10 grams of acrylic resin (producers：Fine horse nation, model：32221), 30 grams of phthalocyanine blues, 7 grams of acrylic acid obtained above
Ester block copolymer and 53 grams of dimethylbenzene one reinstate three-roll grinder and are ground to fineness qualification, obtain blue paste 1.
By 10 grams of acrylic resin (producers：Fine horse nation, model：32221), 30 grams of phthalocyanine blues, 7 grams of certain commercial dispersants and 53
Gram dimethylbenzene one reinstates three-roll grinder and is ground to fineness qualification, obtains blue paste 2.
Blue paste 1 obtained and blue paste 2 are observed, as a result as shown in Figure 8 and Figure 9, Fig. 8 is of the invention real
The coating observation figure of the offer of example 3 is provided, wherein, label B1 is blue paste 1, and label B2 is blue paste 2；Fig. 9 is this hair
Observation figure of the coating standing that bright embodiment 3 provides after 60 days, wherein, label B1 is blue paste 1, and label B2 is blue
Coating 2.
As seen in Figure 8, acrylate block copolymer provided in this embodiment and commercial dispersants are to phthalocyanine blue
There is good dispersibility.As seen in Figure 9, it is commercially available compared to acrylate block copolymer provided in this embodiment
Dispersant is poor to the dispersion stabilization of phthalocyanine blue, and coating lamination has occurred after standing 60 days, and provided in this embodiment third
Olefin(e) acid ester block copolymer is very stable to the dispersibility of phthalocyanine blue, is not layered.So as to prove propylene provided in this embodiment
With excellent dispersion performance when acid esters block copolymer is used as coating dispersant, pigment can be effectively facilitated and applied in resin
Dispersion in material.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (7)
1. a kind of acrylate block copolymer, including formula (I-3) building block and formula (II) building block；
Wherein, a and b represents the degree of polymerization, X2Selected from H or alkyl, Y2For with formula (Y2- 1)~formula (Y2- 6) in the group of structure
Any one：
2. block copolymer according to claim 1, which is characterized in that the X2Independent is selected from C1~C5Alkyl.
3. block copolymer according to claim 1, which is characterized in that 5≤a≤300；5≤b≤100.
4. block copolymer according to claim 1, which is characterized in that formula (II) building block is with formula (II-
3) block of structure：
5. a kind of preparation method of acrylate block copolymer described in claim 1, includes the following steps：
A), isobornyl acrylate carries out polymerisation in the presence of chain-transferring agent and initiator, obtains prepolymer；
B), the prepolymer and formula (IV) structural compounds carry out polymerisation in the presence of initiator, and it is embedding to obtain acrylate
Section copolymer；
Wherein, X2Selected from H or alkyl, Y2For with formula (Y2- 1)~formula (Y2- 6) any one in the group of structure：
6. a kind of block copolymerization made from Claims 1 to 4 any one of them block copolymer or claim 5 the method
Application of the object as dispersant in coating.
7. application according to claim 6, which is characterized in that the coating includes the acrylic acid tree of 10~100 parts by weight
The block copolymer of fat, the pigment of 10~100 parts by weight and 1~10 parts by weight.
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| CN1735636A (en) * | 2002-11-07 | 2006-02-15 | 罗地亚化学公司 | Controlled structure copolymer comprising an amphoteric or zwitterionic part |
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| CN1386794A (en) * | 2001-05-21 | 2002-12-25 | 西巴特殊化学品控股有限公司 | Pigment compositions with modified block copolymer dispersants |
| CN1735636A (en) * | 2002-11-07 | 2006-02-15 | 罗地亚化学公司 | Controlled structure copolymer comprising an amphoteric or zwitterionic part |
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