CN115485333A - 水性涂料组合物 - Google Patents
水性涂料组合物 Download PDFInfo
- Publication number
- CN115485333A CN115485333A CN202180027188.7A CN202180027188A CN115485333A CN 115485333 A CN115485333 A CN 115485333A CN 202180027188 A CN202180027188 A CN 202180027188A CN 115485333 A CN115485333 A CN 115485333A
- Authority
- CN
- China
- Prior art keywords
- vinyl polymer
- weight
- ethylenically unsaturated
- aqueous
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000008199 coating composition Substances 0.000 title claims abstract description 40
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 194
- 239000000178 monomer Substances 0.000 claims abstract description 131
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 44
- 239000004815 dispersion polymer Substances 0.000 claims abstract description 41
- -1 polyoxyethylene Polymers 0.000 claims abstract description 40
- 239000006185 dispersion Substances 0.000 claims abstract description 23
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 21
- 125000000524 functional group Chemical group 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 7
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims abstract description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004132 cross linking Methods 0.000 claims abstract description 5
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical class NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004094 surface-active agent Substances 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 230000009477 glass transition Effects 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000000049 pigment Substances 0.000 claims description 10
- 239000003480 eluent Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 238000001542 size-exclusion chromatography Methods 0.000 claims description 8
- 239000002562 thickening agent Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000006096 absorbing agent Substances 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 239000000080 wetting agent Substances 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 239000000975 dye Substances 0.000 claims description 4
- 239000012760 heat stabilizer Substances 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 238000005227 gel permeation chromatography Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 238000011088 calibration curve Methods 0.000 claims 2
- 239000003973 paint Substances 0.000 abstract description 34
- 229920000642 polymer Polymers 0.000 abstract description 28
- 238000009472 formulation Methods 0.000 abstract description 10
- 239000001978 cystine tryptic agar Substances 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 47
- 239000003999 initiator Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 239000010410 layer Substances 0.000 description 15
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 239000000839 emulsion Substances 0.000 description 9
- 238000012546 transfer Methods 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000010526 radical polymerization reaction Methods 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 4
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000002877 alkyl aryl group Chemical group 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 235000010350 erythorbic acid Nutrition 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229940026239 isoascorbic acid Drugs 0.000 description 4
- 239000004922 lacquer Substances 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 4
