CN109456452A - A kind of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion and preparation method thereof - Google Patents
A kind of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion and preparation method thereof Download PDFInfo
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- CN109456452A CN109456452A CN201811175032.XA CN201811175032A CN109456452A CN 109456452 A CN109456452 A CN 109456452A CN 201811175032 A CN201811175032 A CN 201811175032A CN 109456452 A CN109456452 A CN 109456452A
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- Prior art keywords
- ether ketone
- aryl ether
- poly
- preparation
- parts
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- 229920006260 polyaryletherketone Polymers 0.000 title claims abstract description 82
- 239000000839 emulsion Substances 0.000 title claims abstract description 63
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 40
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 40
- 239000011258 core-shell material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000004945 emulsification Methods 0.000 title claims description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 23
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 16
- 239000006210 lotion Substances 0.000 claims abstract description 11
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 10
- 150000002989 phenols Chemical class 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 230000032050 esterification Effects 0.000 claims abstract description 4
- 238000005886 esterification reaction Methods 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- 238000007789 sealing Methods 0.000 claims abstract description 3
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 42
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000000178 monomer Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 21
- 238000010792 warming Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 238000004321 preservation Methods 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 239000004971 Cross linker Substances 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- -1 acrylic ester Chemical class 0.000 claims description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 239000000872 buffer Substances 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 230000000977 initiatory effect Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000003643 water by type Substances 0.000 claims description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 4
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 4
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 4
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 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
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000003995 emulsifying agent Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- LJUBBYQPEAGIFB-UHFFFAOYSA-N 4-phthalazin-1-ylphenol Chemical compound OC1=CC=C(C=C1)C1=NN=CC2=CC=CC=C12 LJUBBYQPEAGIFB-UHFFFAOYSA-N 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- LLJNTLUXOZPFQB-UHFFFAOYSA-N [4-(4-fluorobenzoyl)phenyl]-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(C(=O)C=2C=CC(F)=CC=2)C=C1 LLJNTLUXOZPFQB-UHFFFAOYSA-N 0.000 claims description 3
- 125000005336 allyloxy group Chemical group 0.000 claims description 3
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical group CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical class C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims description 2
- NVDZKUSTRLIYSF-UHFFFAOYSA-N 4-cinnolin-4-yl-3-methylphenol Chemical compound CC1=C(C=CC(=C1)O)C2=CN=NC3=CC=CC=C32 NVDZKUSTRLIYSF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims 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 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- PISLKPDKKIDMQT-UHFFFAOYSA-N [3-(4-fluorobenzoyl)phenyl]-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=CC(C(=O)C=2C=CC(F)=CC=2)=C1 PISLKPDKKIDMQT-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- JPICKYUTICNNNJ-UHFFFAOYSA-N anthrarufin Chemical compound O=C1C2=C(O)C=CC=C2C(=O)C2=C1C=CC=C2O JPICKYUTICNNNJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims description 2
- 229940071161 dodecylbenzenesulfonate Drugs 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
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- IRZFQKXEKAODTJ-UHFFFAOYSA-M sodium;propan-2-yloxymethanedithioate Chemical compound [Na+].CC(C)OC([S-])=S IRZFQKXEKAODTJ-UHFFFAOYSA-M 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims 1
- CJSHOTIROCCXSP-UHFFFAOYSA-N C1(=CC=CC=C1)C=1C=C(C=CC1O)C1=NN=CC2=C1C=CC=C2 Chemical compound C1(=CC=CC=C1)C=1C=C(C=CC1O)C1=NN=CC2=C1C=CC=C2 CJSHOTIROCCXSP-UHFFFAOYSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 2
- 239000003973 paint Substances 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 125000005395 methacrylic acid group Chemical class 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 235000013618 yogurt Nutrition 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000006115 industrial coating Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 150000004351 1,5-dihydroxyanthraquinones Chemical class 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- PEYSOIUPGIDWCZ-UHFFFAOYSA-N OC(C1=C(C=CC=C2)C2=C(C(C=C2)=CC(C3=CC=CC=C3)=C2O)N=N1)=O Chemical compound OC(C1=C(C=CC=C2)C2=C(C(C=C2)=CC(C3=CC=CC=C3)=C2O)N=N1)=O PEYSOIUPGIDWCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000006332 fluoro benzoyl group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 229920000090 poly(aryl ether) Polymers 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000005199 trimethylbenzenes Chemical class 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C08F290/062—Polyethers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to a kind of poly(aryl ether ketone) modified core shell structural acrylic resin emulsions and preparation method thereof, pass through the ratio of control binary substituted phenol, two fluorinated aromatic hydrocarbons first, using the linear poly(aryl ether ketone) of the gradually low molecular weight of polymerization synthesis of hydroxy sealing end, then the linear poly(aryl ether ketone) of propylene acid blocked is obtained by esterification, then seeded emulsion polymerization is participated in by the linear poly(aryl ether ketone) of propylene acid blocked and prepares poly(aryl ether ketone) modified core shell structural acrylic resin emulsion.Lotion cured coating film made from the preparation method has the characteristics that chemical stability is good, hardness is high, mechanical property is excellent, relative to general emulsion polymerization, has the advantages that its viscosity is lower in identical mass fraction, lotion is more stable.
