CN109851706A - A kind of water-based acrylic resin and preparation method thereof of Visible Light Induced Photocatalytic formaldehyde - Google Patents
A kind of water-based acrylic resin and preparation method thereof of Visible Light Induced Photocatalytic formaldehyde Download PDFInfo
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- CN109851706A CN109851706A CN201811575321.9A CN201811575321A CN109851706A CN 109851706 A CN109851706 A CN 109851706A CN 201811575321 A CN201811575321 A CN 201811575321A CN 109851706 A CN109851706 A CN 109851706A
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- water
- visible light
- acrylic resin
- based acrylic
- light induced
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 99
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910001868 water Inorganic materials 0.000 title claims abstract description 75
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 53
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 53
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- -1 alkyl methacrylate Chemical compound 0.000 claims abstract description 25
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 12
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 5
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 28
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 239000000839 emulsion Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 235000019504 cigarettes Nutrition 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 238000002525 ultrasonication Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 claims description 3
- PRJNEUBECVAVAG-UHFFFAOYSA-N 1,3-bis(ethenyl)benzene Chemical group C=CC1=CC=CC(C=C)=C1 PRJNEUBECVAVAG-UHFFFAOYSA-N 0.000 claims description 2
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical group C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 claims description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 2
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims description 2
- 229960004756 ethanol Drugs 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims description 2
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims description 2
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims 2
- 229940077388 benzenesulfonate Drugs 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- 239000003086 colorant Substances 0.000 claims 1
- 229920000058 polyacrylate Polymers 0.000 claims 1
- 235000019394 potassium persulphate Nutrition 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 13
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 description 9
- 239000006210 lotion Substances 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000004816 latex Substances 0.000 description 8
- 229920000126 latex Polymers 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 235000011194 food seasoning agent Nutrition 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000003183 carcinogenic agent Substances 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 231100000357 carcinogen Toxicity 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000013618 yogurt Nutrition 0.000 description 2
- 239000004908 Emulsion polymer Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 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 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
The present invention discloses a kind of water-based acrylic resin of Visible Light Induced Photocatalytic formaldehyde, is mainly made of alkyl methacrylate, alkyl acrylate, alkyl carboxylic acid, crosslinking agent, visible light catalyst, initiator, emulsifier.Invention additionally discloses a kind of preparation methods of the water-based acrylic resin of Visible Light Induced Photocatalytic formaldehyde.The beneficial effects of the present invention are: showing good film forming and water resistance；Physical-chemical performance, mechanical performance and the cementability of polymer have all obtained good improvement；Under the premise of not changing water-based acrylic resin various aspects of performance, make TiO2 that energy level transition catalysis oxidation can occur under visible light photograph and goes out hydroxyl group anion and superoxide anion, achieve the purpose that fixed and/or remove formaldehyde 0, and can be widely applied to the every field of coatings industry.
Description
Technical field
The present invention relates to water-based acrylic resin field, specially a kind of water-based acrylic resin of Visible Light Induced Photocatalytic formaldehyde
And preparation method thereof.
Background technique
Formaldehyde is a kind of volatile colourless gas, has special penetrating odor, can all generate to human eye, nose etc. strong
Stimulation is paid high attention to by national health tissue or even International Health Organization.International cancer research institution (IARC) is true by formaldehyde
It is set to 1 class carcinogenic substance；Formaldehyde is risen to 1 class by 2 class carcinogens by international cancer research institution, the World Health Organization (IARC)
Carcinogen.For formaldehyde to many hazards of human body, many documents propose the method for removing formaldehyde at present.It is big according to mechanism
Cause can be divided into three categories, first is that physical absorption, rely primarily on adsorbent for free formaldehyde storage, fixed, the method is easy to operate,
It is at low cost, but time longer the problem of there may be desorptions；Second is that catalysis oxidation, oxidizes the formaldehyde into harmless CO2And H2O,
The method is easy to operate, effect is preferable, but there are higher cost, condition is harsh the problems such as, it usually needs ultraviolet light, institute
Not to be widely adopted；Third is that chemical reaction, is reacted using the characteristic of carbonyl on formaldehyde or α-H, to remove free
Formaldehyde, the method removal effect of formaldehyde is best and secondary emission is not present, and is relatively easily applied to textile and except aldehyde spray agent etc.
Aspect, but since functional monomer can react with coating additive, coating property is influenced, so less be applied to coating
Aspect.