- 150000003568 thioethers Chemical class 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- WQPMYSHJKXVTME-UHFFFAOYSA-N 3-hydroxypropane-1-sulfonic acid Chemical compound OCCCS(O)(=O)=O WQPMYSHJKXVTME-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 239000004908 Emulsion polymer Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 125000005336 allyloxy group Chemical group 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000006184 cosolvent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 150000001988 diarylethenes Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000004318 erythorbic acid Substances 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 2
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 2
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229940096992 potassium oleate Drugs 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 229940114930 potassium stearate Drugs 0.000 description 2
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 2
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
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- XZTJQQLJJCXOLP-UHFFFAOYSA-M sodium;decyl sulfate Chemical compound [Na+].CCCCCCCCCCOS([O-])(=O)=O XZTJQQLJJCXOLP-UHFFFAOYSA-M 0.000 description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
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Abstract
本发明涉及包含可交联的水性乙烯基聚合物分散体的涂料组合物,包含所述可交联的水性乙烯基聚合物分散体的漆配制剂,和用涂料组合物或漆配制剂涂覆的制品。特别地,本发明提供一种水性乙烯基聚合物分散体PD,其包含以下聚合物:1)可通过单体混合物的自由基乳液聚合获得的乙烯基聚合物P1的水性分散体,所述单体混合物包含:a)5‑20重量%的酸官能的烯属不饱和单体M1或其前体;b)5‑25重量%的含有聚氧乙烯或单烷氧基聚氧乙烯部分的烯属不饱和单体M2;c)最多90重量%的不同于M1或M2的非离子烯属不饱和单体M3;d)0‑10重量%的具有在成膜后交联的官能团的烯属不饱和单体M4;(e)0‑10重量%的至少一种链转移剂CTA;其中M1+M2+M3+M4+CTA的重量%之和=100重量%;2)可通过以下物质的自由基共聚合获得的乙烯基聚合物P2的水性分散体或溶液:a)25‑95重量%的选自具有以下一般结构的N‑乙烯基酰胺的烯属不饱和单体M5:其中R1和R2是C1‑C5烷基且可连接以形成环结构,优选N‑乙烯基吡咯烷酮或N‑乙烯基己内酰胺;b)5‑75重量%的不同于M5的非离子烯属不饱和单体M3′;c)0‑5重量%的具有在成膜后交联的官能团的烯属不饱和单体M4′;d)0‑10重量%的酸官能的烯属不饱和单体M1′或其前体;e)0‑5重量%的至少一种链转移剂CTA′;其中M5+M3′+M4′+M1′+CTA′的重量%之和=100重量%;3)水性分散体形式的成膜性乙烯基聚合物P3,其包含:i)20‑60重量%的通过乳液聚合单体混合物获得的水溶性或水分散性可交联的乙烯基低聚物OL,所述单体混合物包括:1)至少一种酸官能的烯属不饱和单体M1″;2)至少一种不同于M1″具有在成膜后交联的官能团的烯属不饱和单体M4″;3)至少一种不同于M1″和M2″的烯属不饱和单体M3″,和5)任选地,至少一种链转移剂CTA″,和ii)40‑80重量%的高分子量乙烯基聚合物P4,其通过在存在水溶性或水分散性可交联的乙烯基低聚物OL的情况下乳液聚合单体混合物制备,所述单体混合物包括:1)任选地,至少一种酸官能的烯属不饱和单体M1″′;2)任选地,一种或多种不同于M1″′具有在成膜后交联的官能团的烯属不饱和单体M4″′;3)至少一种不同于M1″′和M2″′的烯属不饱和单体M3″′,和4)任选地,一种或多种用于预交联的多官能烯属不饱和单体M5″′,优选其量小于5重量%,其中成膜性乙烯基聚合物P3的总重量=水溶性或水分散性可交联的乙烯基低聚物OL的重量%+高分子量乙烯基聚合物P4的重量%=i)+ii)=100重量%,和其中水性乙烯基聚合物分散体PD中乙烯基聚合物的总重量=乙烯基聚合物P1的重量%+乙烯基聚合物P2的重量%+成膜性乙烯基聚合物P3的重量%=100重量%。
Description
本发明涉及可交联的水性乙烯基聚合物分散体,包含所述可交联的水性乙烯基聚合物分散体的涂料组合物,包含所述可交联的水性乙烯基聚合物分散体的漆配制剂,和用所述涂料组合物或漆配制剂涂覆的制品。
背景技术
挥发性化合物排放的法规正驱使从溶剂型向水性涂料组合物转变。然而,水性涂料组合物仍然需要改进以实现或匹配它们的溶剂型对应物的有利性能。水性涂料组合物的一个特别问题是可再次操作新施涂的涂料层而没有在固化涂层中留下可见缺陷如刷痕、辊痕、喷雾灰尘(通常称为“过喷”)或在相邻涂层之间的接合处的可见线条的时间段短。
当新施涂到基材的涂料组合物层仍处于其中可在干燥过程中操作而没有在干燥涂料中留下明显可见缺陷的状态时,其被称为“开放的”。开放时间是在涂层的第一次施涂的时刻直至在不留下可见缺陷的情况下湿漆膜中不可再进行修正的时刻之间的时间段。
长期以来期望改进基于水性成膜涂料组合物的水性漆的开放时间。水性涂料组合物中的成膜聚合物通常是指具有足够低的玻璃化转变温度以在环境使用温度下在基材上形成粘附膜的聚合物,优选具有在0-60℃的最低成膜温度。
据信在涂料的配制中可通过使用水溶性添加剂或助粘结剂来实现更长的开放时间。例如,水溶性共溶剂例如亚烷基二醇(例如乙二醇、丙二醇、2-甲基-2,4-戊二醇)被认为对开放时间具有有益影响。或者,已经提出水溶性聚合物例如聚乙烯醇、聚氧乙烯、聚(甲基)丙烯酰胺和聚2-乙基噁唑啉可用于延长水性涂料的开放时间。然而,已知的水溶性聚合物开放时间改进剂的一般问题是所得涂层表现出差的耐水性。这实际上意味着仅可使用非常低的水平,因此降低了改进开放时间或湿边时间的有效性。当第一漆层需要被相同漆的第二层覆盖时,例如为了提供对基材的充分遮盖,水溶性添加剂也产生问题。一般来说,这些漆的再涂性差。
EP 136025 B1公开了包括含有离子和非离子结构部分的水溶性共聚物的漆配制剂。尽管这些共混物可改进装饰性漆的开放时间和可刷涂性,但没有提及关于这样施涂的相关数据或权利要求。
EP 0593151 B1描述增强水性涂料的开放时间的方法。该方法包括共混含有反应官能团的丙烯酸类胶乳与含有与聚合物胶乳的反应基团互补的反应性基团的改性两亲性-较低分子量化合物。改性化合物的加入确实增强仅用丙烯酸类胶乳制备的对照漆的开放时间。然而,开放时间达到最大为仅15分钟,并且没有提及关于第二层的开放时间及其再涂性的数据。
US 2001/0031826A1描述乳液聚合物用于配制具有改进的开放时间的高光泽度漆的用途。使用(甲基)丙烯酸类单体与聚环氧烷官能的单体的混合物制备乳液聚合物。在一些实例中,用这些共聚物制备的漆的开放时间确实显著高于20分钟。然而,未提供关于漆的再涂性的数据。
WO 2012130817 A1描述了由两种成膜聚合物分散体的共混物制备的水性组合物,与常规的商购装饰漆相比,其对于第一层表现出延长的开放时间和优异的耐化学性和粘连性。第一聚合物分散体含有用于环境交联性基团和羧酸/聚氧乙烯官能团。第二聚合物分散体来自聚氨酯、乙烯基聚合物或醇酸树脂。
