CN114891154B - 一种丙烯酸树脂及其制备方法和应用 - Google Patents
一种丙烯酸树脂及其制备方法和应用 Download PDFInfo
- Publication number
- CN114891154B CN114891154B CN202210738794.6A CN202210738794A CN114891154B CN 114891154 B CN114891154 B CN 114891154B CN 202210738794 A CN202210738794 A CN 202210738794A CN 114891154 B CN114891154 B CN 114891154B
- Authority
- CN
- China
- Prior art keywords
- monomer
- acrylic resin
- citric acid
- parts
- methacrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 77
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 176
- 239000000178 monomer Substances 0.000 claims abstract description 83
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 229960004106 citric acid Drugs 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 20
- 229960004543 anhydrous citric acid Drugs 0.000 claims description 15
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 15
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- -1 glycidyl ester Chemical group 0.000 claims description 11
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 10
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 7
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 7
- 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 6
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 claims description 6
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-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 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 claims description 3
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 claims description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 229940117955 isoamyl acetate Drugs 0.000 claims description 3
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 claims description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000006115 industrial coating Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 description 13
- 239000003973 paint Substances 0.000 description 10
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 6
- 239000012855 volatile organic compound Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- NPKKFQUHBHQTSH-UHFFFAOYSA-N 2-(decoxymethyl)oxirane Chemical compound CCCCCCCCCCOCC1CO1 NPKKFQUHBHQTSH-UHFFFAOYSA-N 0.000 description 1
- BRNGPGXGRUQXOJ-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O BRNGPGXGRUQXOJ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 244000099147 Ananas comosus Species 0.000 description 1
- 235000007119 Ananas comosus Nutrition 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000021552 granulated sugar Nutrition 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000021374 legumes Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
-
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- 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
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明涉及一种丙烯酸树脂及其制备方法和应用,属于精细化工合成领域。本发明提供一种丙烯酸树脂,由以下重量份的原料制成:柠檬酸改性单体5‑20份、硬单体5‑35份、软单体5‑20份、羟基单体5‑25份、羧基单体1‑3份、引发剂1‑6份和有机溶剂20‑40份。本发明丙烯酸树脂具有高固体份、低黏度的特征,用于涂料中能够满足汽车涂料、工业涂料等领域的涂装要求;同时VOC含量低,进一步降低了丙烯酸树脂涂料在使用过程中的碳排放。
Description
技术领域
本发明属于精细化工合成领域,具体涉及一种丙烯酸树脂及其制备方法和应用。
背景技术
丙烯酸树脂是一种由含双键的不饱和单体经自由基聚合得到的高分子聚合物,是涂料、胶黏剂、油墨等领域的核心原材料。尤其在涂料领域,因丙烯酸树脂具有干燥速度快、光泽高、硬度高、耐候性好等优点而深受涂料行业的喜爱。含有羟基的丙烯酸树脂可以与多异氰酸酯固化剂反应获得聚氨酯涂料,还可以与氨基树脂反应获得高温氨基涂料,这些涂料在汽车制造与维修、轨道列车、工程机械、风电叶片等领域获得了广泛的使用。
常规方法制备丙烯酸树脂的单体原料主要来源于石油产业,石化原料的使用造成了碳排放居高不下、石化资源越来越短缺,导致目前的产业难以实现可持续化发展。而生物基材料是指农作物、其他植物、谷物、豆科、秸秆等可再生的生物质以及从这些生物质中提取的原料,这些物质和原料再经过生物、化学以及物理等方法可生成新型材料,使用生物质材料替代石化原料,可以减少石油原料的消耗,对环境友好,符合绿色发展的理念。
柠檬酸在自然界中分布很广,天然的柠檬酸存在于植物如柠檬、柑橘、菠萝等果实和动物的骨骼、肌肉、血液中。人工合成的柠檬酸是用砂糖、糖蜜、淀粉、葡萄等含糖物质发酵而制得的。其来源广泛、价格低廉,是一种常用的酸度调节剂和食品添加剂。柠檬酸分子结构中含有三个羧基,可以和醇、环氧等化合物反应,柠檬酸与乙醇、丁醇等酯化反应的产物可以代替传统的邻苯二甲酸二丁酯作为增塑剂使用,已经获得工业化的应用。
专利公开号CN201610236643.5提供了一种基于无水柠檬酸的4官能度聚氨酯丙烯酸酯及其制备方法和应用。该低粘度4官能度UV光固化聚氨酯丙烯酸酯固化后,具有硬度高、耐磨、耐刮、耐热、耐候性等优良性能,能够作为UV涂料、油墨、粘合剂的原料应用;但其无法作为合成丙烯酸树脂的原料。专利公开号CN201811443699.3提供了一种柠檬酸甲基丙烯酸酯单体聚合得到的聚合物。该单体的聚合物可用于水中重金属离子的吸附,吸附效率较高。可见,生物质材料柠檬酸在工业领域有广泛的应用前景,但是,现有技术中鲜有报道将生物质材料柠檬酸引入丙烯酸树脂体系制备低挥发性有机化合物(VOC)涂料,因此,制备一种基于柠檬酸的丙烯酸树脂材料是目前需解决的技术问题。