Summary of the invention
The purpose of the present invention is directed to existing deficiency during degradation of formaldehyde described above, provides a kind of Visible Light Induced Photocatalytic first
The water-based acrylic resin of aldehyde is relatively stable functional resin, while introducing has the function of internally plasticized cross-linking type list
Body and under visible light conditions degradation of formaldehyde visible light catalyst, and lotion obtained has good film forming and water-fast
Property, the fine and close hardness that forms a film is high, can be used for preparing the preparation of the water-borne acrylic coatings of Visible Light Induced Photocatalytic formaldehyde and is able to satisfy people
Requirement to functional coating.
In order to achieve the above objectives, the present invention is implemented as follows: a kind of water-based acrylic resin of Visible Light Induced Photocatalytic formaldehyde,
It is made of the component of following mass percent:
The alkyl methacrylate is methyl methacrylate, ethyl methacrylate, propyl methacrylate, first
1 kind or 2 kinds in base butyl acrylate, pentylmethacrylate, hexyl methacrylate and/or isooctyl methacrylate with
Upper combination.
The alkyl acrylate is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid
One kind or two or more combination in pentyl ester, Hexyl 2-propenoate and/or Isooctyl acrylate monomer.
The alkyl carboxylic acid is methacrylic acid and/or acrylic acid.
The crosslinking agent is adjacent divinylbenzene, m-divinyl benzene or p-divinyl benzene.
The visible light catalyst is titanium dioxide (TiO2), titanium dioxide/manganese dioxide (TiO2/MnO2), titanium dioxide
Titanium/silica (TiO2/SiO2) or Er titanium oxide/?phosphorus (TiO2/ BP) it one or two kinds of above combines.
The initiator is persulfuric acid salt initiator potassium persulfate, sodium peroxydisulfate and/or ammonium persulfate.
The emulsifier is dodecly diphenyl ether sulfonate disodium, neopelex and/or dodecyl sulphate
The anion emulsifiers such as sodium.
The steps included are as follows for the preparation method of the water-based acrylic resin of the Visible Light Induced Photocatalytic formaldehyde:
(1) alkyl methacrylate, alkyl acrylate, alkyl carboxylic acid, crosslinking agent, visible light are weighed by said ratio
Mix monomer is made after catalyst mixing；Then the initiator for accounting for initiator gross mass 40%~50% and the total matter of emulsifier will be accounted for
The emulsifier of amount 40%~60%, which is dissolved in the water for accounting for water gross mass 20%~40%, is made the first solution；
(2) it is added in reaction kettle, is dispersed with stirring 10~20 minutes by remaining water, emulsifier and with initiator, to
Temperature rises to 78~85 DEG C, by the mix monomer of 5%~15% mass in 15~30 minutes instillation reaction kettles, after being added dropwise
Seed emulsion is made in heat preservation 15~30 minutes；
(3) in 1.5~2 hours, remaining 85%~95% mix monomer and the first solution are added drop-wise to step simultaneously
Suddenly it in the seed emulsion that (2) obtain, is reacted 30~60 minutes under the conditions of 78~85 DEG C after being added dropwise；It and then will reaction temperature
Degree is increased to 85~90 DEG C, keeps the temperature 0.5~1 hour, is then cooled to 40~50 DEG C, filtering and discharging is to get Visible Light Induced Photocatalytic first
The water-based acrylic resin of aldehyde.
The steps included are as follows for the preparation method of the visible light catalyst: (1) accurate measuring 20~28 volume parts
Dehydrated alcohol is added in container；Then under rapid stirring, the titanium tetrachloride of 2~8 volume parts is added to above-mentioned
In dehydrated alcohol, transparent yellow mixed liquor is obtained；It stirs to the benzene first for when not having white cigarette, adding 60~120 volume parts
Alcohol is warming up to 78~82 DEG C, reacts 7.8~9.5 hours, mixed liquor color becomes micro- opaque；350 are added after being cooled to room temperature
~420 volume parts anhydrous ethers, stand overnight, and supernatant is outwelled after layering, and centrifugation obtains nano-titanium dioxide precipitating, precipitating
It is washed with dehydrated alcohol and obtains nano-titanium dioxide three times；(2) by BP (black phosphorus) and/or MnO2And/or SiO2It is carried out by ultrasound
Removing 3~6 hours；It is small that continuation ultrasonication 2~3 in (2) solution then is added in nano-titanium dioxide obtained in (1)
When to get arrive functional monomer；
Polymer glass temperature Tg is -10~10 DEG C.