尽管在本领域中取得了进步,但是主要关注开放时间和所施涂的第一漆层的干膜性能。然而,装饰和建筑漆通常作为多层体系施涂以便获得基材的充分遮盖。因此,在第二层的施涂期间的开放时间必须与第一漆层的开放时间处于相同水平。WO 2015107163 A1公开了允许第一漆层的开放时间为22-25分钟的技术。然而,当施涂随后的一个或多个漆层时,这个性能不再存在,开放时间减少约30-50%。而且施涂的第二漆层的流动和流平性差。因此需要在以多层施涂的漆中具有好的开放时间、流动和流平性的水性涂料。
发明详述
本发明涉及用于在本发明的涂料组合物中使用的水性乙烯基聚合物分散体。这种水性乙烯基聚合物分散体PD包含以下聚合物:
1)可通过单体混合物的自由基乳液聚合获得的乙烯基聚合物P1的水性分散体,所述单体混合物包括:
a)5-20重量%的酸官能的烯属不饱和单体M1或其前体;
b)5-25重量%的含有聚氧乙烯或单烷氧基聚氧乙烯部分的烯属不饱和单体M2;
c)最多90重量%的不同于M1或M2的非离子烯属不饱和单体M3;
d)0-10重量%的具有在成膜后交联的官能团的烯属不饱和单体M4;
(e)0-10重量%的至少一种链转移剂CTA;
其中M1+M2+M3+M4+CTA的重量%之和=100重量%;
2)可通过以下单体的自由基共聚合获得的乙烯基聚合物P2的水性分散体或溶液:
a)25-95重量%的选自具有以下一般结构的N-乙烯基酰胺的烯属不饱和单体M5:
其中R1和R2是C1-C5烷基且可连接形成环结构,优选N-乙烯基吡咯烷酮或N-乙烯基己内酰胺;
b)5-75重量%的非离子烯属不饱和单体M3′;
c)0-5重量%的具有在成膜后交联的官能团的烯属不饱和单体M4′;
d)0-10重量%的酸官能的烯属不饱和单体M1′或其前体;
(e)0-5重量%的至少一种链转移剂CTA′;
其中M5+M3′+M4′+M1′+CTA′的重量%之和=100重量%;
3)水性分散体形式的成膜性乙烯基聚合物P3,其包含:
i)20-60重量%的通过单体混合物的乳液聚合获得的水溶性或水分散性可交联的乙烯基低聚物OL,所述单体混合物包括:
1)至少一种酸官能的烯属不饱和单体M1”;
2)至少一种不同于M1”的具有在成膜后交联的官能团的烯属不饱和单体M4”;
3)至少一种不同于M1”和M2”的烯属不饱和单体M3”,和
5)任选地,至少一种链转移剂CTA”,和
ii)40-80重量%的高分子量乙烯基聚合物P4,其通过在存在水溶性或水分散性可交联的乙烯基低聚物OL的情况下乳液聚合单体混合物制备,所述单体混合物包括:
1)任选地,一种酸官能的烯属不饱和单体M1’”;
2)任选地,一种或多种不同于M1’”的具有在成膜后交联的官能团的烯属不饱和单体M4’”;
3)至少一种不同于M1’”和M2’”的烯属不饱和单体M3’”,和
4)任选地,一种或多种用于预交联的多官能的烯属不饱和单体M5’”,优选其量小于5重量%;
其中成膜性乙烯基聚合物P3的总重量=水溶性或水分散性可交联的乙烯基低聚物OL的重量%+高分子量乙烯基聚合物P4的重量%=i)+ii)=100重量%,和
其中水性乙烯基聚合物分散体PD中的乙烯基聚合物的总重量=乙烯基聚合物P1的重量%+乙烯基聚合物P2的重量%+成膜性乙烯基聚合物P3的重量%=100重量%。
乙烯基聚合物P1、P2和P3可单独合成并可通过共混它们各自的水性分散体而将其结合以构成聚合物分散体PD。乙烯基聚合物P1、P2与P3之比为(1:1:98)至(65:15:20),优选(9:1:90)至(50:10:40),更优选(25:1.5:73.5)至(35:4.5:60.5)和最优选(27:2:70)-(32:4:65)。
水性乙烯基聚合物分散体PD由以下组成:30-60重量%的乙烯基聚合物P1+P2+P3,剩余是水、表面活性剂、中和碱和抗微生物剂等。
“烯属不饱和单体”意指在本发明中具有至少一个可经历自由基聚合的碳-碳双键的单体。
前缀“(甲基)丙烯酰基”当用于命名本发明的化合物时包含“丙烯酰基”和“甲基丙烯酰基”并指包含至少一个CH2=CHCOO-基团或CH2=C(CH3)COO-基团及其混合物的化合物和这样的化合物的混合物。
“乙烯基低聚物”意为借助于烯属不饱和单体的自由基聚合获得的低分子量聚合物。
“乙烯基聚合物”意为来源于含有碳-碳双键的乙烯基单体的聚合物。
“M1+M2+M3+M4+CTA的重量%之和=100重量%时”意为乙烯基聚合物P1基本上由以上定义的单体M1、M2、M3、M4和至少一种链转移剂CTA组成。因此,乙烯基聚合物P1的总重量对应于单体M1、M2、M3、M4和至少一种链转移剂CTA的重量百分比之和。
“M5+M3′+M4′+M1′+CTA′的重量%之和=100重量%时”意为乙烯基聚合物P2基本上由单体M5、M3′、M4′、M1′和至少一种链转移剂CTA′组成。因此,乙烯基聚合物P2的总重量对应于单体M5、M3′、M4′、M1′和至少一种链转移剂CTA′的重量百分比之和。
“成膜性乙烯基聚合物P3的总重量=水溶性或水分散性可交联的乙烯基低聚物OL的重量%+高分子量乙烯基聚合物P4的重量%=i)+ii)=100重量%”意为成膜性乙烯基聚合物P3基本上由水溶性或水分散性可交联的乙烯基低聚物OL和高分子量乙烯基聚合物P4组成。因此,成膜性乙烯基聚合物P3的总重量对应于水溶性或水分散性可交联的乙烯基低聚物OL和高分子量乙烯基聚合物P4的重量百分比之和。
“水性乙烯基聚合物分散体PD中乙烯基聚合物的总重量=乙烯基聚合物P1的重量%+乙烯基聚合物P2的重量%+成膜性乙烯基聚合物P3的重量%=100重量%时”意为这种乙烯基聚合物基本上由乙烯基聚合物P1、乙烯基聚合物P2和成膜性乙烯基聚合物P3组成。因此,水性乙烯基聚合物分散体PD中乙烯基聚合物的总重量对应于乙烯基聚合物P1、乙烯基聚合物P2和成膜性乙烯基聚合物P3的重量百分比之和。因此,水性乙烯基聚合物分散体PD基本上由乙烯基聚合物P1的水性分散体、乙烯基聚合物P2的水性分散体或溶液和成膜性乙烯基聚合物P3的水性分散体组成。
乳液聚合物的方法描述于“Chemistry and Technology of EmulsionPolymerisation”,编者A..van Herk,(2005),Blackwell Publishing Ltd。
单体的定义
-单体M1、M1′、M1”和M1’”
酸官能的烯属不饱和单体M1、M1′、M1”和M1’”可每个独立地选自羧酸官能的单体或它的前体例如丙烯酸、甲基丙烯酸、马来酸或它的半酯、富马酸或它的半酯和衣康酸或它的半酯。这些单体可以由石化原料生产。或者,它们可以来源于可再生原料。生物基丙烯酸可由甘油或羟基丙酸、羟基丙酸衍生物或它们的混合物生产。衣康酸由糖的发酵获得和生物基甲基丙烯酸可来源于衣康酸。
其它酸官能的含非羧基的单体可例如为硫酸盐或磺酸单体。作为非限制性实例可以提到2-丙烯酰胺基-2-甲基丙烷磺酸或它的碱、氨或胺盐,和烯丙基缩水甘油醚与亚硫酸氢钠的加合物的钠盐,甲基丙烯酸2-磺基乙酯或1-(烯丙氧基)-2-羟基丙烷-1-磺酸。此外可使用磷酸酯或膦酸酯官能的单体。这样的单体的非限制性实例是磷酸单丙烯酰氧基乙酯 PAM-100和 PAM-200(都来自Solvay),磷酸二氢10-甲基丙烯酰氧基癸酯(Kuraray),膦酸二甲基(2-甲基丙烯酰氧基乙酯)和膦酸二甲基(2-甲基丙烯酰氧基丙酯)或丙烯酸乙基2-[4-(二羟基磷酰基)-2-氧丁酯]。
-单体M2、M2′、M2”和M2”’
含有聚氧乙烯的烯属不饱和单体M2、M2′、M2”和M2”’优选包括通式R3-O-(CH2-CH2-O)n-R2的单体,其中R3是丙烯酰基或甲基丙烯酰基;R2是H或烷基,优选包含1-4个碳原子,n是1-35、优选更优选2-20和最优选3-15的整数。含聚氧乙烯的烯属不饱和单体优选包含2-50个氧化乙烯单元、更优选2-20和最优选2-15。单体优选是聚氧乙烯(甲基)丙烯酸酯单体或单甲氧基(甲基)丙烯酸酯单体。聚氧乙烯烯属不饱和单体ii)的合适实例是甲氧基聚氧乙烯550甲基丙烯酸酯和甲氧基聚氧乙烯350甲基丙烯酸酯。实例是ETMA、MPEG550MA(可从Evonik得到)、S20W、PEA6(可从GEO Specialty Chemicals得到)。
-单体M3、M3′、M3”和M3”’
非离子烯属不饱和单体M3、M3′、M3”和M3”’优选包括苯乙烯和苯乙烯衍生物例如α-甲基苯乙烯,叔丁基苯乙烯,乙烯基甲苯,邻位、间位和对位甲基苯乙烯,邻位、间位和对位乙基苯乙烯,(甲基)丙烯酸的烷基酯,乙烯基酯,含羟基基团的乙烯基单体;优选的单体包括丙烯酸和甲基丙烯酸的酯例如(甲基)丙烯酸正丁酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸环烷酯例如(甲基)丙烯酸环己酯。衣康酸的酯例如衣康酸二甲酯和二丁酯。这些单体可以由石化原料生产。或者它们可以来源于可再生原料例如生物基丙烯酸和甲基丙烯酸。在酯化(酯交换)中使用的烷醇也可为生物来源的。这样的单体的非限制性实例是 Terra C13-MA、 Terra C17.4-MA、丙烯酸正辛酯和(甲基)丙烯酸异冰片酯;以及二烯例如1,3-丁二烯或异戊二烯;或它们的混合物。此外,在单体组成中可使用乙烯基酯例如乙酸乙烯酯、链烷酸乙烯酯或它们的衍生物或混合物。还可使用腈类例如(甲基)丙烯腈。