Description
Technical field
The present invention relates to a kind of water-base resin more particularly to a kind of poly(aryl ether ketone) modified core shell structural acrylic resin emulsions
And preparation method thereof, belong to environmental technology field.
Background technique
Coating Water-borne modification is the main flow direction of world's paint development.With industrialization, the continuous propulsion of urbanization process, people
Gradually recognize that economic development cannot start to pursue low pollution even free of contamination industrial development mould at the cost of the environment
Formula.To adapt to environmental protection and energy-efficient requirement, the environment protecting water-based paint for developing low VOC becomes the inexorable trend of coating industry development.
The development speed of domestic water paint is very fast in recent years, and especially industrial water paint demand is the most urgent.China's industry applies
The annual requirement of material is at 1,900,000 tons or so, wherein can possess huge potential with aqueous industrial coating substitution up to 1,200,000 tons
Market, it is contemplated that the development of water-based industrial paint will bring huge economic benefit and social benefit.
High-performance environmentally-friendly aqueous industrial coating is urgently developed in the industry, but in current domestic industrial field, since country is right
Paint environmental protection characteristic does not have special coercion policy, and the place used is also so high to environmental requirement unlike house decoration, therefore,
The fields overwhelming majority such as automobile coating, mechanized equipment paint, special anticorrosive paint, plastic paint, glass lacquer are also applied using traditional solvent type
Material.
CN201710517322.7 discloses a kind of preparation of metallic paint mesopore molecular sieve/aqueous polyurethane multiple emulsion
Method weighs 13~24 parts of oligomer dihydric alcohol, 12~22 parts of diisocyanate cpd, SBA-15 is situated between according to the mass fraction
0.05~0.5 part of porous molecular sieve, 3~10 parts of chain extender, 2~5 parts of salt forming agent and 40~60 parts of deionized water;By oligomer two
Diisocyanate cpd and SBA-15 mesopore molecular sieve are added after first alcohol vacuum dehydration, is warming up to 75~95 DEG C, reaction 2~
4h after chain extender, catalyst and organic solvent then is added, reacts 4~6h, then addition salts agent, ionized water at 58~80 DEG C
Emulsification, last vacuum removal organic solvent obtain metallic paint mesopore molecular sieve/aqueous polyurethane multiple emulsion.The invention institute
The multiple emulsion of preparation takes water as a solvent, can be extensive with big, heat-resist, non-toxic and tasteless, the environmentally protective advantage of cohesive force
Applied to aqueous metallic paint.But its hardness, wearability, high temperature resistance need to be improved.
Summary of the invention
It is in order to overcome the shortcomings of the prior art and insufficient, the present invention is intended to provide a kind of poly(aryl ether ketone) modified core shell structure propylene
Acid resin lotion and preparation method thereof.
The present invention takes following technical scheme, a kind of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion, feature
It is, linear poly(aryl ether ketone) branch is contained in molecular structure;The present invention has synthesized the polyarylether with propylene acid blocked first
Ketone, then poly(aryl ether ketone) participates in the seeding polymerization of acrylic emulsion, prepares core-shell structure emulsion acrylic resin.