The present invention by BP (?phosphorus) and/or MnO2And/or SiO2Removing dispersion is carried out in the water of deoxygenation, and system is then added
Standby nano-TiO2And homogeneous blend is carried out with ultrasound, surface is made and has TiO2Visible light catalyst；Finally using cream in situ
Liquid polymerization has TiO with surface2Visible light catalyst as seed, introduce surfactant and function monomer, preparation can
See the water-based acrylic resin of formaldehyde degradation by photocatalytic oxidation process.In the water-based acrylic resin of above-mentioned preparation, BP and/or MnO is introduced2
And/or SiO2With TiO2It is compound, TiO is changed with this2Only under ultraviolet irradiation condition could by the limitation of catalysis oxidation, make its
The purpose of degradation of formaldehyde can be had reached by catalysis oxidation under visible illumination level.In view of its good effect and simply
Manufacture craft, it is prepared by the present invention that light degradation formaldehyde water-based acrylic resin can will be widely used in functional paint neck
Domain, and have important economic significance and social effect to the development of functional coating.
Compared with prior art, the present invention has following prominent effect:
1) emulsion polymerization is used, reaction process is easily controllable, and water-based acrylic resin molecular weight obtained is high, viscous
Degree is big, shows good film forming and water resistance；
2) introducing crosslinked monomer, obtained lotion filming performance under room temperature and low temperature is all fine, while the object of polymer
Reason-chemical property, mechanical performance and cementability have all obtained good improvement；
3) resin introduces BP, changes TiO2Only under the conditions of UV Light could catalysis oxidation limitation, not
Under the premise of changing water-based acrylic resin various aspects of performance, make TiO2Energy level transition catalysis oxygen can occur under visible light photograph
Hydroxyl group anion and superoxide anion are dissolved, achieve the purpose that fixed and/or removes formaldehyde, and can be widely applied to coating work
The every field of industry.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below, it should be noted that embodiment is not constituted
Limitation to the claimed scope of the invention.
The water-based acrylic resin of visible light photocatalytic degradation formaldehyde prepared by the present invention can be characterized with the following method: lotion
Particle size it is different and distribution use the automatic particle size analyzer determination of Autosizer Lo-c；The chemical structure of emulsion polymer is used
FTIR measurement；Glass Transition Temperature of Latex Tg is analyzed with differential scanning calorimeter (DSC)；Minimum film formation temperature minimum film formation temperature
Instrument measurement；The latex particle form of lotion is analyzed with transmission electron microscope (TEM)；The film forming situation of lotion scanning electron microscope (SEM) and
Atomic Mechanics microscope (AFM) analysis.
The water-based acrylic resin of Visible Light Induced Photocatalytic formaldehyde of the present invention, is made of the component of following mass percent:
Wherein, the steps included are as follows for the preparation method of the visible light catalyst: (1) 20~28mL of accurate measuring is anhydrous
Ethyl alcohol is added in 250mL three neck round bottom flask, and flask is fixed with iron stand and is placed in room temperature water-bath；Then quick
Under conditions of stirring (revolving speed 500-1000rmp), 2~8mL titanium tetrachloride is slowly added to above-mentioned dehydrated alcohol with syringe
In, obtain transparent yellow mixed liquor；Stirring adds 60~120mL benzyl alcohol, is warming up to 78~82 to when not having white cigarette
DEG C, it reacts 7.8~9.5 hours, mixed liquor color becomes micro- opaque；It is transferred to 800mL beaker, is added after being cooled to room temperature
350~420mL anhydrous ether, stands overnight, and supernatant is outwelled after layering, and centrifugation obtains nano-titanium dioxide precipitating, and precipitating is used
Dehydrated alcohol washing obtains nano-titanium dioxide three times；(2) by BP (black phosphorus) and/or MnO2And/or SiO2It is shelled by ultrasound
From 3~6 hours；Then nano-titanium dioxide obtained in (1) is added in (2) solution and is continued ultrasonication 2~3 hours,
Obtain functional monomer.