发明内容
本发明的目的在于克服上述现有技术中存在的问题,提供一种丙烯酸树脂及其制备方法和应用。
本发明是通过下述技术方案进行实现的:
本发明提供一种丙烯酸树脂,由以下重量份的原料制成:柠檬酸改性单体5-20份、硬单体5-35份、软单体5-20份、羟基单体5-25份、羧基单体1-3份、引发剂1-6份和有机溶剂20-40份。
本发明的丙烯酸树脂由柠檬酸改性单体和其他单体复配,使得丙烯酸树脂具有高固体份、低黏度的特征,从而降低了丙烯酸树脂涂料中有机溶剂的使用量,降低了丙烯酸树脂涂料的VOC含量,进一步降低了丙烯酸树脂涂料在使用过程中的碳排放。
优选地,所述丙烯酸树脂,由以下重量份的原料制成:柠檬酸改性单体10-15份、硬单体15-30份、软单体10-15份、羟基单体15-20份、羧基单体1.5-2.5份、引发剂2-4份和有机溶剂23-35份。
作为本发明所述丙烯酸树脂的优选实施方式,所述柠檬酸改性单体由无水柠檬酸、叔碳酸缩水甘油酯和甲基丙烯酸缩水甘油酯制成。
本发明的柠檬酸改性单体由无水柠檬酸、叔碳酸缩水甘油酯和甲基丙烯酸缩水甘油酯反应得到,本发明的柠檬酸改性单体具有较大的空间位阻,进而使得丙烯酸树脂具有高固体份、低黏度的性能。
作为本发明所述丙烯酸树脂的优选实施方式,所述硬单体为甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、苯乙烯、甲基丙烯酸异冰片酯中的至少一种;所述软单体为丙烯酸乙酯、丙烯酸丁酯、丙烯酸异辛酯中的至少一种。
作为本发明所述丙烯酸树脂的优选实施方式,所述羟基单体为丙烯酸羟乙酯、丙烯酸羟丙酯、丙烯酸羟丁酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、甲基丙烯酸羟丁酯中至少一种;所述羧基单体为丙烯酸和/或甲基丙烯酸。
作为本发明所述丙烯酸树脂的优选实施方式,所述引发剂为偶氮二异丁腈、过氧化二苯甲酰、过氧化苯甲酸叔丁酯、过氧化-2-乙基己酸叔丁酯、过氧化二异丙苯、过氧化二叔丁基、过氧化二叔戊基中的至少一种。
作为本发明所述丙烯酸树脂的优选实施方式,所述有机溶剂为二甲苯、三甲苯、醋酸乙酯、醋酸丁酯、醋酸异戊酯、乙二醇乙醚醋酸酯、丙二醇甲醚醋酸酯、丁酮、甲基异丁基酮、甲基异戊基酮中的至少一种。
本发明的又一目的在于提供上述丙烯酸树脂的制备方法,包括以下步骤:
取所述柠檬酸改性单体、硬单体、软单体、羟基单体、羧基单体、引发剂混合,得混合物;加入预加热的有机溶剂中聚合反应,即成。
优选地,所述丙烯酸树脂的制备方法为:取所述柠檬酸改性单体、硬单体、软单体、羟基单体、羧基单体、引发剂混合,得混合物;滴入预加热的有机溶剂中,2.5h-6h滴完,保温2h-4h,降温,即成。
作为本发明所述丙烯酸树脂的制备方法的优选实施方式,所述柠檬酸改性单体的制备方法为:取无水柠檬酸、叔碳酸缩水甘油酯、甲基丙烯酸缩水甘油酯混合,加入催化剂,加热搅拌,即得;
所述无水柠檬酸、叔碳酸缩水甘油酯和甲基丙烯酸缩水甘油酯的摩尔比为:无水柠檬酸:叔碳酸缩水甘油酯:甲基丙烯酸缩水甘油酯=1:(2~3):(1~2);所述催化剂为辛酸亚锡和/或亚磷酸三壬基苯酯;所述加热搅拌的温度为120℃~130℃,时间为3h~5h。
优选地,所述无水柠檬酸、叔碳酸缩水甘油酯和甲基丙烯酸缩水甘油酯的摩尔比为:无水柠檬酸:叔碳酸缩水甘油酯:甲基丙烯酸缩水甘油酯=1:2:1;所述加热搅拌的时间为4h。
作为本发明所述丙烯酸树脂的制备方法的优选实施方式,所述预加热的温度为80℃~180℃。
本发明的再一目的在于提供上述丙烯酸树脂及其制备方法在涂料中的应用。
与现有技术相比,本发明具有如下有益效果:
(1)本发明的丙烯酸树脂中,柠檬酸改性单体具有较大的空间位阻,进而使得丙烯酸树脂具有高固体份、低黏度的特征,从而降低了丙烯酸树脂涂料中有机溶剂的使用量,降低了丙烯酸树脂涂料的VOC含量。
(2)本发明的制备方法中将柠檬酸、叔碳酸缩水甘油酯和甲基丙烯酸缩水甘油酯反应,得到含有不饱和双键的柠檬酸改性单体,并将该单体与其他原料复配聚合,制得基于柠檬酸的生物基丙烯酸树脂,符合绿色发展理念,拓宽了丙烯酸树脂的原料来源。