-单体M4、M4′、M4”和M4”’
具有不同于酸性基团的官能团的单体M4、M4′、M4”和M4”’可用于在成膜后交联。M4、M4′、M4”和M4”’可为相同或不同的。这些单体的实例包括羟基官能的单体例如(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酸羟丁酯,以及具有潜在羟基基团的单体例如甲基丙烯酸缩水甘油酯。羟基官能的基团可与聚异氰酸酯在环境温度至稍微升高的温度下交联。另外的实例包括(甲基)丙烯酰胺的衍生物例如N-羟甲基(甲基)丙烯酰胺。单体的其它实例是含有羰基基团的那些,例如丙烯醛、甲基丙烯醛、丁烯醛、4-乙烯基苯甲醛、4-7个碳原子的乙烯基烷基酮例如乙烯基甲基酮。另外的实例包括丙烯酰胺新戊醛、甲基丙烯酰胺新戊醛、3-丙烯酰胺甲基茴香醛、二丙酮丙烯酸酯和二丙酮甲基丙烯酸酯,和含酮酰胺例如二丙酮丙烯酰胺。还可使用具有乙酰乙酸基官能团的单体。这样的单体的实例是甲基丙烯酸乙酰乙酸基乙酯、丙烯酸乙酰乙酸基乙酯、丙烯酸乙酰乙酸基丙酯、乙酰乙酸烯丙酯和丙烯酸乙酰乙酸基丁酯。单体M4、M4′、M4”、M4”’和M4””的优选官能团分别优选是羰基或乙酰乙酸酯基团。
在特别优选的实施方案中,单体M4、M4′、M4”、M4”’和M4””分别选自甲基丙烯酸乙酰乙酸基乙酯和二丙酮丙烯酰胺或它们的混合物。用于与以上官能团组合使用的交联剂对本领域技术人员是已知的并包括二或多胺和二或多羧酸酰肼。交联可发生在环境温度或稍微升高的温度下。交联剂可以已引入聚合物P1、P2或P3的分散体中或可在之后的阶段加入。
-单体M5
单体M5可每个独立地选自具有以下一般结构的N-乙烯基酰胺:
其中R1和R2是C1-C5烷基且可连接形成环结构,优选N-乙烯基吡咯烷酮或N-乙烯基己内酰胺。
-链转移剂CTA、CTA′和CTA”
使用链转移剂CTA、CTA′、CTA”来控制聚合物P1、P2和OL的分子量。示例性链转移剂是丁硫醇、巯基丙酸、巯基丙酸2-乙基己酯、正十二烷硫醇、叔十二烷硫醇、巯基丙酸正丁酯、2-巯基乙醇、辛硫醇、异癸硫醇、十八烷硫醇、巯基乙酸、巯基丙酸烯丙酯、巯基乙酸烯丙酯、巯基丙酸巴豆酯、巯基乙酸巴豆酯。其它非硫基链转移剂包括卤化烃或催化链转移剂。还可使用α-甲基苯乙烯二聚体或α-甲基苯乙烯二聚体的低聚物。合成具有明确限定分子量的聚合物的另一方法是使用二芳基乙烯。常使用的二芳基乙烯包括二苯基乙烯。
乙烯基聚合物P1、P2和P3的定义
-乙烯基聚合物P1
乙烯基聚合物P1可通过自由基水性乳液聚合在存在至少一种自由基引发剂和至少一种表面活性剂、任选的包含自由基反应性双键的可共聚合表面活性剂的情况下获得。
乙烯基聚合物P1具有2,000-120,000g/mol,且优选4,000-12,000g/mol和最优选5,000-10,000g/mol的数均分子量Mn。重均分子量(Mw)优选8,000-50,000g/mol和最优选10,000-25,000g/mol。使用尺寸排阻色谱法(SEC)使用THF和2%乙酸作为洗脱剂来测定分子量和分子量分布。乙烯基聚合物P1具有1.2-3.0、优选1.5-2.5的多分散度,其中多分散度通过Mn/Mw的比定义。乙烯基聚合物P1含有5-25重量%、优选7-20重量%和最优选9-15重量%的聚氧乙烯烯属不饱和单体M2。乙烯基聚合物P1优选具有30-150mg KOH/g的酸值,通过ISO 3682测定。当使用水性乳液聚合时,乙烯基聚合物P1以聚合物分散体的形式获得,其中将聚合物中的酸官能团中和至0.05-0.70、优选0.10-0.25的α值和P1的水性分散体具有6.0-8.0、最优选6.5-7.5的pH。
根据一个实施方案,乙烯基聚合物P1具有:2,000-120,000g/mol的数均分子量(通过尺寸排阻色谱法使用四氢呋喃和2%乙酸作为洗脱剂和使用聚苯乙烯标准物测定),30-150mg KOH/g的酸值(通过ISO 3682测定),和相对于聚合物P1的总重量5-25重量%的选自以下的烯属不饱和单体M2:聚氧乙烯和单烷氧基聚氧乙烯(甲基)丙烯酸酯。
-乙烯基聚合物P2
乙烯基聚合物P2是可在大气压或升高的压力下在0-200℃的温度下通过本领域已知的自由基共聚合技术制备的加成聚合物。优选的是乙烯基聚合物P2是无规共聚物。其中来自单体A的侧基未均匀分布在第二聚合物中的嵌段共聚物或梯度共聚物不是优选的,因为它们疑似未形成水溶性的基本上牛顿溶液。优选地,通过溶液聚合在可借助于蒸馏容易去除的有机溶剂例如甲乙酮、丙酮或异丙醇中或在水混溶性溶剂例如丁二醇、二乙二醇单丁醚或二乙二醇单乙醚中制备乙烯基聚合物P2。
乙烯基聚合物P2通常具有1,000-50,000、优选2,000-40,000、更优选4,000-25,000和最优选8,000-12,500g/mol的重均分子量Mw(通过凝胶渗透色谱法使用六氟异丙醇作为洗脱剂并使用聚(甲基丙烯酸甲酯)标准物用于曲线矫正来测定)。
乙烯基聚合物P2优选具有-30℃至180℃的玻璃化转变温度Tg。优选地,Tg为至少0℃、优选至少20℃、更优选至少35℃和最优选至少45℃。使用甚至大于60、70、80和大于90和100℃的Tg获得好的结果。优选地第二聚合物的Tg在0-180℃之间。
如以上描述,乙烯基聚合物P2具有非离子但亲水的、源自水溶性的单体M5的官能团。
考虑到设想的涂料性能,优选的是乙烯基聚合物P2中至少80%、优选90%或甚至95%的单体M3′具有小于120、优选小于100、50或20和更优选小于-10℃的单体Tg。
乙烯基聚合物P2还包含0-5重量%的不同于单体M1′和M2′的交联性单体M4′。单体M3′的有效量范围在5-75重量%之间。
乙烯基聚合物P2还包含0-5重量%的链转移剂CTA′。
在最优选的实施方案中,乙烯基聚合物P2是N-乙烯基吡咯烷酮和丙烯酸乙酯的共聚物。还优选N-乙烯基己内酰胺和丙烯酸乙酯的共聚物。
-成膜性乙烯基聚合物P3
乙烯基聚合物P3是通过在存在水溶性或水分散性乙烯基低聚物OL的情况下聚合乙烯基聚合物P4获得的成膜聚合物。
-水溶性或水分散性可交联的乙烯基低聚物OL
水溶性或水分散性可交联的乙烯基低聚物OL通常是由单体M1”、M3”和M4”和链转移剂CTA”构成的酸官能的低聚物。所述低聚物优选具有500-50,000g/mol、更优选2,500-25,000g/mol和最优选5,000-15,000g/mol的数均分子量Mn。低聚物的数均分子量和重均分子量(Mn和Mw)可以通过使用凝胶渗透色谱法使用已知分子量的聚合物例如聚苯乙烯作为标准物和含有2%乙酸的THF作为洗脱剂来测定。可交联的乙烯基低聚物OL优选具有在10-150℃、更优选20-125℃和最优选25-115℃范围内的玻璃化转变温度。
本文中低聚物OL的Tg代表计算的玻璃化转变温度并众所周知是聚合物由玻璃状脆性状态改变为橡胶状态的温度。使用众所周知的Fox等式(T.G.Fox,Bull.Am.Phys.Soc.1,123(1956))来计算Tg值,这是本领域众所周知的并由下式表示:
1/Tg=W1/Tg(1)+W2/Tg(2)+W3/Tg(3)+…
其中W1、W2、W3等是共聚单体(1)、(2)和(3)等的重量分数和Tg(1)、Tg(2)、Tg(3)是它们各自均聚物的玻璃化转变温度。使用在Polymer Handbook第4版(编者:J.Brandrup,E.H.Immergut,E.A.Grulke,John Wiley&Sons,Inc.1999)中给出的均聚物的玻璃化转变值来进行计算。以开氏度为单位的计算的Tg可以容易地转换为摄氏度。
乙烯基低聚物OL优选具有至少45mg KOH/g、更优选至少50mg KOH/g和最优选至少55mg KOH/g的酸值。
在乳液聚合中影响分子量以便实现期望的数均分子量的方法对本领域技术人员是众所周知的。可以通过使用链转移剂例如硫醇和卤化烃来控制低聚物的分子量。合适的硫醇包括正十二烷硫醇、正辛硫醇、叔十二烷硫醇、2-巯基乙醇、巯基乙醇酸异辛酯、C2-C8巯基羧酸和它们的酯例如3-巯基丙酸和2-巯基丙酸。
可交联的乙烯基低聚物OL可以通过任何已知的技术制备,并且可以包括在含水方法中,即在存在水的情况下(例如通过乳液聚合、悬浮聚合、微悬浮聚合或微乳液聚合),或者通过溶液聚合直接合成低聚物,其中在溶液聚合中溶剂可以是水或者任何与水混溶的或者在低聚物转移到水中之后通过蒸馏去除的有机溶剂。当低聚物是大分子单体时,它可以通过包括但不限于使用可逆加成断裂(RAFT)试剂的许多方法,通过使用催化链转移剂例如钴链转移来制备。还可使用α-甲基苯乙烯二聚体或α-甲基苯乙烯二聚体的低聚物,如在US2007/0043156A1和US 6,872,789中所解释的。合成具有明确限定分子量的聚合物的另一方法是使用二芳基乙烯例如二苯基乙烯,或高温方法。