A kind of preparation method of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion, includes the following steps:
The preparation of the linear poly(aryl ether ketone) of I, propylene acid blocked: the ratio by controlling binary substituted phenol, two fluorinated aromatic hydrocarbons,
Using the linear poly(aryl ether ketone) of the gradually low molecular weight of polymerization synthesis of hydroxy sealing end, propylene acid seal is then obtained by esterification
The linear poly(aryl ether ketone) at end;
The reaction of II, water soluble acrylic acid seeded emulsion polymerization: seed emulsion is participated in by the linear poly(aryl ether ketone) of propylene acid blocked
Polymerization preparation poly(aryl ether ketone) modified core shell structural acrylic resin emulsion.
Further, a kind of preparation method of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion, by weight
Number meter, includes the following steps:
The preparation of the linear poly(aryl ether ketone) of I, propylene acid blocked: under logical condition of nitrogen gas, equipped with division box, heating dress
It sets, 22-30 parts of binary substituted phenols, two fluorinated aromatic hydrocarbon of 9-13 part, 5-8 parts of weak base, 40-50 parts is added in the reactor of agitating device
Atent solvent is heated to 130-150 DEG C under stirring, and the water generated in dereaction, 130-150 DEG C of guarantor are constantly removed by division box
Temperature reaction 3-4h, is then warming up to 190-200 DEG C with the heating rate of 5 DEG C/h, then is down to 180 DEG C of heat preservation polymerization 6-8h;Then
It is cooled to 100-120 DEG C, 1-2 parts of acrylic acid, 2-3 parts of methacrylic acids are added, 180- is warming up to the heating rate of 10 DEG C/h
190 DEG C of reaction 5-8h remove atent solvent by vacuum distillation, obtain acrylic acid modified poly(aryl ether ketone);
The reaction of II, water soluble acrylic acid seeded emulsion polymerization:
A, the pre-emulsion stage: in four mouthfuls of reaction vessels for being furnished with speed-adjustable stir device, return pipe, dropping funel and thermometer
In, be added 30-40 parts of deionized waters, 2-4 parts of emulsifiers, 0.2-0.5 parts of acrylic acid, 3-5 parts of hard monomers, 4-6 parts of soft monomers,
0.5-1 parts of acrylic acid modified poly(aryl ether ketone), 0.2-1 parts of crosslinkers monomers, 1-2 portions of pH value buffers, in 1200-1500r/min
High-speed stirred is emulsified, obtains milky pre-emulsification mix monomer lotion;
B, milky pre-emulsification mix monomer lotion made from a stage seed emulsion stage: is heated to 75-90
DEG C, while revolving speed is turned down to 800-900r/min, 0.05-0.1 parts of initiator solution initiation reactions at 75-90 DEG C are added dropwise, out
Existing blue light heat preservation 1-2h is to get seed emulsion;
C, the emulsion polymerization stage: by 0.5-2 parts of acrylic acid, 12-15 parts of hard monomers, 15-25 parts of soft monomers, 8-12 parts of propylene
Sour modified polyarylether ketone, 1-2 parts of crosslinkers monomers, 0.2-0.5 parts of initiators, 20-35 parts of water reactions, are made dropping liquid;75-90
DEG C dropping liquid is slowly added dropwise into seed emulsion, is dripped off in 1-2h, 100-105 DEG C is warming up to after being added dropwise, heat preservation is anti-
Answer 0.5h;Add alkali regulation system pH value to be discharged after being cooled to room temperature to 8~9, be obtained by filtration solid content be 50% or so it is milky white
Color liquid, as poly(aryl ether ketone) modified core shell structural acrylic resin emulsion.
Binary substituted phenol in the step I, two fluorinated aromatic hydrocarbons, weak base, atent solvent, acrylic acid, methacrylic acid
Weight fraction ratio is (22-30): (9-13): (5-8): (40-50): (1-2): (2-3).