(3)本发明的丙烯酸树脂减少了石化原料的消耗,由其制备的涂料VOC含量低,能够满足作为汽车、工业领域涂装使用的要求,对环境友好,具有更好的可持续发展前景。
具体实施方式
为更好地说明本发明的目的、技术方案和优点,下面将结合具体实施例对本发明作进一步说明。本领域技术人员应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。
实施例中所用的试验方法如无特殊说明,均为常规方法;所用的材料、试剂等,如无特殊说明,均可从商业途径得到。
实施例1
一种丙烯酸树脂,其制备方法包括以下步骤:
(1)将1mol(192.1g)的无水柠檬酸与2mol(468g)的叔碳酸缩水甘油酯、1mol(142.1g)的甲基丙烯酸缩水甘油酯及0.8g辛酸亚锡、8.0g亚磷酸三壬基苯酯混合,在125℃下搅拌反应4小时,得柠檬酸改性单体;
(2)取150g步骤(1)得到的柠檬酸改性单体与100g甲基丙烯酸甲酯、150g苯乙烯、100g甲基丙烯酸丁酯、65g丙烯酸丁酯、150g丙烯酸羟乙酯、10g丙烯酸和25g过氧化苯甲酸叔丁酯混合,得混合物,将溶剂250g二甲苯加热至137℃,将所得混合物滴入预加热的溶剂中聚合,4小时滴完,保温3小时,降温,即得丙烯酸树脂。该树脂的固含量为75.1%,基于固体的羟基含量为4.2%。
实施例2
一种丙烯酸树脂,其制备方法包括以下步骤:
(1)柠檬酸改性单体的制备方法同实施例1;
(2)取150g步骤(1)得到的柠檬酸改性单体与50g甲基丙烯酸甲酯、50g甲基丙烯酸乙酯、100g苯乙烯、120g甲基丙烯酸丁酯、45g丙烯酸乙酯、40g丙烯酸异辛酯、50g丙烯酸羟乙酯、60g丙烯酸羟丙酯、15g甲基丙烯酸和15g过氧化二苯甲酰、5g过氧化-2-乙基己酸叔丁酯混合,得混合物,将溶剂150g三甲苯、50g醋酸乙酯、100g醋酸丁酯加热至128℃,将所得混合物滴入预加热的溶剂中聚合,4小时滴完,保温3小时,降温,即得丙烯酸树脂。该树脂的固含量为70.2%,基于固体的羟基含量为3.4%。
实施例3
一种丙烯酸树脂,其制备方法包括以下步骤:
(1)柠檬酸改性单体的制备方法同实施例1;
(2)取50g步骤(1)得到的柠檬酸改性单体与80g甲基丙烯酸甲酯、75g甲基丙烯酸异冰片酯、90g苯乙烯、85g丙烯酸乙酯、40g丙烯酸异辛酯、40g丙烯酸羟丁酯、30g甲基丙烯酸羟丁酯、45g甲基丙烯酸羟丙酯、30g丙烯酸和35g偶氮二异丁腈混合,得混合物,将溶剂150g醋酸异戊酯、150g乙二醇乙醚醋酸酯、100g丙二醇甲醚醋酸酯加热至80℃,将所得混合物滴入预加热的溶剂中聚合,2.5小时滴完,保温3小时,降温,即得丙烯酸树脂。该树脂的固含量为60.1%,基于固体的羟基含量为2.8%。
实施例4
一种丙烯酸树脂,其制备方法包括以下步骤:
(1)柠檬酸改性单体的制备方法同实施例1;
(2)取20g步骤(1)得到的柠檬酸改性单体与85g甲基丙烯酸甲酯、65g甲基丙烯酸乙酯、105g苯乙烯、150g丙烯酸异辛酯、120g丙烯酸羟丁酯、15g甲基丙烯酸和15g过氧化二异丙苯、15g过氧化二叔丁基、30g过氧化二叔戊基混合,得混合物,将溶剂50g丁酮、50g甲基异丁基酮、100g甲基异戊基酮加热至180℃,将所得混合物滴入预加热的溶剂中聚合,6小时滴完,保温3小时,降温,即得丙烯酸树脂。该树脂的固含量为79.8%,基于固体的羟基含量为3.3%。
实施例5
一种丙烯酸树脂,其制备方法包括以下步骤:
(1)柠檬酸改性单体的制备方法同实施例1;
(2)取50g步骤(1)得到的柠檬酸改性单体与50g甲基丙烯酸甲酯、50g甲基丙烯酸乙酯、100g苯乙烯、120g甲基丙烯酸丁酯、145g丙烯酸乙酯、40g丙烯酸异辛酯、110g丙烯酸羟乙酯、15g甲基丙烯酸和15g过氧化二苯甲酰、5g过氧化-2-乙基己酸叔丁酯混合,得混合物,将溶剂150g三甲苯、50g醋酸乙酯、100g醋酸丁酯加热至128℃,将所得混合物滴入预加热的溶剂中聚合,4小时滴完,保温3小时,降温,即得丙烯酸树脂。该树脂的固含量为70.2%,基于固体的羟基含量为2.8%。
实施例6
一种丙烯酸树脂,其制备方法包括以下步骤:
(1)柠檬酸改性单体的制备方法同实施例1;
(2)取100g步骤(1)得到的柠檬酸改性单体与50g甲基丙烯酸甲酯、50g甲基丙烯酸乙酯、100g苯乙烯、120g甲基丙烯酸丁酯、95g丙烯酸乙酯、40g丙烯酸异辛酯、110g丙烯酸羟乙酯、15g甲基丙烯酸和15g过氧化二苯甲酰、5g过氧化-2-乙基己酸叔丁酯混合,得混合物,将溶剂150g三甲苯、50g醋酸乙酯、100g醋酸丁酯加热至128℃,将所得混合物滴入预加热的溶剂中聚合,4小时滴完,保温3小时,降温,即得丙烯酸树脂。该树脂的固含量为70.4%,基于固体的羟基含量为3.2%。