优选地乙烯基低聚物OL通过溶液聚合、乳液聚合或悬浮聚合制备。优选地低聚物通过含水方法制备。优选地含水方法的连续相包含>50重量%、更优选>80重量%和最优选>95重量%的水。
最优选地乙烯基低聚物OL通过含水自由基乳液聚合方法制备。
自由基聚合可以间歇或半连续聚合方法进行。
自由基乳液聚合将经常需要使用产生自由基的引发剂以引发聚合。合适的产生自由基的引发剂包括无机过氧化物例如K、Na或铵过硫酸盐、过氧化氢或过碳酸盐;有机过氧化物例如酰基过氧化物,包括例如苯甲酰过氧化物、烷基过氧化氢例如叔丁基过氧化氢和氢过氧化枯烯;二烷基过氧化物例如二叔丁基过氧化物;过氧酯例如过苯甲酸叔丁酯等;还可以使用混合物。过氧化合物在一些情况下有利地与合适的还原剂(氧化还原体系)例如Na或K焦亚硫酸盐或亚硫酸氢盐、FF6(来自L.Brüggemann GmbH&Co.KG的商品名)和异抗坏血酸组合使用。金属化合物例如Fe.EDTA(EDTA是四乙酸乙二胺)也可以用作氧化还原引发剂体系的一部分。还可以使用偶氮官能的引发剂例如偶氮双(异丁腈),2,2'-偶氮-双(2-甲基丁腈)(ANBN)和4,4'-偶氮双(4-氰基戊酸)。可以使用在水相和有机相之间分配的引发剂体系,例如叔丁基过氧化氢、异抗坏血酸或FF6和Fe.EDTA的组合。使用的引发剂或引发剂体系的量是常规的,例如在0.05-6重量%的范围内,基于使用的总乙烯基单体。制备可交联的低聚物的优选引发剂包括过硫酸铵、过硫酸钠、过硫酸钾、偶氮双(异丁腈)和/或4,4'-偶氮双(4-氰基戊酸)。制备可交联的低聚物的最优选引发剂包括如以上描述的氧化还原体系和过硫酸盐。可以任选在聚合工艺结束时添加另外量的引发剂以帮助去除任何残余的乙烯基单体。
如果可交联的乙烯基低聚物OL借助于乳液聚合制备,则可使用表面活性剂以帮助乙烯基共聚物在水中分散或乳化(即使它是可自分散的)。合适的表面活性剂是离子或非离子表面活性剂。阴离子乳化剂的实例是:月桂酸钾、硬脂酸钾、油酸钾、硫酸癸酯钠、硫酸十二烷酯钠和松脂酸钠。非离子乳化剂的实例是:直链和支化的烷基和烷芳基聚乙二醇醚和硫醚以及直链和支化的烷基和烷芳基聚丙二醇醚和硫醚,烷基苯氧基聚(乙烯氧基)乙醇例如1摩尔的壬基苯酚与5-50摩尔的氧化乙烯的加合物或所述加合物的硫酸或磷酸的碱盐或铵盐。
还可使用可参与自由基聚合的含有烯属不饱和基团的表面活性剂。合适的可聚合的表面活性剂包括式M+.OOC-CH=CHCOOR的马来酸酐的半酯,其中R是C6-C22烷基和M+是Na+、K+、Li+、NH4+或质子化胺或季胺。所述表面活性剂包括具有烯属不饱和键的聚氧乙烯烷基苯基醚,其以商品名RN(得自Montello,Inc.)例如NOIGENTM RN-10、NOIGENTMRN-20、NOIGENTM RN-30、NOIGENTM RN-40和NOIGENTM RN-5065销售;或它们的硫酸盐,其以商品名BC(得自Montello,Inc.)例如BC-10、BC-1025、BC-20、BC-2020、BC-30销售;6106(可从Croda得到),其具有膦酸酯和乙氧基亲水性以及具有丙烯酸酯反应性基团的标称C18烷基链。适合于这样反应的其它代表性的具有磷酸酯官能团的反应性表面活性剂包括但不限于6112、5011、5010(全部可从Croda IndustrialSpecialties得到)。适合于与本发明的各种实施方案一起使用的供选择的反应性表面活性剂包括烯丙氧基羟丙基磺酸钠(可从Solvay作为COPS-1得到),ADEKASR/ER系列例如ADEKAER-10、ER-20、ER-30和ER-40,AkedaReasoap SR-10、SR-20、SR-30(全部可从Asahi Denka Co.,Ltd.得到)和烯丙基磺基琥珀酸酯衍生物(例如LT-40(可从BASF得到))。
低聚物的合成中使用的表面活性剂的量优选0-15重量%、更优选0-8重量%、仍更优选0-5重量%、尤其是0.1-3重量%。
-高分子量乙烯基聚合物P4
优选地乙烯基聚合物P4在含水方法中在存在可交联的乙烯基低聚物OL的情况下制备。在乙烯基聚合物P4的聚合之前,可交联的乙烯基低聚物可以部分或完全溶解。最优选地乙烯基聚合物P4通过水性乳液聚合方法制备。
制备乙烯基聚合物P4的方法可以在许多模式下进行,包括但不限于在一个批次中聚合所有乙烯基低聚物OL和单体M3”’和任选的M1”’和/或M2”’和/或M4”’,将溶解或部分溶解的乙烯基低聚物OL预填充至反应器并在一个或多个阶段中和/或使用梯度加料技术随后加入单体(或反之亦然),将低聚物OL和单体都加入反应器(任选用一些低聚物预填充),通过将单体加入低聚物(其被同时加入反应器,任选用一些乙烯基低聚物预填充)或将乙烯基低聚物和单体的混合物连续加入反应器来制备乙烯基聚合物。
优选地获得乙烯基聚合物P4的自由基聚合通过将反应器内容物加热至30-100℃和更优选50-90℃的温度来进行。
乙烯基聚合物P4的玻璃化转变温度为-70℃至50℃,更经常-25℃至40℃并应小于乙烯基低聚物OL的Tg至少25℃、更优选至少40℃。乙烯基聚合物P4的重均分子量应至少高于60,000g/mol、优选高于100,000g/mol。
包含低聚物OL和聚合物P4的成膜性乙烯基聚合物P3优选为水性聚合物分散体的形式。
乙烯基聚合物P3包含20-60重量%的乙烯基低聚物OL,优选25-55重量%的乙烯基低聚物OL和最优选25-52.5重量%的乙烯基低聚物OL。
乙烯基聚合物P3的水性分散体的固体含量优选在20-60重量%的范围内和最优选在30-50重量%的范围内。
-引发剂
自由基聚合将需要使用产生自由基的引发剂以引发聚合。合适的产生自由基的引发剂包括无机过氧化物例如钾、钠或铵过硫酸盐、过氧化氢或过碳酸盐;有机过氧化物例如酰基过氧化物,包括例如苯甲酰过氧化物、烷基过氧化氢例如叔丁基过氧化氢和氢过氧化枯烯;二烷基过氧化物例如二叔丁基过氧化物;过氧酯例如过苯甲酸叔丁酯等;还可以使用混合物。过氧化合物在一些情况下有利地与合适的还原剂(氧化还原体系)例如钠或钾焦亚硫酸盐或亚硫酸氢盐、甲醛次硫酸氢钠和异抗坏血酸组合使用。还可使用不释放甲醛的还原剂例如FF6。金属化合物例如Fe.EDTA(EDTA是四乙酸乙二胺)还可以用作氧化还原引发剂体系的一部分。还可以使用偶氮官能的引发剂例如偶氮双(异丁腈),2,2'-偶氮-双(2-甲基丁腈)(ANBN)和4,4'-偶氮双(4-氰基戊酸)。可以使用在水相和有机相之间分配的引发剂体系,例如叔丁基氢过氧化物、异抗坏血酸和Fe.EDTA的组合。使用的引发剂或引发剂体系的量是常规的,例如在0.05-6重量%的范围内,基于使用的总乙烯基单体。制备乙烯基聚合物P1、P3和P4和乙烯基低聚物OL的优选引发剂包括过硫酸铵、过硫酸钠、过硫酸钾、偶氮双(异丁腈)和/或4,4'-偶氮双(4-氰基戊酸)。可以任选在聚合工艺结束时添加另外量的引发剂以帮助去除任何残余的乙烯基单体。
-表面活性剂
当作为乳液聚合进行合成P1和P3的自由基聚合时,不得不使用表面活性剂。合适的表面活性剂是离子或非离子表面活性剂。阴离子乳化剂的实例是:月桂酸钾、硬脂酸钾、油酸钾、硫酸癸酯钠、硫酸十二烷酯钠和松脂酸钠。非离子乳化剂的实例是:直链和支化的烷基和烷芳基聚乙二醇醚和硫醚以及直链和支化的烷基和烷芳基聚丙二醇醚和硫醚,烷基苯氧基聚(乙烯氧基)乙醇例如1摩尔的壬基苯酚与5-50摩尔的氧化乙烯的加合物或所述加合物的硫酸或磷酸的碱盐或铵盐。
还可使用可参与自由基聚合的含有烯属不饱和基团的表面活性剂。合适的可聚合的表面活性剂包括式M+-OOC-CH=CHCOOR的马来酸酐的半酯,其中R是C6-C22烷基和M+是Na+、K+、Li+、NH4+或质子化胺或季胺。所述表面活性剂包括具有烯属不饱和键的聚氧乙烯烷基苯基醚,其以商品名RN(得自Montello,Inc.)例如RN-10、RN-20、RN-30、RN-40和RN-5065销售;或它们的硫酸盐,其以商品名BC(得自Montello,Inc.)例如BC-10、BC-1025、BC-20、BC-2020、BC-30销售;MAXEMULTM 6106(可从Uniquema得到),其具有膦酸酯和乙氧基亲水性以及具有丙烯酸酯反应性基团的标称C18烷基链。适合于这样反应的其它代表性的具有磷酸酯官能团的反应性表面活性剂包括但不限于6112、5011、5010(全部可从Croda Industrial Specialties得到)。适合于与本发明的各种实施方案一起使用的供选择的反应性表面活性剂包括烯丙氧基羟丙基磺酸钠(可从Solvay以COPS-1得到),ADEKASR/ER系列例如ADEKAER-10、ER-20、ER-30和ER-40,AkedaSR-10、SR-20、SR-30(全部可从Asahi Denka Co.,Ltd.得到)和烯丙基磺基琥珀酸酯衍生物(例如LT-40(可从BASF得到))。
本发明还涉及包含水性乙烯基聚合物分散体PD的涂料组合物COA。
涂料组合物COA可具有在2.0-9.0、优选4.5-8.5、最优选7.5-8.0之间的pH。可优选通过添加通常的漆添加剂来配制以上描述的涂料组合物COA。这样的组合物仍可被称作涂料组合物。涂料组合物COA还可以包含一种或多种帮助成膜的有机溶剂、颜料(有机或无机的)和/或本领域已知的其它添加剂和填料。当使用有机溶剂时,优选水混溶性溶剂。应选择有机溶剂的量以提供具有低挥发有机含量(VOC)的涂料组合物,并优选包含小于50g/l、优选小于30g/l涂料组合物,包括挥发性有机化合物中的水,如通过ISO方法11890-2以备用形式计算。
根据一个实施方案,包含水性乙烯基聚合物分散体PD的涂料组合物COA可以进一步包含至少一种或多种选自下述的常规成分:颜料、染料、乳化剂、表面活性剂、增塑剂、增稠剂、热稳定剂、流平剂、防缩孔剂、填料、沉淀抑制剂、UV吸收剂、抗氧化剂、干燥盐、有机共溶剂、润湿剂等、或它们的混合物。
根据另一实施方案,涂料组合物COA还可以包含一种或多种的涂料添加剂,包括但不限于流平、流变学、抗粘连和流动控制剂例如硅氧烷、氟烃、氨基甲酸酯或纤维素,增量剂,消光剂,颜料润湿和分散剂以及表面活性剂,紫外(UV)吸收剂,UV光稳定剂,着色颜料,消泡剂和防泡剂,抗沉降、抗垂挂和增稠剂,防结皮剂,防浮色剂和防浮剂,杀真菌剂和防霉剂,腐蚀抑制剂,增稠剂,增塑剂,反应性增塑剂,干燥剂,催化剂,或聚结剂。本发明还涉及包含所述涂料组合物和1-70重量%的颜料或填料的漆组合物。优选地使用的颜料是金红石二氧化钛,最优选具有油吸收率小于25g油/100g的颜料,如通过ASTM D281-12(2016)测定。
本发明的涂料组合物COA还可以包含:最多20重量%、优选最多15、10或5的异氰酸酯交联剂,最多20重量%、优选最多5重量%的聚酰肼交联剂,最多10重量%的硅烷交联剂,最多10%的(甲基)丙烯酰低聚物。
如之前提到的,本发明的涂料组合物适合于各种涂料用途,例如作为漆,浸渍、密封和粘结组合物。优选的应用是作为底漆、面涂层或透明涂层。涂料组合物可以任何方便的方式例如通过刷涂、喷涂或浸渍来施涂至基材。合适的基材包括金属、木材、纸板、塑料和皮革。
本发明还涉及制备涂料组合物COA的方法,其包括共混水性乙烯基聚合物分散体PD与至少一种或多种常规成分的步骤,所述常规成分选自颜料、染料、乳化剂、表面活性剂、增塑剂、增稠剂、热稳定剂、流平剂、防缩孔剂、填料、沉淀抑制剂、UV吸收剂、抗氧化剂、干燥盐、有机共溶剂、润湿剂等、或它们的混合物。
优选地涂料组合物COA是水性涂料组合物。
本发明还涉及包含涂料组合物COA或包含乙烯基聚合物分散体PD的漆配制剂。根据一个实施方案,漆配制剂优选是着色配制剂。
本发明还涉及水性乙烯基聚合物分散体PD用来提高涂料组合物的开放时间、湿边时间和/或硬度的用途。
本发明还涉及用涂料组合物COA或用漆配制剂涂覆的制品。
将通过以下非限制性实施例更详细地解释本发明。
可以合理合并所有之前描述的实施方案。
实施例
测试方法
通过在锡制杯中称重1g的分散体并将杯放入125℃下空气循环烘箱60分钟来测量固体含量(SC)。重量差涉及挥发性含量且剩余非挥发部分是固体含量。如果粘度高,在加热之前添加1g的水。如果聚合物含有共溶剂,描述的方法没有提供正确的固体含量值。因此使用理论固体含量。
使用尺寸排阻色谱法(SEC)来测定分子量和分子量分布。使用的SEC设备是由泵、自动送样机和He-脱气器(来自Uniflows的Degasys DG-1210)组成的Alliance系统,配备有PLgel 5μm混合-C 600x7.5mm柱和PLgel 5μm保护柱(50×7.5mm–Polymer Laboratories)。柱烘箱(Separations Analytical Instruments)5设置在30℃。将0.8ml/min流速的四氢呋喃(THF-Extra Dry,Biosolve 206347)+2%乙酸(Baker 6052)用作洗脱剂。二硫化碳(Backer)用作标记物。Waters 410折射率用作检测器。注入体积为100μl,浓度为1.5mg/ml。使用三阶多项式,采用聚(苯乙烯)标准物(Polymer Laboratories,Easical PS-1,2010-0501(M为580-8,500,000g/mol)和Easical PS-2,2010-0601(M为580-400,000g/mol))用于校准。用于数据分析的软件是Empower(Waters)。为了分析聚合物P2的分子量,洗脱剂被六氟异丙醇取代和聚(苯乙烯)标准物被聚(甲基丙烯酸甲酯)标准物取代。
Brookfield粘度使用Brookfield RVT粘度计在23±1℃的温度下根据ISO 2555-1974测量。
粒度通过动态光散射使用Malvern Zetasizer型号Nano–S90测定。Z均值报道为粒度。z均直径是平均流体动力学直径并根据动态光散射的国际标准ISO13321计算。
早期耐水性(EWR)通过在Leneta平面图表上施涂80μm湿膜来测量。在23℃下45-55%相对湿度下干燥24小时之后将水滴置于漆表面并静置0.5小时、1小时和2小时。在这时间之后用布去除水。直接和在24小时恢复之后,判断气泡形式的损伤。报道的EWR是1小时水接触和24小时恢复之一。使用1(完全去除或完全起泡)到5(无损坏)的等级。
漆的开放时间通过使用棒式施涂器以125微米在23℃和45-55%相对湿度的适用条件下将它施涂至Leneta平面图表FORM WH上来测定。水性漆的蒸发速度为22mg/m2/s。使用具有至少2mm宽度的铅笔橡皮擦,在施涂之后立即将X形十字施加至漆层中。用刷(Elmaacryl 93-14或Pro-Gold Exclusive 7200-12)负载新漆并通过沿罐的边缘刮去过量的漆。将新负载的刷在X形十字的位置在基材宽度的垂直方向上移动两次,并在基材长度的水平方向上移动两次。在相同十字上重复这个移动十次(“10次交叉刷”)。在下一个十字上在一或两分钟间隔后重复这个工序,直至十字即使在10次“交叉刷”后仍保持可见(一次移动=在基材宽度的方向上两次和在基材长度的方向上两次)。开放时间报告为其中在接下来的1或2分钟间隔内在10次“交叉刷”之后可完全去除新施涂膜中的X形十字损伤的时间。可以选择2分钟间隔来得到开放时间的第一表示;更精确的开放时间测量之后是1分钟间隔。
早期抗粘连性通过以150μm湿层厚度将涂料施涂在测试图表上来测量。在室温下干燥涂层24小时。在50℃的温度下使用1kg/cm2的压力根据ASTM D4946-89测试粘连4小时。
实施例1:借助于乳液聚合制备乙烯基聚合物P1的水性分散体
在配备有冷却器、搅拌器、单体进料加入罐和引发剂加入罐的乳液聚合反应器中,如下制备预乳液:添加454g的水和5g的阴离子可聚合的表面活性剂(SR-1025)并加热至70℃。在进料罐中混合117g的水、22.8g的阴离子可聚合的表面活性剂SR-1025(得自Adeka Corporation)和0.3g的月桂基硫酸钠的混合物5分钟。通过在进料罐中添加以下原材料来制备单体预乳液:109.5g的甲基丙烯酸甲酯、24.2g的ETMA(甲基丙烯酸乙基三甘醇酯,Rohm GmbH)、24.2g的的甲基丙烯酸、145.7g的甲基丙烯酸正丁酯、3.56辛硫醇和1.75g的2-巯基乙醇。搅拌进料罐的内容物直至获得稳定的预乳液。
将5重量%的预乳液计量加入反应器。将反应器加热至80℃。当达到这个温度时,将0.3g的过硫酸铵在6.3g的水中的溶液加入反应器。在等待5分钟之后,将反应器加热至85℃。开始将预乳化的单体加入反应器。同时,开始加入由0.75g的过硫酸铵在15.2g的水中组成的引发剂溶液。在60分钟内完成单体进料计量加入。引发剂进料计量加入花费70分钟。进行以下整理步骤:用21.0g的水漂洗进料罐和用6.7g的水漂洗引发剂罐。在完成加料之后维持温度另外60分钟。将该批料冷却至65℃,并加入与0.75g的叔丁基氢过氧化物(70重量%水溶液)混合的4.0g的水的浆料。在15分钟时间段内将16.0g的水和0.35g的甲醛次硫酸氢钠的溶液计量加入反应器。将反应器的内容物保持在65℃的温度下另外30分钟。在这之后将反应器冷却至25℃。在25℃的温度下,添加3.1g的AQ(苯并异噻唑酮的10%溶液,得自Lonza)在4.0g的水中的溶液,用4.0g的水漂洗烧杯。将1.65g的25重量%氨溶液在4.0g的水中的溶液加入反应器。用4.0g的水漂洗烧杯。获得具有以下性能的具有环氧乙烯和羧酸官能团的水性乙烯基聚合物分散体:SC=32%,pH=7.5,残余单体<100ppm,粒度=122nm。分子量测量为Mn=5,000和Mw=13,200。