Acrylic acid, hard monomer, soft monomer, acrylic acid modified poly(aryl ether ketone), crosslinkers monomers, initiation in the step II
Agent, water weight fraction ratio be (0.5-2): (12-15): (15-25): (8-12): (1-2): (0.2-0.5): (20-35).
The binary substituted phenol is 1- hydroxyl -4- (4- hydroxy benzenes)-benzodiazine, 4,4' dihydroxy diphenyl, 4- (2-
Methyl -4- hydroxy phenyl) benzodiazine, 1,5- dihydroxy anthraquinone, 4- (3- phenyl -4- hydroxy phenyl) -2,3- benzodiazine -1-
At least one of ketone, 4- (4- hydroxy phenyl) -2,3- benzodiazine -1- ketone.
Two fluorinated aromatic hydrocarbons are 4,4 '-difluoro benzophenones, 1,4- bis--(4 '-fluoro benzoyl) benzene, bis- (4- of 1,3-
At least one of fluorobenzoyl) benzene.
The weak base is at least one of sodium carbonate, potassium carbonate.
The atent solvent is at least one of dimethylbenzene, trimethylbenzene, ethylbenzene, methyl-ethyl benzene, diethylbenzene.
The hard monomer is at least one of methyl methacrylate, styrene;The soft monomer is acrylic ester
The combination of one or more of butyl ester, ethyl acrylate, isobutyl acrylate, propylene ester methyl ester, butyl methacrylate.
The emulsifier is dodecyl benzene sulfonate, allyloxy fatty alcohol ethylene oxide ether sulfate, propylene
At least one of amide groups sodium isopropyl xanthate;The crosslinkers monomers are β-hydroxy-ethyl acrylate, Beta-methyl acrylic acid
The combination of one or more of hydroxypropyl acrylate, methacrylic acid amino.
The initiator be potassium peroxydisulfate, benzoyl peroxide, peroxidized t-butyl perbenzoate, azodiisobutyronitrile,
Azobisisoheptonitrile, perbenzoic acid, ammonium persulfate, at least one of.
A kind of water-base resin, using the preparation method system of above-mentioned poly(aryl ether ketone) modified core shell structural acrylic resin emulsion
Standby gained.
Compared with the existing technology, the present invention has the following advantages that or beneficial outcomes:
(1) hydroxy-end capped low using gradually having synthesized by the ratio of control binary substituted phenol, two fluorinated aromatic hydrocarbons
Then the linear poly(aryl ether ketone) of molecular weight obtains the linear poly(aryl ether ketone) of propylene acid blocked, propylene acid blocked by esterification
Linear poly(aryl ether ketone) participate in seeded emulsion polymerization prepare poly(aryl ether ketone) modified core shell structural acrylic resin emulsion, the lotion
Cured coating film protects the feature that the chemical stability having is good, hardness is high, mechanical property is excellent;
(2) on microcosmic, acrylic resin of the present invention has using poly(aryl ether ketone) as branch, using acrylic resin as the knot of main chain
Structure has when soft monomer additional amount is relatively small compared with high-flexibility, and glass transition temperature is not high;
(3) present invention is core-shell structure emulsion acrylic resin, relative to general emulsion polymerization, is had in phase homogenous quantities point
The advantage that its viscosity is lower, lotion is more stable when number.
Specific embodiment
Below with reference to embodiment to a kind of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion of the invention and its system
Preparation Method is further described.It is understood that specific embodiment described herein is used only for explaining related invention,
Rather than the restriction to the invention.
Embodiment 1
A kind of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion, which is characterized in that containing wired in its molecular structure
Property poly(aryl ether ketone) branch;The present invention has synthesized the poly(aryl ether ketone) with propylene acid blocked first, and then poly(aryl ether ketone) participates in propylene
The seeding polymerization of yogurt liquid prepares core-shell structure emulsion acrylic resin, and according to parts by weight, preparation method includes following step
It is rapid:
The preparation of the linear poly(aryl ether ketone) of I, propylene acid blocked: under logical condition of nitrogen gas, equipped with division box, heating dress
It sets, 30 parts of 1,5- dihydroxy anthraquinones, 13 parts of 1,3- bis- (4- fluorobenzoyl) benzene, 5 parts of carbonic acid is added in the reactor of agitating device
Potassium, 40 parts of trimethylbenzenes, are heated to 150 DEG C under stirring, the water generated in dereaction, 150 DEG C of heat preservations are constantly removed by division box
3h is reacted, is then warming up to 190 DEG C with the heating rate of 5 DEG C/h, 180 DEG C of heat preservations polymerize 8h;Then 120 DEG C are cooled to, is added 1
Part acrylic acid, 2 parts of methacrylic acids, are warming up to 190 DEG C of reaction 8h with the heating rate of 10 DEG C/h, are removed by vacuum distillation lazy
Property solvent, obtains acrylic acid modified poly(aryl ether ketone);
The reaction of II, water soluble acrylic acid seeded emulsion polymerization: a, pre-emulsion stage: it be furnished with speed-adjustable stir device, return pipe, drop
In four mouthfuls of reaction vessels of liquid funnel and thermometer, 40 parts of deionized waters, 4 parts of allyloxy fatty alcohol ethylene oxide ether sulfuric acid are added
Salt, 0.5 part of acrylic acid, 3 parts of methyl methacrylates, 6 parts of isobutyl acrylates, 1 part of acrylic acid modified poly(aryl ether ketone), 1 part of β-
Hydroxy propyl methacrylate, 2 portions of pH value buffers;It is emulsified in 1500r/min high-speed stirred, obtain the mixing of milky pre-emulsification
Monomer emulsions;B, the seed emulsion stage: being heated to 90 DEG C, while turning down revolving speed to 900r/min, and 0.1 part of persulfuric acid is added dropwise
There is blue light heat preservation 2h in potassium solution initiation reaction at 90 DEG C;C, the emulsion polymerization stage: by 2 parts of acrylic acid, 15 parts of metering systems
Sour methyl esters, 25 parts of isobutyl acrylates, 12 parts of acrylic acid modified poly(aryl ether ketone), 2 parts of Beta-methyl hydroxypropyl acrylates, 0.5 part of mistake
Potassium sulfate, 35 parts of water obtain dropping liquid;90 DEG C dropping liquid is slowly added dropwise into seed emulsion, drips off in 2h, after being added dropwise
105 DEG C are warming up to, insulation reaction 0.5h;Add alkali regulation system pH value to 8, discharges after being cooled to room temperature, solid content is obtained by filtration
For 50% or so milky white liquid, as poly(aryl ether ketone) modified core shell structural acrylic resin emulsion.
Embodiment 2
A kind of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion, which is characterized in that containing wired in its molecular structure
Property poly(aryl ether ketone) branch;The present invention has synthesized the poly(aryl ether ketone) with propylene acid blocked first, and then poly(aryl ether ketone) participates in propylene
The seeding polymerization of yogurt liquid prepares core-shell structure emulsion acrylic resin, and according to parts by weight, preparation method includes following step
It is rapid:
The preparation of the linear poly(aryl ether ketone) of I, propylene acid blocked: under logical condition of nitrogen gas, equipped with division box, heating dress
It sets, 22 parts of 4- (4- hydroxy phenyl) -2,3- benzodiazine -1- ketone, 9 part of 4,4 '-difluoro two is added in the reactor of agitating device
Benzophenone, 8 parts of sodium carbonate, 50 parts of ethylbenzene, are heated to 130 DEG C, the water generated in dereaction are constantly removed by division box under stirring,
Then 130 DEG C of insulation reaction 4h are warming up to 200 DEG C with the heating rate of 5 DEG C/h, 180 DEG C of heat preservations polymerize 6h;Then it is cooled to
100 DEG C, 2 parts of acrylic acid, 3 parts of methacrylic acids are added, 180 DEG C of reaction 5h are warming up to the heating rate of 10 DEG C/h, by subtracting
Atent solvent is distilled off in pressure, obtains acrylic acid modified poly(aryl ether ketone);
The reaction of II, water soluble acrylic acid seeded emulsion polymerization: a, pre-emulsion stage: it be furnished with speed-adjustable stir device, return pipe, drop
In four mouthfuls of reaction vessels of liquid funnel and thermometer, 30 parts of deionized waters, 2 parts of dodecyl benzene sulfonates, 0.2 part of propylene is added
Acid, 5 parts of styrene, 4 parts of acrylic ester butyl esters, 0.5 part of acrylic acid modified poly(aryl ether ketone), 0.2 part of methacrylic acid amino, 1 part of pH value
Buffer;It is emulsified in 1200r/min high-speed stirred, obtain milky pre-emulsification mix monomer lotion;B, the seed emulsion stage:
75 DEG C are heated to, while turning down revolving speed to 800r/min, 0.05 part of perbenzoic acid solution is added dropwise and causes at 75 DEG C
There is blue light heat preservation 1h in reaction;C, the emulsion polymerization stage: by 0.5 part of acrylic acid, 12 parts of styrene, 15 parts of acrylic ester butyl esters, 8
The acrylic acid modified poly(aryl ether ketone) of part, 1 part of methacrylic acid amino, 0.2 part of perbenzoic acid, 20 parts of water obtain dropping liquid;75 DEG C will
Dropping liquid is slowly added dropwise into seed emulsion, drips off in 1h, 100 DEG C is warming up to after being added dropwise, insulation reaction 0.5h;Add alkali
Regulation system pH value discharges after being cooled to room temperature to 8, the milky white liquid that solid content is 50% or so is obtained by filtration, as gathers
Aryl ether ketone modified core shell structural acrylic resin emulsion.
Embodiment 3
A kind of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion, which is characterized in that containing wired in its molecular structure
Property poly(aryl ether ketone) branch;The present invention has synthesized the poly(aryl ether ketone) with propylene acid blocked first, and then poly(aryl ether ketone) participates in propylene
The seeding polymerization of yogurt liquid prepares core-shell structure emulsion acrylic resin, and according to parts by weight, preparation method includes following step
It is rapid:
The preparation of the linear poly(aryl ether ketone) of I, propylene acid blocked: under logical condition of nitrogen gas, equipped with division box, heating dress
It sets, 24 parts of 4,4' dihydroxy diphenyls, 10 parts of 1,4- bis--(4 '-fluoro benzoyl) benzene, 6 parts is added in the reactor of agitating device
Potassium carbonate, 43 parts of dimethylbenzene, are heated to 141 DEG C under stirring, constantly remove the water generated in dereaction by division box, and 141 DEG C
Then insulation reaction 3.3h is warming up to 195 DEG C with the heating rate of 5 DEG C/h, 180 DEG C of heat preservation polymerase 17 h;Then 110 are cooled to
DEG C, 1.4 parts of acrylic acid, 2.5 parts of methacrylic acids are added, 185 DEG C of reaction 6h are warming up to the heating rate of 10 DEG C/h, by subtracting
Atent solvent is distilled off in pressure, obtains acrylic acid modified poly(aryl ether ketone);
The reaction of II, water soluble acrylic acid seeded emulsion polymerization: a, pre-emulsion stage: it be furnished with speed-adjustable stir device, return pipe, drop
In four mouthfuls of reaction vessels of liquid funnel and thermometer, 36 parts of deionized waters, 3 parts of acrylamido sodium isopropyl xanthates, 0.4 are added
Part acrylic acid, 4 parts of methyl methacrylates, 5 parts of butyl methacrylates, 0.9 part of acrylic acid modified poly(aryl ether ketone), 0.4 part of β-
Hydroxy-ethyl acrylate, 1.6 portions of pH value buffers;It is emulsified in 1300r/min high-speed stirred, it is single to obtain the mixing of milky pre-emulsification
Precursor emulsion;B, the seed emulsion stage: being heated to 78 DEG C, while turning down revolving speed to 850r/min, and 0.07 part of peroxidating is added dropwise
There is blue light heat preservation 1.5h in the initiation reaction at 78 DEG C of t-butyl perbenzoate solution;C, the emulsion polymerization stage: by 0.8 part of propylene
Acid, 14 parts of methyl methacrylates, 20 parts of butyl methacrylates, 9 parts of acrylic acid modified poly(aryl ether ketone), 1.6 parts of β-acrylic acid
Hydroxyl ethyl ester, 0.3 part of peroxidized t-butyl perbenzoate, 28 parts of water obtain dropping liquid;78 DEG C dropping liquid is slowly added dropwise to seed emulsion
In, it is dripped off in 1.6h, 102 DEG C is warming up to after being added dropwise, insulation reaction 0.5h;Add alkali regulation system pH value to 9, is cooled to
It discharges after room temperature, the milky white liquid that solid content is 50% or so, as poly(aryl ether ketone) modified core shell structure propylene is obtained by filtration
Acid resin lotion.
Storage stability test: by the poly(aryl ether ketone) modified core shell structural acrylic resin emulsion sample of 0.5L embodiment 1-3
Product are fitted into suitable plastic containers, are taken out after 180 days, are stirred without agglomeration, precipitating, gelatinization phenomenon.
Paint film property test: by poly(aryl ether ketone) modified core shell structural acrylic resin emulsion embodiment of the invention and market
The competing product acrylic emulsion (comparative example) of upper purchase carries out the test comparison of application performance, and selection example and comparative example are according to phase
Industrial paint is prepared with formula, tests impact resistance of the paint film after tinplate is fully cured, water resistance, adhesive force, hardness and resistance to
Salt fog, stability, the performance being prepared into after finishing coat, test result is as follows table:
As can be seen from the above table, poly(aryl ether ketone) modified core shell structural acrylic resin emulsion of the invention is with higher resistance to
Aqueous, salt fog resistance, and hardness is higher, wearability is preferable.
Although the present invention has been explained in detail and has referred to embodiment, for those of ordinary skill in the art, show
Various schemes, modification and the change that can so make as specified above, should be construed as being included within the scope of the claims.
Claims (10)
1. a kind of preparation method of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion, which is characterized in that including walking as follows
It is rapid:
The preparation of the linear poly(aryl ether ketone) of I, propylene acid blocked: it by the ratio of control binary substituted phenol, two fluorinated aromatic hydrocarbons, uses
The gradually linear poly(aryl ether ketone) of the low molecular weight of polymerization synthesis of hydroxy sealing end, then obtains propylene acid blocked by esterification
Linear poly(aryl ether ketone);
The reaction of II, water soluble acrylic acid seeded emulsion polymerization: seeded emulsion polymerization is participated in by the linear poly(aryl ether ketone) of propylene acid blocked
Prepare poly(aryl ether ketone) modified core shell structural acrylic resin emulsion.
2. a kind of preparation method of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion according to claim 1,
It is characterized in that, the preparation process of the linear poly(aryl ether ketone) of the step I propylene acid blocked are as follows: under logical condition of nitrogen gas, reacting
Binary substituted phenol, two fluorinated aromatic hydrocarbons, weak base, atent solvent are added in device, 130-150 DEG C is heated under stirring, by dividing water to fill
It sets constantly except the water generated in dereaction, then 130-150 DEG C of insulation reaction 3-4h is warming up to the heating rate of 5 DEG C/h
190-200 DEG C, then it is down to 180 DEG C of heat preservation polymerization 6-8h;Then it is cooled to 100-120 DEG C, acrylic acid, methacrylic acid is added,
It is warming up to 180-190 DEG C of reaction 5-8h with the heating rate of 10 DEG C/h, atent solvent is removed by vacuum distillation, acrylic acid is obtained and changes
Property poly(aryl ether ketone).
3. a kind of preparation method of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion according to claim 2,
It is characterized in that, binary substituted phenol in the step I, two fluorinated aromatic hydrocarbons, weak base, atent solvent, acrylic acid, methacrylic acid
Weight fraction ratio is (22-30): (9-13): (5-8): (40-50): (1-2): (2-3).
4. a kind of preparation method of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion according to claim 2,
It is characterized in that, binary substituted phenol is 1- hydroxyl -4- (4- hydroxy benzenes)-benzodiazine, 4,4'- dihydroxybiphenyl, 4- (2- methyl -
4- hydroxy phenyl) benzodiazine, 1,5- dihydroxy anthraquinone, 4- (3- phenyl -4- hydroxy phenyl) -2,3- benzodiazine -1- ketone, 4-
At least one of (4- hydroxy phenyl) -2,3- benzodiazine -1- ketone;Two fluorinated aromatic hydrocarbons be 4,4 '-difluoro benzophenones,
At least one of 1,4- bis--(4 '-fluoro benzoyl) benzene, 1,3- bis- (4- fluorobenzoyl) benzene;The weak base be sodium carbonate,
At least one of potassium carbonate;The atent solvent be dimethylbenzene, trimethylbenzene, ethylbenzene, methyl-ethyl benzene, in diethylbenzene at least
It is a kind of.
5. a kind of preparation method of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion according to claim 1,
Be characterized in that, the step II water soluble acrylic acid seeded emulsion polymerization reaction process are as follows: by acrylic acid, hard monomer, soft monomer,
Acrylic acid modified poly(aryl ether ketone), crosslinkers monomers, initiator, water reaction, are made dropping liquid;It will drop under conditions of 75-90 DEG C
Liquid feeding is slowly added dropwise into seed emulsion, drips off in 1-2h, and post-reactor is added dropwise and is warming up to 100-105 DEG C, heat preservation is anti-
Answer 0.5h;Add alkali regulation system pH value to be discharged after being cooled to room temperature to 8~9, be obtained by filtration solid content be 50% or so it is milky white
Color liquid, as poly(aryl ether ketone) modified core shell structural acrylic resin emulsion.
6. a kind of preparation method of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion according to claim 5,
It is characterized in that, acrylic acid in the step II, soft monomer, acrylic acid modified poly(aryl ether ketone), crosslinkers monomers, draws hard monomer
Send out agent, the weight fraction ratio of water is (0.5-2): (12-15): (15-25): (8-12): (1-2): (0.2-0.5): (20-35).
7. a kind of preparation method of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion according to claim 5,
It is characterized in that, according to parts by weight, the preparation process of the seed emulsion are as follows:
A, the pre-emulsion stage: in the reaction vessel be added 30-40 parts of deionized waters, 2-4 parts of emulsifiers, 0.2-0.5 parts of acrylic acid,
3-5 parts of hard monomers, 4-6 parts of soft monomers, 0.5-1 parts of acrylic acid modified poly(aryl ether ketone), 0.2-1 parts of crosslinkers monomers, 1-2 parts of pH value
Buffer, it is emulsified in 1200-1500r/min high-speed stirred, obtain milky pre-emulsification mix monomer lotion;
B, the seed emulsion stage: milky pre-emulsification mix monomer lotion made from a stage is heated to 75-90 DEG C, together
When turn down revolving speed to 800-900r/min, 0.05-0.1 parts of initiator solution initiation reactions at 75-90 DEG C are added dropwise, blue light occur
1-2h is kept the temperature to get seed emulsion.
8. a kind of preparation method of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion according to claim 5,
It is characterized in that, the hard monomer is at least one of methyl methacrylate, styrene;The soft monomer is acrylic ester
The combination of one or more of butyl ester, ethyl acrylate, isobutyl acrylate, propylene ester methyl ester, butyl methacrylate;Institute
The crosslinkers monomers stated are one or more of β-hydroxy-ethyl acrylate, Beta-methyl hydroxypropyl acrylate, methacrylic acid amino
Combination;The initiator is potassium peroxydisulfate, benzoyl peroxide, peroxidized t-butyl perbenzoate, azodiisobutyronitrile, idol
At least one of the different heptonitrile of nitrogen two, perbenzoic acid, ammonium persulfate.
9. a kind of preparation method of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion according to claim 7,
It is characterized in that, the emulsifier is dodecyl benzene sulfonate, allyloxy fatty alcohol ethylene oxide ether sulfate, acrylamide
At least one of base sodium isopropyl xanthate.
10. a kind of preparation of such as described in any item poly(aryl ether ketone) modified core shell structural acrylic resin emulsions of claim 1-9
Method prepares resulting water-base resin.
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