实施例7
一种丙烯酸树脂,其制备方法包括以下步骤:
(1)柠檬酸改性单体的制备方法同实施例1;
(2)取150g步骤(1)得到的柠檬酸改性单体与50g甲基丙烯酸甲酯、50g甲基丙烯酸乙酯、100g苯乙烯、120g甲基丙烯酸丁酯、45g丙烯酸乙酯、40g丙烯酸异辛酯、110g丙烯酸羟乙酯、15g甲基丙烯酸和15g过氧化二苯甲酰、5g过氧化-2-乙基己酸叔丁酯混合,得混合物,将溶剂150g三甲苯、50g醋酸乙酯、100g醋酸丁酯加热至128℃,将所得混合物滴入预加热的溶剂中聚合,4小时滴完,保温3小时,降温,即得丙烯酸树脂。该树脂的固含量为70.1%,基于固体的羟基含量为3.6%。
实施例8
一种丙烯酸树脂,其制备方法包括以下步骤:
(1)柠檬酸改性单体的制备方法同实施例1;
(2)取200g步骤(1)得到的柠檬酸改性单体与50g甲基丙烯酸甲酯、50g甲基丙烯酸乙酯、100g苯乙烯、120g甲基丙烯酸丁酯、35g丙烯酸异辛酯、110g丙烯酸羟乙酯、15g甲基丙烯酸和15g过氧化二苯甲酰、5g过氧化-2-乙基己酸叔丁酯混合,得混合物,将溶剂150g三甲苯、50g醋酸乙酯、100g醋酸丁酯加热至128℃,将所得混合物滴入预加热的溶剂中聚合,4小时滴完,保温3小时,降温,即得丙烯酸树脂。该树脂的固含量为70.1%,基于固体的羟基含量为4.1%。
对比例1
一种丙烯酸树脂,其制备方法包括以下步骤:
(1)将1mol(192.1g)的无水柠檬酸与3mol(426.3g)的甲基丙烯酸缩水甘油酯及0.8g辛酸亚锡、8.0g亚磷酸三壬基苯酯混合,在125℃下搅拌反应4小时,得柠檬酸改性单体;
(2)取150g步骤(1)得到的柠檬酸改性单体与100g甲基丙烯酸甲酯、150g苯乙烯、100g甲基丙烯酸丁酯、65g丙烯酸丁酯、150g丙烯酸羟乙酯、10g丙烯酸和25g过氧化苯甲酸叔丁酯混合,得混合物,将溶剂250g二甲苯加热至137℃,将所得混合物滴入预加热的溶剂中聚合,在滴加过程中发生了凝胶现象,该对比例丙烯酸树脂的制备实验未能成功,无法获得丙烯酸树脂成品。
对比例2
一种丙烯酸树脂,其制备方法包括以下步骤:
(1)将1mol(192.1g)的无水柠檬酸与2mol(1202g)的癸基缩水甘油醚、1mol(114.1g)的烯丙醇缩水甘油醚及0.8g辛酸亚锡、8.0g亚磷酸三壬基苯酯混合,在125℃下搅拌反应4小时,得柠檬酸改性单体;
(2)取150g步骤(1)得到的柠檬酸改性单体与100g甲基丙烯酸甲酯、150g苯乙烯、100g甲基丙烯酸丁酯、65g丙烯酸丁酯、150g丙烯酸羟乙酯、10g丙烯酸和25g过氧化苯甲酸叔丁酯混合,得混合物,将溶剂250g二甲苯加热至137℃,将所得混合物滴入预加热的溶剂中聚合,4小时滴完,保温3小时,降温,即得丙烯酸树脂。
本对比例步骤(1)中的柠檬酸改性单体中出现固体析出物,经检测酸值为105.6mgKOH/g,表明缩水甘油醚类化合物与柠檬酸难以发生化学反应,柠檬酸基本未参与反应;最终制得的丙烯酸树脂出现分层和白色沉淀,难以实际应用。
对比例1和2表明同时采用叔碳酸缩水甘油酯和甲基丙烯酸缩水甘油酯与柠檬酸反应是获得柠檬酸改性单体的必要选择,选择其他环氧化合物难以制得柠檬酸改性的丙烯酸树脂,进而达到理想的应用效果。
将实施例1-4的丙烯酸树脂制备成试验例1-4的涂料,所述试验例1-4的涂料组分及配比如表1所示;表1中所述催化剂为二月桂酸二丁基锡,所述流平剂为埃夫科纳流平剂3700,所述固化剂为万华化学HT100。
表1试验例1-4的涂料的组分及配比
试验例1-4的涂料性能如表2所示:
表2试验例1-4的涂料的性能测试结果
可见,采用基于柠檬酸的生物基丙烯酸树脂所制备的聚氨酯涂料的VOC含量能够满足国家标准GB24409-2020的要求,漆膜的表干时间、实干时间、最终硬度、光泽度、耐水、耐化学品性等指标均能够满足汽车涂料、工业涂料等领域的涂装要求。
实施例5-8的丙烯酸树脂的原料总量相同,制备方法相同,但柠檬酸改性单体的添加量逐渐增多,柠檬酸改性单体的添加量对丙烯酸树脂的粘度的影响结果如表3所示。
表3实施例5-8的丙烯酸树脂的固含量和粘度
编号 | 实施例5 | 实施例6 | 实施例7 | 实施例8 |
柠檬酸改性单体的添加量 | 5% | 10% | 15% | 20% |
固含量(%) | 70.2 | 70.4 | 70.1 | 70.1 |