Embodiment 1:
A kind of water-based acrylic resin of Visible Light Induced Photocatalytic formaldehyde is by including methyl methacrylate, butyl acrylate, first
Base acrylic acid, divinylbenzene Yi Ji ?P Modification nano-titanium dioxide be made, concrete component formula it is as follows:
The preparation method of the water-based acrylic resin of the Visible Light Induced Photocatalytic formaldehyde, its step are as follows:
A, ?P Modification nano-titanium dioxide preparation；By the nano-titanium dioxide prepared and removing ?phosphorus be mixed
Visible light catalyst；
B, methyl methacrylate, butyl acrylate, methacrylic acid, divinyl are weighed by above-mentioned mass percent proportion
Base Ben, ?P Modification nano-titanium dioxide be mixed and made into mix monomer；Then it the initiator for accounting for initiator quality 41% and will account for
The emulsifier of emulsifier gross mass 41%, which is dissolved in the water deionized water for account for water gross mass 21%, is made the first solution.According to FOX
Formula, wherein mix monomer forms Tg=8 DEG C of copolymer；
C, it prepares seed emulsion: the water of water gross mass 79% will be accounted for, account for the emulsifier of total emulsifiers quality 59% and account for and draw
The initiator of hair agent quality 59% is added in reaction kettle, is dispersed with stirring 11 minutes, is risen to 79 DEG C to temperature, by 6% mass
Mix monomer keeps the temperature 16 minutes after being added dropwise in 16 minutes instillation reaction kettles, and seed emulsion is made；
D, in 1.6 hours, remaining 94% mix monomer, the first solution are added drop-wise to the kind that step c is obtained simultaneously
In sub- lotion, reacted 31 minutes under the conditions of 79 DEG C after being added dropwise；And then reaction temperature is increased to 86 DEG C, heat preservation 0.6
Hour, be then cooled to 41 DEG C, filtering and discharging to get Visible Light Induced Photocatalytic formaldehyde water-based acrylic resin.
It is detected, the average grain diameter of the water-based acrylic resin for the Visible Light Induced Photocatalytic formaldehyde tested is 62nm；TEM points
Analysis shows the latex particle of resin at of uniform size spherical；SEM and Atomic Mechanics microscope (AFM) are analysis shows aqueous acrylamide
Yogurt glue film has good filming performance, and without phenomenon of phase separation；The minimum film formation temperature of water-based acrylic resin is 2
℃；Nuclear magnetic resonance (NMR) is analysis shows the composition of aqueous acrylamide ester resin obtained is in gradually change from micelle center to surface.
It is formed a film using seasoning and measures solid content, be closer to theoretical value, up to 41.8%, and visible light obtained is urged
Change degradation of formaldehyde water-based acrylic resin and aldehyde performance is removed using the test of climate box method, obtains preferable effect.It will be obtained aqueous
Acrylic resin film forming places to impregnate in deionized water tests its water resistance for 24 hours, and water absorption rate is only 1.2%.
Embodiment 2
A kind of water-based acrylic resin of Visible Light Induced Photocatalytic formaldehyde, by including methyl methacrylate, butyl acrylate, third
Olefin(e) acid, divinylbenzene Yi Ji ?P Modification nano-titanium dioxide be made, concrete component formula it is as follows:
The preparation method of the water-based acrylic resin of the Visible Light Induced Photocatalytic formaldehyde, its step are as follows:
A, ?P Modification nano-titanium dioxide preparation: the BP of the nano-titanium dioxide prepared and removing is mixed
Visible light catalyst；
B, methyl methacrylate, butyl acrylate, acrylic acid, divinyl are weighed by above-mentioned mass percent proportion
Ben, ?P Modification nano-titanium dioxide be mixed and made into mix monomer；Then the initiator for accounting for initiator quality 49% and cream will be accounted for
The emulsifier of agent gross mass 59%, which is dissolved in the water deionized water for account for water gross mass 39%, is made the first solution.According to FOX public affairs
Formula, wherein mix monomer forms Tg=10 DEG C of copolymer；
C, it prepares seed emulsion: the water of water gross mass 61% will be accounted for, account for the emulsifier of total emulsifiers quality 41% and account for and draw
The initiator of hair agent quality 51% is added in reaction kettle, is dispersed with stirring 19 minutes, is risen to 84 DEG C to temperature, by 14% mass
Mix monomer keeps the temperature 29 minutes after being added dropwise in 29 minutes instillation reaction kettles, and seed emulsion is made；
D, in 1.9 hours, remaining 86% mix monomer and the first solution are added drop-wise to the kind that step b is obtained simultaneously
In sub- lotion, reacted 59 minutes under the conditions of 84 DEG C after being added dropwise；And then reaction temperature is increased to 89 DEG C, heat preservation 0.91
Hour, be then cooled to 49 DEG C, filtering and discharging to get Visible Light Induced Photocatalytic formaldehyde water-based acrylic resin.
It is detected, the average grain diameter of the water-based acrylic resin for the Visible Light Induced Photocatalytic formaldehyde tested is 58nm；TEM points
Analysis shows the latex particle of resin at of uniform size spherical；SEM and Atomic Mechanics microscope (AFM) are analysis shows aqueous acrylamide
Yogurt glue film has good filming performance, and without phenomenon of phase separation；The minimum film formation temperature of water-based acrylic resin is 4
℃；Nuclear magnetic resonance (NMR) is analysis shows the composition of aqueous acrylamide ester resin obtained is in gradually change from micelle center to surface.
It is formed a film using seasoning and measures solid content, be closer to theoretical value, up to 39.2%, and visible light obtained is urged
Change degradation of formaldehyde water-based acrylic resin and aldehyde performance is removed using the test of climate box method, obtains preferable effect.It will be obtained aqueous
Acrylic resin film forming places to impregnate in deionized water tests its water resistance for 24 hours, and water absorption rate is only 1.4%.
Embodiment 3
A kind of water-based acrylic resin of Visible Light Induced Photocatalytic formaldehyde, by including ethyl methacrylate, amyl acrylate, first
Base acrylic acid, divinylbenzene and silica modified nano titanium dioxide are made, and concrete component formula is as follows:
The preparation method of the water-based acrylic resin of the Visible Light Induced Photocatalytic formaldehyde, its step are as follows:
A, the preparation of silica modified nano titanium dioxide: by the nano-titanium dioxide prepared and nano silica
It is mixed and made into visible light catalyst；
B, weighed ethyl methacrylate, amyl acrylate, methacrylic acid, diethyl are matched by above-mentioned mass percent
Alkenyl benzene, silica modified nano titanium dioxide are mixed and made into mix monomer；Then the initiation of initiator quality 45% will be accounted for
Agent and the emulsifier for accounting for emulsifier gross mass 50%, which are dissolved in the water deionized water for account for water gross mass 30%, is made the first solution.It presses
According to FOX formula, wherein mix monomer forms copolymer
Tg=6 DEG C
C, it prepares seed emulsion: the water of water gross mass 70% will be accounted for, account for the emulsifier of total emulsifiers quality 50% and account for and draw
The initiator of hair agent quality 55% is added in reaction kettle, is dispersed with stirring 15 minutes, is risen to 80 DEG C to temperature, by 10% mass
Mix monomer keeps the temperature 20 minutes after being added dropwise in 20 minutes instillation reaction kettles, and seed emulsion is made；
D, in 1.8 hours, remaining 90% mix monomer and the first solution are added drop-wise to the kind that step b is obtained simultaneously
In sub- lotion, reacted 30~60 minutes under the conditions of 80 DEG C after being added dropwise；And then reaction temperature is increased to 88 DEG C, heat preservation
0.8 hour, be then cooled to 45 DEG C, filtering and discharging to get Visible Light Induced Photocatalytic formaldehyde water-based acrylic resin.
The average grain diameter for testing the water-based acrylic resin of obtained Visible Light Induced Photocatalytic formaldehyde is 75nm；Tem analysis shows
The latex particle of resin is at of uniform size spherical；SEM and Atomic Mechanics microscope (AFM) are analysis shows Aqueous acrylic latex
Film has good filming performance, and without phenomenon of phase separation；The minimum film formation temperature of water-based acrylic resin is 6.5 DEG C；Core
Magnetic resonance (NMR) is analysis shows the composition of aqueous acrylamide ester resin obtained is in gradually change from micelle center to surface.
Through detecting, is formed a film using seasoning and measure solid content, be closer to theoretical value, up to 37.5%, and obtained
Visible light photocatalytic degradation formaldehyde water-based acrylic resin removes aldehyde performance using the test of climate box method, obtains preferable effect.It will system
The water-based acrylic resin film forming obtained places to impregnate in deionized water tests its water resistance for 24 hours, and water absorption rate is only 1.35%.
Embodiment 4:
A kind of water-based acrylic resin of Visible Light Induced Photocatalytic formaldehyde, by different pungent including methyl methacrylate, acrylic acid
Ester, acrylic acid, divinylbenzene Yi Ji ?phosphorus and manganese dioxide modified nano-titanium dioxide be made, concrete component is formulated such as
Under:
The preparation method of the water-based acrylic resin of Visible Light Induced Photocatalytic formaldehyde, its step are as follows:
A, ?phosphorus and manganese dioxide modified nano-titanium dioxide preparation: by the nano-titanium dioxide He prepared ?phosphorus and
Manganese dioxide is mixed and made into visible light catalyst；
B, methyl methacrylate is weighed by above-mentioned mass percent proportion, Isooctyl acrylate monomer, acrylic acid, hand over divinyl
Base benzene, silica modified nano titanium dioxide are mixed and made into mix monomer；Then the initiator of initiator quality 45% will be accounted for
It is dissolved in the emulsifier for accounting for emulsifier gross mass 45% in the water deionized water for account for water gross mass 25% and the first solution is made.According to
FOX formula, wherein mix monomer I forms copolymer
Tg=8 DEG C；
C, it prepares seed emulsion: the water of water gross mass 75% will be accounted for, account for the emulsifier of total emulsifiers quality 55% and account for and draw
The initiator of hair agent quality 55% is added in reaction kettle, is dispersed with stirring 16 minutes, is risen to 82 DEG C to temperature, by 11% mass
Mix monomer keeps the temperature 25 minutes after being added dropwise in 25 minutes instillation reaction kettles, and seed emulsion is made；
D, in 2 hours, remaining 89% mix monomer and the first solution are added drop-wise to the seed that step b is obtained simultaneously
In lotion, reacted 40 minutes under the conditions of 82 DEG C after being added dropwise；And then reaction temperature is increased to 86 DEG C, keeps the temperature 1 hour,
Then be cooled to 45 DEG C, filtering and discharging to get Visible Light Induced Photocatalytic formaldehyde water-based acrylic resin.
The average grain diameter for testing the water-based acrylic resin of obtained Visible Light Induced Photocatalytic formaldehyde is 102nm；Tem analysis shows
The latex particle of resin is at of uniform size spherical；SEM and Atomic Mechanics microscope (AFM) are analysis shows Aqueous acrylic latex
Film has good filming performance, and without phenomenon of phase separation；The minimum film formation temperature of water-based acrylic resin is 7.5 DEG C；Core
Magnetic resonance (NMR) is analysis shows the composition of aqueous acrylamide ester resin obtained is in gradually change from micelle center to surface.
It is formed a film using seasoning and measures solid content, be closer to theoretical value, up to 41.2%, and visible light obtained is urged
Change degradation of formaldehyde water-based acrylic resin and aldehyde performance is removed using the test of climate box method, obtains preferable effect.It will be obtained aqueous
Acrylic resin film forming places to impregnate in deionized water tests its water resistance for 24 hours, and water absorption rate is only 2%.
Wherein, preferred the steps included are as follows for the preparation method of the visible light catalyst: (1) accurate measuring 25mL without
Water-ethanol is added in 250mL three neck round bottom flask, and flask is fixed with iron stand and is placed in room temperature water-bath；Then fast
Under conditions of speed stirring, 6mL titanium tetrachloride is slowly added into above-mentioned dehydrated alcohol with syringe, obtains transparent yellow mixing
Liquid；Stirring adds 90mL benzyl alcohol to when not having white cigarette, is warming up to 80 DEG C, reacts 8.5 hours, mixed liquor color becomes micro-
It is opaque；It is transferred to 800mL beaker, 400mL anhydrous ether is added after being cooled to room temperature, stands overnight, supernatant is outwelled after layering
Liquid, centrifugation obtain nano-titanium dioxide precipitating, and precipitating is washed with dehydrated alcohol and obtains nano-titanium dioxide three times；(2) BP is (black
Phosphorus) and/or MnO2 and/or SiO2 by ultrasound carry out removing 5 hours；Then nano-titanium dioxide obtained in (1) is added
(2) continue ultrasonication in solution 2.5 hours to get corresponding visible light catalyst is arrived.Wherein, the frequency of ultrasound removing is
45-55KHz, power are 450~700W, it is preferable that the frequency of ultrasound removing is 50KHz, power 55W, has highest efficiency,
And it is minimum to material lateral dimension extent of the destruction.
As described above, only presently preferred embodiments of the present invention, when cannot be limited the scope of implementation of the present invention with this,
I.e. generally according to simple equivalent changes and modifications made by scope of the present invention patent and invention description content, all still belong to the present invention
In the range of patent covers.
Claims (8)
1. a kind of water-based acrylic resin of Visible Light Induced Photocatalytic formaldehyde, which is characterized in that by the component system of following mass percent
At:
2. a kind of water-based acrylic resin of Visible Light Induced Photocatalytic formaldehyde according to claim 1, which is characterized in that the first
Base alkyl acrylate be methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate,
One kind or two or more combination in pentylmethacrylate, hexyl methacrylate and/or isooctyl methacrylate.
3. a kind of water-based acrylic resin of Visible Light Induced Photocatalytic formaldehyde according to claim 1, which is characterized in that described third
Olefin(e) acid Arrcostab is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, Hexyl 2-propenoate
And/or the one kind or two or more combination in Isooctyl acrylate monomer；The alkyl carboxylic acid is methacrylic acid and/or acrylic acid；Institute
Crosslinking agent is stated as adjacent divinylbenzene, m-divinyl benzene or p-divinyl benzene.
4. a kind of water-based acrylic resin of Visible Light Induced Photocatalytic formaldehyde according to claim 1, which is characterized in that it is described can
Light-exposed catalyst is titanium dioxide, titanium dioxide/manganese dioxide, titania/silica and/or titanium dioxide/black phosphorus one
Kind or two or more combinations.
5. a kind of water-based acrylic resin of Visible Light Induced Photocatalytic formaldehyde according to claim 1, which is characterized in that described to draw
Hair agent is potassium peroxydisulfate, sodium peroxydisulfate and/or ammonium persulfate；The emulsifier is dodecly diphenyl ether sulfonate disodium, 12
Sodium alkyl benzene sulfonate and/or dodecyl sulphate.
6. a kind of a kind of preparation side of the water-based acrylic resin of -5 any Visible Light Induced Photocatalytic formaldehyde according to claim 1
Method, which is characterized in that the steps included are as follows:
(1) alkyl methacrylate, alkyl acrylate, alkyl carboxylic acid, crosslinking agent, visible light catalytic are weighed by said ratio
Mix monomer is made after agent mixing；Then the initiator for accounting for initiator gross mass 40%~50% and emulsifier gross mass will be accounted for
40%~60% emulsifier, which is dissolved in the water for accounting for water gross mass 20%~40%, is made the first solution；
(2) it is added in reaction kettle, is dispersed with stirring 10~20 minutes, to temperature by remaining water, emulsifier and with initiator
78~85 DEG C are risen to, by the mix monomer of 5%~15% mass in 15~30 minutes instillation reaction kettles, is kept the temperature after being added dropwise
15~30 minutes, seed emulsion is made；
(3) in 1.5~2 hours, remaining 85%~95% mix monomer and the first solution are added drop-wise to step (2) simultaneously
In obtained seed emulsion, reacted 30~60 minutes under the conditions of 78~85 DEG C after being added dropwise；And then reaction temperature is mentioned
Height keeps the temperature 0.5~1 hour, is then cooled to 40~50 DEG C to 85~90 DEG C.
7. a kind of preparation method of the water-based acrylic resin of Visible Light Induced Photocatalytic formaldehyde according to claim 6, feature
Be, the steps included are as follows for the preparation method of the visible light catalyst: (1) 20~28 volume parts of accurate measuring is anhydrous
Ethyl alcohol is added in container；The titanium tetrachloride of 2~8 volume parts is then added into above-mentioned dehydrated alcohol, obtains transparent Huang
Mixture of colours liquid；Stirring adds the benzyl alcohol of 60~120 volume parts to when not having white cigarette, is warming up to 78~82 DEG C, reaction
7.8~9.5 hours, mixed liquor color became micro- opaque；350~420 volume parts anhydrous ethers are added after being cooled to room temperature,
It stands overnight, supernatant is outwelled after layering, centrifugation obtains nano-titanium dioxide precipitating, and precipitating is washed with dehydrated alcohol and obtained three times
Nano-titanium dioxide；(2) BP (black phosphorus) and/or MnO2 and/or SiO2 are subjected to removing 3~6 hours by ultrasound；Then will
(1) nano-titanium dioxide obtained in, which is added in (2) solution, to be continued ultrasonication 2~3 hours.
8. the preparation method of acrylate polymer emulsion according to claim 6, which is characterized in that the mix monomer
Glass transition temperature Tg is -10~10 DEG C.
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