实施例2:制备乙烯基聚合物P2的水溶液
在聚合反应器中加入930.80g的甲乙酮并加热以回流(86℃)。然后在3小时的时间段内与1438.00g的(N)-乙烯基吡咯烷酮和359.30g的丙烯酸乙酯同时将31.90g的甲乙酮和3.20g的引发剂AMBN(2,2'-偶氮双(2-甲基丁腈),得自Nouryon)的混合物加入反应器。将反应器保持在回流温度下进行30分钟后反应。将反应器冷却至75℃并添加1237g的软化水。开始甲乙酮蒸馏直至残余的甲乙酮<0.1%。最后,加入额外的水以达到50%理论固体含量。所得的第二聚合物是具有轻微雾度的清澈溶液并具有49.7%的固体含量。它具有51,300g/mol的重均分子量和12,600g/mol的数均分子量。
实施例3:制备聚合物P3的水性分散体
初始步骤是合成乙烯基低聚物OL:在7升反应器中填充3,089g的软化水和35.44g的SR-1025。加热反应器内容物至80℃,同时在反应器中产生氮气氛。在整个聚合过程中维持氮气氛。通过将99.21g的SR-1020溶解在779.8g的软化水中制备预乳液。在搅拌下向此加入1,297g的甲基丙烯酸甲酯、231g的二丙酮丙烯酰胺、164.5g的甲基丙烯酸、294.7g的甲基丙烯酸正丁酯、22.1g的正辛硫醇和11.34g的2-巯基乙醇。
将这种预乳液的5%加入反应器。当温度达到80℃时,将溶解在85.03g的软化水中的1.754g的过硫酸铵加入反应器。将温度提高至85℃并在60分钟的时间段内计量加入剩余的预乳液。用177.2g的软化水漂洗容纳预乳液的烧杯。用42.51g的水漂洗引发剂溶液的烧杯。将该批料保持在85℃下30分钟,这之后在30分钟的时间段内添加溶解在255.3g水中的124.8g的氨(25%浓度)。溶液的pH为8.2。将该批料保持在85℃下另外120分钟。在这个保持时间段之后,将反应器的内容物冷却至室温。将产物通过过滤袋过滤并储存在聚乙烯接收器中。分析显示可交联的低聚物具有7,000g/mol的数均分子量和16,500g/mol的重均分子量。
在第二步骤中在存在以上描述的乙烯基低聚物的情况下制备乙烯基聚合物P4。在7升反应器中填充4.549g的来自初始步骤的低聚物溶液并在搅拌下在氮气氛下加热至45℃。制备由391.3g的甲基丙烯酸甲酯、933.3g的丙烯酸正丁酯、20.71g的二乙烯基苯和43.58g的苯乙烯组成的单体混合物。将该混合物的50%加入反应器。在混合30分钟之后,添加0.59g的叔丁基氢过氧化物(70%水溶液),之后50%的0.0382g的七水硫酸铁(II)、0.0478g的二水合乙二胺四乙酸二钠在58.16g的软化水中的溶液。制备2.533g的FF6M(得自L.Brüggemann GmbH&Co.KG)在290.5g的软化水中的溶液并将43.95g的该溶液加入反应器。将该批料升温至54.9℃并保持在55℃下45分钟。在保持时间段后,将反应器冷却至50℃并添加剩余单体。将该批料保持在50℃下30分钟。用316.4g的软化水漂洗容纳单体混合物的烧杯并将这加入反应器。将2.46g的叔丁基氢过氧化物(70%水溶液)和剩余的七水硫酸铁(II)/乙二胺二钠溶液加入反应器,之后43.95g的FF6M溶液。批料放热从而提高温度至60℃。在15分钟之后,在30分钟的时间段内将剩余的FF6M溶液计量加入反应器。通过加料漏斗添加64.63g的己二酰肼。用316.4g的软化水漂洗漏斗。将批料冷却降至环境温度。向反应器中添加21.31g的AQ,之后用21.78g的软化水漂洗。将批料通过过滤袋过滤并储存在合适的接收器中。分散体具有39.8%的固体含量、8.1的pH、198cPa.s的Brookfield粘度和49nm的粒度。MFFT为17℃。
实施例4和5(对照):水性涂料组合物
使用来自表1的成分制备白色涂料配制剂。
在室温下在冷却容器中制备漆浆。在配备具有溶解叶片的搅拌设备的容器中装入软化水、消泡剂、分散剂和表面活性剂。随后在高速搅拌(2,000-3,000rpm,50mm盘大小,容器直径80mm)下缓慢添加二氧化钛。在添加之后继续搅拌30分钟。研磨细度低于10μm。
一旦制备了漆浆,则在搅拌(1,000-1,500rpm,80mm盘大小,容器直径150mm)下在预先装有包含粘结剂的涂料组合物的调漆容器中将它加入粘结剂(与本发明的组合物一起)。当准备好时,在搅拌下添加软化水、消泡剂、防滑剂、共溶剂、胺、抗微生物剂、增稠剂和共溶剂。
在一夜稳定化之后,添加额外的增稠剂直至ICI粘度为2.7-3.0泊(10,000sec-1)。第二天,将漆应用于所有测试。
表1:着色涂料(量以g为单位)
表2显示表1中举出的着色涂料配制剂的性能。
表2:漆的性能
从表2可清楚地看出,本发明的涂料组合物在施涂第二涂层期间具有优异的开放时间而没有损害其它涂料性能。
Claims (16)
1.一种水性乙烯基聚合物分散体PD,其包含:
1)可通过单体混合物的自由基乳液聚合获得的乙烯基聚合物P1的水性分散体,所述单体混合物包括:
a)5-20重量%的酸官能的烯属不饱和单体M1或其前体;
b)5-25重量%的含有聚氧乙烯或单烷氧基聚氧乙烯部分的烯属不饱和单体M2;
c)最多90重量%的不同于M1或M2的非离子烯属不饱和单体M3;
d)0-10重量%的具有在成膜后交联的官能团的烯属不饱和单体M4;
e)0-10重量%的至少一种链转移剂CTA;
其中M1+M2+M3+M4+CTA的重量%之和=100重量%;
2)可通过以下物质的自由基共聚合获得的乙烯基聚合物P2的水性分散体或溶液:
a)25-95重量%的选自具有以下一般结构的N-乙烯基酰胺的烯属不饱和单体M5:
其中R1和R2是C1-C5烷基且可连接形成环结构,优选N-乙烯基吡咯烷酮或N-乙烯基己内酰胺;
b)5-75重量%的不同于M5的非离子烯属不饱和单体M3′;
c)0-5重量%的具有在成膜后交联的官能团的烯属不饱和单体M4′;
d)0-10重量%的酸官能的烯属不饱和单体M1′或其前体;
e)0-5重量%的至少一种链转移剂CTA′;
其中M5+M3′+M4′+M1′+CTA′的重量%之和=100重量%;
3)水性分散体形式的成膜性乙烯基聚合物P3,其包含:
i)20-60重量%的通过乳液聚合单体混合物获得的水溶性或水分散性可交联的乙烯基低聚物OL,所述单体混合物包括:
1)至少一种酸官能的烯属不饱和单体M1”;
2)至少一种不同于M1”的具有在成膜后交联的官能团的烯属不饱和单体M4”;
3)至少一种不同于M1”和M2”的烯属不饱和单体M3”,和
5)任选地,至少一种链转移剂CTA”,和
ii)40-80重量%的高分子量乙烯基聚合物P4,其通过在水溶性或水分散性可交联的乙烯基低聚物OL的存在下乳液聚合单体混合物制备,所述单体混合物包括:
1)任选地,一种酸官能的烯属不饱和单体M1”’;
2)任选地,一种或多种不同于M1”’的具有在成膜后交联的官能团的烯属不饱和单体M4”’;
3)至少一种不同于M1”’和M2”’的烯属不饱和单体M3”’,和
4)任选地,一种或多种用于预交联的多官能的烯属不饱和单体M5’”,优选其量小于5重量%,
其中成膜性乙烯基聚合物P3的总重量=水溶性或水分散性可交联的乙烯基低聚物OL的重量%+高分子量乙烯基聚合物P4的重量%=i)+ii)=100重量%,和
其中水性乙烯基聚合物分散体PD中乙烯基聚合物的总重量=乙烯基聚合物P1的重量%+乙烯基聚合物P2的重量%+成膜性乙烯基聚合物P3的重量%=100重量%。
2.根据权利要求1所述的水性乙烯基聚合物分散体PD,其中乙烯基聚合物P1、P2与P3的重量比为(1:1:98)至(65:15:20)。
3.根据前述权利要求中任一项所述的水性乙烯基聚合物分散体PD,其中乙烯基聚合物P1具有:
2,000-120,000g/mol的数均分子量,通过尺寸排阻色谱法使用四氢呋喃和2%乙酸作为洗脱剂和使用聚苯乙烯标准物测定;
30-150mg KOH/g的酸值,通过ISO 3682测定;和
5-25重量%的选自以下的烯属不饱和单体M2:聚氧乙烯或单烷氧基聚氧乙烯(甲基)丙烯酸酯,相对于乙烯基聚合物P1的总重量。
4.根据前述权利要求中任一项所述的水性乙烯基聚合物分散体PD,其中乙烯基聚合物P2具有1,000-50,000g/mol的数均分子量Mn,通过凝胶渗透色谱法使用六氟异丙醇作为洗脱剂和使用聚甲基丙烯酸甲酯标准物用于校准曲线测定。
5.根据前述权利要求中任一项所述的水性乙烯基聚合物分散体PD,其中乙烯基聚合物P2包含至少80%的具有低于120℃的单体玻璃化转变温度Tg的单体M3′。
6.根据前述权利要求中任一项所述的水性乙烯基聚合物分散体PD,其中乙烯基聚合物P2是N-乙烯基吡咯烷酮和丙烯酸乙酯的共聚物或N-乙烯基己内酰胺和丙烯酸乙酯的共聚物。
7.根据前述权利要求中任一项所述的水性乙烯基聚合物分散体PD,其中水溶性或水分散性可交联的乙烯基低聚物OL具有至少45mg KOH/g的酸值。
8.根据前述权利要求中任一项所述的水性乙烯基聚合物分散体PD,其中水溶性或水分散性可交联的乙烯基低聚物OL具有500-50,000g/mol的数均分子量,通过尺寸排阻色谱法使用四氢呋喃和2%乙酸作为洗脱剂和使用聚苯乙烯标准物用于校准曲线测定。
9.根据前述权利要求中任一项所述的水性乙烯基聚合物分散体PD,其中水溶性或水分散性可交联的乙烯基低聚物OL优选具有10-150℃的玻璃化转变温度Tg。
10.根据前述权利要求中任一项所述的水性乙烯基聚合物分散体PD,其中高分子量乙烯基聚合物P4的玻璃化转变温度为-70℃至50℃且低于水溶性或水分散性可交联的乙烯基低聚物OL的玻璃化转变温度至少25℃。
11.根据前述权利要求中任一项所述的水性乙烯基聚合物分散体PD,其中高分子量乙烯基聚合物P4具有大于或等于60,000g/mol的数均分子量。
12.根据前述权利要求中任一项所述的水性乙烯基聚合物分散体PD,其中成膜性乙烯基聚合物P3为水性聚合物分散体的形式且包含20-60重量%的水溶性或水分散性可交联的乙烯基低聚物OL。
13.根据权利要求12所述的水性乙烯基聚合物分散体PD,其中乙烯基聚合物P3的水性分散体的固体含量为20-60重量%。
14.权利要求1-13中任一项所述的水性乙烯基聚合物分散体PD用于提高涂料组合物的开放时间、湿边时间和/或硬度的用途。
15.一种涂料组合物COA,其包含权利要求1-13中任一项所述的水性乙烯基聚合物分散体PD和一种或多种选自下述的常规成分:非乙烯基聚合物、颜料、染料、乳化剂、表面活性剂、增塑剂、增稠剂、热稳定剂、流平剂、防缩孔剂、填料、沉淀抑制剂、UV吸收剂、抗氧化剂、干燥盐、有机共溶剂、润湿剂、或它们的混合物。
16.一种制备权利要求15所述的涂料组合物COA的方法,其包括共混权利要求1-13中任一项所述的水性乙烯基聚合物分散体PD与一种或多种选自下述的常规成分:非乙烯基聚合物、颜料、染料、乳化剂、表面活性剂、增塑剂、增稠剂、热稳定剂、流平剂、防缩孔剂、填料、沉淀抑制剂、UV吸收剂、抗氧化剂、干燥盐、有机共溶剂、润湿剂、或它们的混合物。
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GB0025212D0 (en) * | 2000-10-14 | 2000-11-29 | Avecia Bv | Vinyl polymer compositions |
WO2012130817A1 (en) * | 2011-03-25 | 2012-10-04 | Nuplex Resins B.V. | Waterborne coating composition |
CN105916895A (zh) * | 2014-01-17 | 2016-08-31 | 树脂核动力工业有限公司 | 改善了开放时间的水性涂料组合物 |
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GB8323241D0 (en) | 1983-08-30 | 1983-09-28 | Ici Plc | Coating compositions |
US5270380A (en) | 1992-10-13 | 1993-12-14 | Rohm And Haas Company | Method for extending the open time of an aqueous coating composition |
DE10011643A1 (de) | 2000-03-10 | 2001-09-13 | Basf Ag | Wässrige Hochglanz-Dispersionsfarbe mit langer offener Zeit |
US6872789B2 (en) | 2001-11-07 | 2005-03-29 | Akzo Nobel N.V. | Cross-linkable polymer composition |
US20070043156A1 (en) | 2003-05-06 | 2007-02-22 | Nuplex Resines B.V. | Emulsion polymerization process, polymer dispersion and film-forming composition |
ES2559405T3 (es) * | 2011-04-11 | 2016-02-12 | Nuplex Resins B.V. | Procedimiento para preparar dispersiones acuosas de polímero de vinilo |
DK3580293T3 (da) * | 2017-02-08 | 2024-04-22 | Swimc Llc | Miljøvenlig vandig belægningssammensætning |
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2020
- 2020-04-09 EP EP20169053.4A patent/EP3892682A1/en not_active Withdrawn
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2021
- 2021-04-02 EP EP21716419.3A patent/EP4133010A1/en active Pending
- 2021-04-02 KR KR1020227038133A patent/KR20220166820A/ko unknown
- 2021-04-02 AU AU2021252096A patent/AU2021252096A1/en active Pending
- 2021-04-02 WO PCT/EP2021/058797 patent/WO2021204723A1/en unknown
- 2021-04-02 JP JP2022561992A patent/JP2023520805A/ja active Pending
- 2021-04-02 US US17/916,264 patent/US20230142644A1/en active Pending
- 2021-04-02 CN CN202180027188.7A patent/CN115485333A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0025212D0 (en) * | 2000-10-14 | 2000-11-29 | Avecia Bv | Vinyl polymer compositions |
WO2012130817A1 (en) * | 2011-03-25 | 2012-10-04 | Nuplex Resins B.V. | Waterborne coating composition |
CN105916895A (zh) * | 2014-01-17 | 2016-08-31 | 树脂核动力工业有限公司 | 改善了开放时间的水性涂料组合物 |
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KR20220166820A (ko) | 2022-12-19 |
EP4133010A1 (en) | 2023-02-15 |
EP3892682A1 (en) | 2021-10-13 |
US20230142644A1 (en) | 2023-05-11 |
AU2021252096A1 (en) | 2022-10-13 |
WO2021204723A1 (en) | 2021-10-14 |
JP2023520805A (ja) | 2023-05-19 |
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