粘度(mPa·s) | 8240 | 6150 | 4230 | 2880 |
从表3可以看出,实施例5-8的丙烯酸树脂中,固含量基本相同,随着柠檬酸改性单体添加量的提高,所获得的丙烯酸树脂的粘度逐渐降低,反映出由于柠檬酸改性单体的空间位阻效应,阻碍了分子链之间的聚集团聚,使得分子间作用力减弱,树脂的粘度变小。
将本发明丙烯酸树脂制备成聚氨酯涂料时,所得涂料不仅能够满足汽车涂料、工业涂料等领域的涂装要求,同时VOC排放量低,对环境友好。
最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (7)
1.一种丙烯酸树脂,其特征在于,由以下重量份的原料制成:柠檬酸改性单体5-20份、硬单体5-35份、软单体5-20份、羟基单体5-25份、羧基单体1-3份、引发剂1-6份和有机溶剂20-40份;所述柠檬酸改性单体由无水柠檬酸、叔碳酸缩水甘油酯和甲基丙烯酸缩水甘油酯制成;所述硬单体为甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、苯乙烯、甲基丙烯酸异冰片酯中的至少一种;所述软单体为丙烯酸乙酯、丙烯酸丁酯、丙烯酸异辛酯中的至少一种;所述羟基单体为丙烯酸羟乙酯、丙烯酸羟丙酯、丙烯酸羟丁酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、甲基丙烯酸羟丁酯中至少一种;
所述柠檬酸改性单体的制备方法为:取无水柠檬酸、叔碳酸缩水甘油酯、甲基丙烯酸缩水甘油酯混合,加入催化剂,加热搅拌,即得;
所述无水柠檬酸、叔碳酸缩水甘油酯和甲基丙烯酸缩水甘油酯的摩尔比为:无水柠檬酸:叔碳酸缩水甘油酯:甲基丙烯酸缩水甘油酯=1:(2~3):(1~2);所述催化剂为辛酸亚锡和/或亚磷酸三壬基苯酯;所述加热搅拌的温度为120℃~130℃,时间为3h~5h。
2.根据权利要求1所述的丙烯酸树脂,其特征在于,所述羧基单体为丙烯酸和/或甲基丙烯酸。
3.根据权利要求1所述的丙烯酸树脂,其特征在于,所述引发剂为偶氮二异丁腈、过氧化二苯甲酰、过氧化苯甲酸叔丁酯、过氧化-2-乙基己酸叔丁酯、过氧化二异丙苯、过氧化二叔丁基、过氧化二叔戊基中的至少一种。
4.根据权利要求1所述的丙烯酸树脂,其特征在于,所述有机溶剂为二甲苯、三甲苯、醋酸乙酯、醋酸丁酯、醋酸异戊酯、乙二醇乙醚醋酸酯、丙二醇甲醚醋酸酯、丁酮、甲基异丁基酮、甲基异戊基酮中的至少一种。
5.权利要求1-4任一项权利要求所述的丙烯酸树脂的制备方法,其特征在于,包括以下步骤:
取所述柠檬酸改性单体、硬单体、软单体、羟基单体、羧基单体、引发剂混合,得混合物;加入预加热的有机溶剂中聚合反应,即成。
6.根据权利要求5所述的丙烯酸树脂的制备方法,其特征在于,所述预加热的温度为80℃~180℃。
7.权利要求1-4任一项权利要求所述的丙烯酸树脂或权利要求5-6任一项权利要求所述的制备方法制备的丙烯酸树脂在涂料中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210738794.6A CN114891154B (zh) | 2022-06-27 | 2022-06-27 | 一种丙烯酸树脂及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210738794.6A CN114891154B (zh) | 2022-06-27 | 2022-06-27 | 一种丙烯酸树脂及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114891154A CN114891154A (zh) | 2022-08-12 |
CN114891154B true CN114891154B (zh) | 2023-11-14 |
Family
ID=82729386
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210738794.6A Active CN114891154B (zh) | 2022-06-27 | 2022-06-27 | 一种丙烯酸树脂及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114891154B (zh) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105418833A (zh) * | 2015-12-25 | 2016-03-23 | 江门市制漆厂有限公司 | 一种高固体份烤漆用丙烯酸树脂及其制备方法 |
CN111978444A (zh) * | 2019-05-22 | 2020-11-24 | 中国科学院宁波材料技术与工程研究所 | 一种基于有机多元酸的光固化树脂及其制备方法与应用 |
CN113429572A (zh) * | 2021-07-15 | 2021-09-24 | 上海能漠新材料有限公司 | 一种水溶性叔碳酸缩水甘油酯树脂的制备方法及应用 |
-
2022
- 2022-06-27 CN CN202210738794.6A patent/CN114891154B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105418833A (zh) * | 2015-12-25 | 2016-03-23 | 江门市制漆厂有限公司 | 一种高固体份烤漆用丙烯酸树脂及其制备方法 |
CN111978444A (zh) * | 2019-05-22 | 2020-11-24 | 中国科学院宁波材料技术与工程研究所 | 一种基于有机多元酸的光固化树脂及其制备方法与应用 |
CN113429572A (zh) * | 2021-07-15 | 2021-09-24 | 上海能漠新材料有限公司 | 一种水溶性叔碳酸缩水甘油酯树脂的制备方法及应用 |
Also Published As
Publication number | Publication date |
---|---|
CN114891154A (zh) | 2022-08-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1687279A (zh) | 一种木材用淀粉胶的制备方法 | |
CN111793160A (zh) | 一种工业烤漆用水性丙烯酸树脂及其制备方法 | |
CN101407568A (zh) | 一种高固低黏丙烯酸树脂及其制备方法 | |
CN114316854B (zh) | 一种高固含量低粘度的丙烯酸胶黏剂及其制备方法 | |
TW201335294A (zh) | 水分散性可自交聯的預聚物組成物 | |
CN109503738B (zh) | 一种磷酸改性聚异戊二烯橡胶、聚异戊二烯橡胶改性丙烯酸酯树脂分散体及制备方法和用途 | |
CN112341566B (zh) | 一种磺酸型羟基丙烯酸树脂水分散体及其制备方法 | |
CN114891154B (zh) | 一种丙烯酸树脂及其制备方法和应用 | |
CN111116857B (zh) | 一种乙烯基树脂及其制备方法 | |
CN101173030A (zh) | 一种超高固含量羟基丙烯酸树脂的制备方法 | |
CN111253577A (zh) | 一种制备改性环氧丙烯酯的方法 | |
CN112759720B (zh) | 一种耐水煮含磷水性丙烯酸改性聚酯分散体树脂及其制备方法与应用 | |
CN113308166B (zh) | 一种高附着抗回粘替塑胶及其制备方法 | |
CN112851870B (zh) | 一种改性聚异戊二烯及制备方法和由其制备的丙烯酸酯树脂分散体 | |
CN111454422B (zh) | 一种高剥离强度的真空吸塑胶及其制备方法 | |
CN111234134B (zh) | 一种高性能叔碳酸缩水甘油酯改性聚硅氧烷树脂及其制备方法 | |
CN113214709A (zh) | 一种用于制作漆膜的水性氟碳漆 | |
CN112500522A (zh) | 一种水性羟基丙烯酸树脂分散体及其制备方法 | |
CN113185910A (zh) | 一种水性替塑胶的涂布工艺 | |
CN108034401B (zh) | 一种含微胶囊的硅棒粘接的单组份胶水 | |
CN111454423B (zh) | 一种水性真空吸塑胶及其制备方法 | |
CN116426162B (zh) | 一种耐低温uv喷墨打印油墨 | |
CN116063919B (zh) | 一种用于三聚氰胺板材uv覆膜上光的附着力树脂 | |
CN115594791B (zh) | 无溶剂丙烯酸树脂及其制备方法、应用 | |
CN112126262B (zh) | 一种uv-led固化涂料及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |