CN108707213B - 一种超支化嵌段高分子共聚物的制备方法与应用 - Google Patents
一种超支化嵌段高分子共聚物的制备方法与应用 Download PDFInfo
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- CN108707213B CN108707213B CN201810485175.4A CN201810485175A CN108707213B CN 108707213 B CN108707213 B CN 108707213B CN 201810485175 A CN201810485175 A CN 201810485175A CN 108707213 B CN108707213 B CN 108707213B
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- lithium
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 238000000576 coating method Methods 0.000 claims abstract description 32
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- 239000011737 fluorine Substances 0.000 claims abstract description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 94
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 63
- 229910052757 nitrogen Inorganic materials 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 37
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- 229920006150 hyperbranched polyester Polymers 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 25
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 13
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 13
- 125000001931 aliphatic group Chemical group 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 9
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-UHFFFAOYSA-N 0.000 claims description 6
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- WXZIKFXSSPSWSR-UHFFFAOYSA-N [Li]CCCCC Chemical compound [Li]CCCCC WXZIKFXSSPSWSR-UHFFFAOYSA-N 0.000 claims description 3
- -1 acrylic ester Chemical class 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 claims description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 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
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims 1
- 238000009835 boiling Methods 0.000 claims 1
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 abstract description 4
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- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 32
- 239000003973 paint Substances 0.000 description 17
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- 230000001376 precipitating effect Effects 0.000 description 11
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
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- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 2
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- IRVZFACCNZRHSJ-UHFFFAOYSA-N 2,4,6,8-tetramethyl-2,4,6,8-tetraphenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si]1(C)C1=CC=CC=C1 IRVZFACCNZRHSJ-UHFFFAOYSA-N 0.000 description 1
- QTRQFVAKGZFBRT-UHFFFAOYSA-N 2-(3,3,3-trifluoropropyl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound FC(F)(F)CC[SiH]1O[SiH2]O[SiH2]O1 QTRQFVAKGZFBRT-UHFFFAOYSA-N 0.000 description 1
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- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
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- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
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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
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
-
- 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F220/14—Methyl esters, e.g. methyl (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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
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Abstract
本发明涉及聚合物技术领域,为解决目前涂料助剂制备过程中安全性差,而且溶剂用量较大、可控性较差等问题,本发明提出一种超支化嵌段高分子共聚物的制备方法,将羟端基脂肪族超支化聚酯在氮气保护下与金属有机锂反应,获得超支化大分子引发剂;接着,用所得超支化大分子引发剂引发环状有机硅单体开环共聚合;随后,继续引发丙烯酸、丙烯酸酯类单体和含氟丙烯酸酯类单体等共聚合,制备了一种新型超支化嵌段高分子共聚物。本方法由于采用了阴离子聚合反应,克服了自由基聚合反应中聚合反应太快,易爆聚,难控制的缺点。
Description
技术领域
本发明涉及聚合物技术领域,具体涉及一种超支化有机氟硅嵌段共聚物涂料助剂的制备方法。
背景技术
涂料是一种流动状态或粉末状态的有机物,能均匀覆盖在物体表面上,并且牢固地附着在物体表面,统称为涂料。涂料不仅能起防护、装饰作用,而且还具有绝缘、导电、防静电、示温、防霉、杀菌等特殊功能,广泛应用于家电、机械、电子、建筑、化工、航天航空、矿山冶金等各个领域。
涂料不管采取何种涂装手段,经施工后,会产生大量的机械泡和反应泡,如果这些泡不能及时破掉,将会使得涂料生产中发生危险、涂料固化后则产生缩孔、针眼等缺陷。在涂料表干过程中,均存在溶剂蒸发、聚合物流动的成膜过程,由于溶剂蒸发、聚合物与基材的润湿程度不同往往造成漆膜出现张力梯度,从而导致漆膜出现皱纹和缩孔,一旦出现这种现象,则漆膜的装饰性及漆膜的耐水性、耐溶剂性均会下降。消泡剂和流平剂是涂料不可缺少的助剂,它能促使涂料在干燥成膜过程中形成一个平整、光滑、均匀的涂膜。
聚丙烯酸酯价格低廉、具有良好粘结性和耐候性等优点,但不具有流平性和消泡性。全氟丙烯酸酯虽然性能优良,但价格昂贵。有机硅、丙烯酸酯类单体和含氟丙烯酸酯单体的共聚物,具有消泡和流平效果,制备过程中需要控制其分子量和分子量分布宽度。目前这类聚合物的制备方法有乳液聚合、离子聚合、自由基聚合等方式。陈永康报道了系列含氟丙烯酸酯流平剂的制备方法(ZL 200810020505.9,CN 201110059353.5和CN201110059479.2),但这些专利都是采用传统自由基聚合方法,需要较高温度,而且溶剂用量也较大,生产过程中容易发生爆聚,可控性较差,且存在一定的危险性。
发明内容
为解决目前涂料助剂制备过程中安全性差,而且溶剂用量较大、可控性较差等问题,本发明提出一种超支化嵌段高分子共聚物的制备方法,本方法由于采用了阴离子聚合反应,克服了自由基聚合反应中聚合反应太快,易爆聚,难控制的缺点。
本发明还提出一种超支化嵌段高分子共聚物在涂料助剂上的应用,该共聚物具有良好的流平性和消泡效果,是一种性能优良的涂料助剂,可用于家具漆、工业漆等涂料领域。
本发明是通过以下技术方案实现的:一种超支化嵌段高分子共聚物的制备方法为以下步骤:
(1)以二羟甲基丙酸、三羟甲基丙烷通过自缩聚反应合成羟端基脂肪族超支化聚酯;
羟端基脂肪族超支化聚酯分别为第一代、第二代、第三代、第四代和第五代羟基封端超支化聚酯,分别标为G1-HBPE,G2-HBPE,G3-HBPE,G4-HBPE和G5-HBPE;超支化聚合物是一种高度支化、有三维网状结构的聚合物,具有粘度低、高溶解性、不易结晶、分子间不易缠绕、大量的末端官能团以及强的化学反应活性等特点。其在结构上虽不如传统的树枝状高分子完美,但在制备过程中不需进行繁琐的分离和纯化,合成相对简单,便于工业化生产,产品成本较低。
本步骤以二羟甲基丙酸为单体、三羟甲基丙烷为中心核,采用“准一步法”常规方法,进行自缩聚反应。二羟甲基丙酸、三羟甲基丙烷的用量按照二羟甲基丙酸中的羧基与三羟甲基丙烷或超支化聚酯中羟基摩尔比1∶1,在原料1.5-3.0wt%对甲苯磺酸催化下,在氮气保护下,140-170℃下常压反应2-3h后,减压到130mmHg继续反应2-3h。最后将产物溶解于丙酮中,然后用正己烷沉淀,过滤后经80℃/130mmHg真空干燥24h后,获得产物。最初由二羟甲基丙酸中的羧基与三羟甲基丙烷中羟基按照摩尔比1∶1进行反应生成第一代羟基封端超支化聚酯,然后按照二羟甲基丙酸的羧基与超支化聚酯中羟基摩尔比1∶1反应制成第二代羟基封端超支化聚酯,如此循环到制成第五代羟基封端超支化聚酯。
(2)在氮气保护下,将所得羟端基超支化聚酯与金属有机锂在甲苯中反应,获得超支化大分子引发剂;
所述的金属有机锂选自叔丁基锂、丁基锂、乙基锂、戊基锂、苯基锂、甲基锂中的一种或几种。其中,有机锂与羟端基脂肪族超支化聚酯用量按照有机锂与羟端基脂肪族超支化聚酯中羟基的摩尔比1~1.5∶1。
甲苯的使用量为使反应充分进行的量,以甲苯能完全浸没羟基封端脂肪族超支化聚酯为宜。
作为优选,在60-130℃下反应0.5-3h,优选为反应0.5-1h。最后用正己烷清洗若干次。
(3)将所得的超支化大分子引发剂与环硅氧烷在促进剂中进行开环聚合反应,得到超支化聚酯-聚硅氧烷嵌段大分子活性种;
所述的环硅氧烷选自六甲基环三硅氧烷(D3)、八甲基环四硅氧烷(D4)、DMC(市售产品,是D3、D4、十甲基环五硅氧烷(D5)和少量线性体混合物)、三甲基三苯基环三硅氧烷(DMePh3)、四甲基四苯基环四硅氧烷(DMePh4)、甲基苯基混合环硅氧烷(DMePh3,DMePh4和五甲基五苯基环五硅氧烷等的混合物)、三氟丙基环三硅氧烷中的一种或几种。
环硅氧烷用量按照环硅氧烷与金属锂离子摩尔比10~500∶1。
所述的促进剂选自DMF(N,N-二甲基甲酰胺)、DMAC(二甲基乙酰胺)、DMSO(二甲基亚砜)中的一种或几种,使用量为环硅氧烷质量的0.5~7.0wt%。
作为优选,反应温度为100℃~150℃,聚合反应时间为1~12h。
(4)然后与由丙烯酸、丙烯酸酯类单体和含氟丙烯酸酯类单体组成的混合单体在有机溶液中进行共聚合反应,反应1-12h后加入醇类与盐酸的混合物来终止反应,得到初产物;
丙烯酸酯类单体选自甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、丙烯酸羟乙酯、丙烯酸羟丙酯中的一种或几种;
含氟丙烯酸酯类单体为丙烯酸六氟丁酯、甲基丙烯酸六氟丁酯、甲基丙烯酸三氟乙酯、甲基丙烯酸十二氟庚酯、丙烯酸十二氟庚酯、丙烯酸十三氟辛酯和甲基丙烯酸十三氟辛酯中的一种或者几种。
混合单体中丙烯酸为混合单体物质的量的1~60%,丙烯酸和丙烯酸酯类单体占混合单体物质的量的5-95%,含氟丙烯酸酯类单体的量为其余量,优选含氟丙烯酸酯类单体占混合单体总摩尔数的1.0~15.0%。
混合单体与步骤(3)中所得超支化聚酯-聚硅氧烷嵌段大分子活性种中金属锂原子的摩尔比为50~1000∶1。
所述的有机溶剂选自甲苯、二甲苯、四氢呋喃、正己烷、环己烷中的一种或几种,使用量为混合单体质量的0.5-6倍,优选为1-3倍。
作为优选,反应温度为80℃-150℃,反应时间为1-12h。
终止反应所用的醇类为甲醇、乙醇、异丙醇、正丁醇、叔丁醇中的一种或几种,其用量为混合单体质量的0.5-3倍。醇类与盐酸混合物中醇类的质量百分比为95%,HCI的质量百分比为5%。
(5)将初产物减压脱除溶剂、低分子和未参与聚合反应的单体,得到超支化嵌段高分子共聚物。
作为优选,压力选在60-80℃/130mmHg下进行脱除0.5-1.5h。
本发明将羟端基脂肪族超支化聚酯在氮气保护下与金属有机锂反应,获得超支化大分子引发剂;接着,用所得超支化大分子引发剂引发环状有机硅单体开环共聚合;随后,继续引发丙烯酸、丙烯酸酯类单体和含氟丙烯酸酯类单体等共聚合,制备了一种新型超支化嵌段高分子共聚物。
本发明制备得到的超支化嵌段高分子共聚物在作为涂料助剂上的应用。超支化聚酯凭借其独特的分子结构和优异的物理、化学性能,为提高涂料性能开辟了新的有效途径,它高度的支化结构使其分子间较少链缠结,不易结晶,使涂料具有良好的成膜性能。同时众多的端基官能团使得其具有很强的可改性能力,能够制备适合多种用途的涂料。高溶解性可减少有机溶剂的使用量,降低涂料成本,减少有害气体排放;低黏度使得很适合于制备高固体分涂料,与线型聚合物涂料共混能降低体系黏度,改善体系流动性。
超支化嵌段高分子共聚物在涂料助剂上的具体应用方法为:将支化嵌段高分子共聚物在溶剂中制成固含量为0.75-95%的涂料助剂。该助剂具有良好的流平性和消泡效果,可用于家具漆、工业漆等涂料领域。
所述溶剂选自甲苯、二甲苯、三甲苯、正己烷、环己烷、环己酮、石油醚、丙二醇甲醚醋酸酯、乙二醇乙醚醋酸酯、乙二醇单甲醚、乙二醇二甲醚、乙酸乙酯、乙酸丁酯、二甲酸酯高沸点环保溶剂、二甲酸酯环保万能溶剂中的一种或几种。
与现有技术相比,本发明的有益效果是:
(1)聚合反应可控,不易爆聚,便于设计聚合物分子结构。
(2)改善了聚合物的流动性和成膜性,得到性能优良的涂料助剂。
具体实施方式
下面通过实施例对本发明作进一步详细说明,实施例中所用原料均可市购或采用常规方法制备。
实施例1
(1)采用“准一步法”,以8.94g二羟甲基丙酸为单体、2.98g三羟甲基丙烷为中心核,0.04g对甲苯磺酸为催化剂,在氮气保护下,搅拌、加热到140℃反应0.5h,然后停止充氮气,减压到130mmHg反应2h,然后加入17.88g二羟甲基丙酸和0.09g对甲苯磺酸,在氮气保护下,140℃反应2h,之后减压到130mmHg反应2h,冷却至室温,再将产物溶解于丙酮中,然后用正己烷沉淀,过滤后经80℃/130mmHg真空干燥24h后,获得27.416g(收率92.0%)羟端基脂肪族超支化聚酯G2-HBPE;
(2)在氮气保护下,将所得羟端基超支化聚酯G2-HBPE 0.157g放入三颈烧瓶,加入甲苯1ml,在氮气氛下加入10ml(1.6mol/L)叔丁基锂,80℃陈化1小时。用10ml正己烷沉淀、清洗3次,获得不含游离Li+离子的超支化大分子引发剂;
(3)在氮气保护下,向所得超支化大分子引发剂中加14.2g促进剂DMSO(D4的3wt%),加入473.6gD4,在120℃下反应4小时,获得超支化聚酯-聚硅氧烷嵌段大分子活性种;
(4)在氮气保护下,加入300g无水无氧的甲苯、72.06g丙烯酸、100.12g甲基丙烯酸甲酯和236.11g丙烯酸六氟丁酯的混合物,在80℃下聚合8h后,降至室温,加入150g质量百分比为5%盐酸的甲醇溶液终止反应。
(5)在130mmHg/65℃下减压3h,脱除溶剂、低分子和未参与聚合反应的单体,获得转化率95.0%的一种新型超支化嵌段高分子共聚物895.96g,其固含量93.5%。应用例1
加入甲苯279.48g、三甲苯100g、乙二醇乙醚醋酸酯200g、50g乙二醇单甲醚和150g二甲酸酯高沸点环保溶剂DBE,将实施例1所得超支化嵌段高分子共聚物配制成固含量50%的涂料助剂1。
实施例2
(1)采用“准一步法”,以8.94g二羟甲基丙酸为单体、2.98g三羟甲基丙烷为中心核,0.04g对甲苯磺酸为催化剂,在氮气保护下,搅拌、加热到140℃反应3h,然后停止充氮气,减压到130mmHg反应2h,然后加入17.88g二羟甲基丙酸和0.09g对甲苯磺酸,在氮气保护下,140℃反应0.5h,之后减压到130mmHg反应2h,冷却至室温,再将产物溶解于丙酮中,然后用正己烷沉淀,过滤后经80℃/130mmHg真空干燥24h后,获得27.416g(收率92.0%)羟端基脂肪族超支化聚酯G2-HBPE;
(2)在氮气保护下,将所得羟端基超支化聚酯G2-HBPE 0.157g放入三颈烧瓶,加入甲苯1ml,在氮气氛下加入10ml(1.6mol/L)正丁基锂,140℃陈化0.5小时。用10ml正己烷沉降、清洗3次,获得不含游离Li+离子的超支化大分子引发剂;
(3)在氮气保护下,向所得超支化大分子引发剂中加7.1g促进剂DMSO(DMC的3wt%),加入236.8gDMC,在120℃下反应4小时,获得超支化聚酯-聚硅氧烷嵌段大分子活性种;
(4)在氮气保护下,加入400g无水无氧的二甲苯、12.01g丙烯酸、10.01g甲基丙烯酸甲酯和236.11g丙烯酸六氟丁酯的混合物,在100℃下聚合6h后,降至室温,加入400g质量百分比为5%盐酸的乙醇溶液终止反应。
(5)在130mmHg/75℃下减压4h,脱除溶剂、低分子和未参与聚合反应的单体,获得转化率94.0%的一种新型超支化嵌段高分子共聚物473.87g,其固含量90.0%。应用例2
加入甲苯200g,乙酸乙酯100g,乙酸丁酯117g,将实施例2所得超支化嵌段高分子共聚物配制成固含量50%的涂料助剂。
实施例3
(1)采用“准一步法”,以8.94g二羟甲基丙酸为单体、2.98g三羟甲基丙烷为中心核,0.04g对甲苯磺酸为催化剂,在氮气保护下,搅拌、加热到140℃反应2h,然后停止充氮气,减压到130mmHg反应2h,然后加入17.88g二羟甲基丙酸和0.09g对甲苯磺酸,在氮气保护下,140℃反应2h,之后减压到130mmHg反应2h,冷却至室温,再将产物溶解于丙酮中,然后用正己烷沉淀,过滤后经80℃/130mmHg真空干燥24h后,获得27.416g(收率92.0%)羟端基脂肪族超支化聚酯G2-HBPE;
(2)在氮气保护下,将所得羟端基超支化聚酯G2-HBPE 0.157g放入三颈烧瓶,加入甲苯1ml,在氮气氛下加入10ml(1.6mol/L)乙基锂,100℃陈化2小时。用10ml正己烷沉淀、清洗3次,获得不含游离Li+离子的超支化大分子引发剂;
(3)在氮气保护下,向所得超支化大分子引发剂中加入21.02g促进剂DMAc(环硅氧烷的4wt%),加入236.8gD4,234.27gD3F,54.4gDMePh3在130℃下反应10小时,获得超支化聚酯-聚硅氧烷嵌段大分子活性种;
(4)在氮气保护下,加入600g无水无氧的四氢呋喃、12.01g丙烯酸、142.2g甲基丙烯酸丁酯、118.06g丙烯酸六氟丁酯和250.14g甲基丙烯酸六氟丁酯的混合物,在70℃下聚合12h后,降至室温,加入400g质量百分比为5%盐酸的异丙醇溶液终止反应。
(5)在130mmHg/40℃下减压3h,脱除溶剂、低分子和未参与聚合反应的单体,获得转化率85.0%的一种新型超支化嵌段高分子共聚物937.58g,其固含量95.0%。应用例3
加入甲苯500g,乙酸乙酯500g,二甲苯200g、二甲酸酯环保万能溶剂MDBE131.41g,乙二醇二甲醚400g、环己酮300g,将实施例3所得超支化嵌段高分子共聚物配制成固含量30%的涂料助剂。
实施例4
(1)采用“准一步法”,以8.94g二羟甲基丙酸为单体、2.98g三羟甲基丙烷为中心核,0.04g对甲苯磺酸为催化剂,在氮气保护下,搅拌、加热到140℃反应2h,然后停止充氮气,减压到130mmHg反应2h,冷却至室温,再将产物溶解于丙酮中,然后用正己烷沉淀,过滤后经80℃/130mmHg真空干燥24h后,获得11.264g(收率94.5%)羟端基脂肪族超支化聚酯G1-HBPE;
(2)在氮气保护下,将所得羟端基超支化聚酯G1-HBPE 0.482g放入三颈烧瓶,加入甲苯2ml,在氮气氛下加入6ml(1.0mol/L)戊基锂,60℃陈化3小时。用30ml正己烷沉淀、清洗3次,获得不含游离Li+离子的超支化大分子引发剂;
(3)在氮气保护下,向所得超支化大分子引发剂中加入21.65g促进剂DMF(环硅氧烷的3wt%),再加入177.6g D3,544gDMePh4在140℃下反应12小时,获得超支化聚酯-聚硅氧烷嵌段大分子活性种;
(4)在氮气保护下,加入200g无水无氧的正己烷、36.01g丙烯酸、128.17g丙烯酸丁酯、118.06g丙烯酸六氟丁酯和400g甲基丙烯酸十二氟庚酯的混合物,在90℃下聚合12h后,降至室温,加入100g质量百分比为5%盐酸的正丁醇溶液终止反应。
(5)在130mmHg/60℃下减压4h,脱除溶剂、低分子和未参与聚合反应的单体,获得转化率91.5%的一种新型超支化嵌段高分子共聚物1352.20g,其固含量95.0%。
应用例4
将(5)所得产品直接作为涂料助剂使用,具有很好的流动性,其粘度(25±0.1℃)1050cp。
实施例5
(1)采用“准一步法”,以8.94g二羟甲基丙酸为单体、2.98g三羟甲基丙烷为中心核,0.04g对甲苯磺酸为催化剂,在氮气保护下,搅拌、加热到140℃反应2.5h,然后停止充氮气,减压到130mmHg反应2h,冷却至室温,再将产物溶解于丙酮中,然后用正己烷沉淀,过滤后经80℃/130mmHg真空干燥24h后,获得11.264g(收率94.5%)羟端基脂肪族超支化聚酯G1-HBPE;
(2)在氮气保护下,将所得羟端基超支化聚酯G1-HBPE 0.482g放入三颈烧瓶,加入甲苯3ml,在氮气氛下加入6ml(1.0mol/L)苯基锂,120℃陈化0.5小时。用10ml正己烷沉淀、清洗3次,获得不含游离Li+离子的超支化大分子引发剂;
(3)在氮气保护下,向所得超支化大分子引发剂中加5.33g促进剂DMF(环硅氧烷的3wt%),加入177.6g DMC在140℃下反应6小时,获得超支化聚酯-聚硅氧烷嵌段大分子活性种;
(4)在氮气保护下,加入200g无水无氧的甲苯、72.02g丙烯酸、128.20g丙烯酸丁酯、8.4g甲基丙烯酸三氟乙酯和40.0g甲基丙烯酸十三氟辛酯的混合物,在90℃下聚合12h后,降至室温,加入200g质量百分比为5%盐酸的乙醇溶液终止反应。
(5)在130mmHg/60℃下减压4h,脱除溶剂、低分子和未参与聚合反应的单体,获得转化率93.5%的一种新型超支化嵌段高分子共聚物430.83g,其固含量92.5%。应用例5
将实施例5所得产品加入10000g石油醚、7012.87g乙二醇乙醚醋酸酯、20000g环己烷,10000g正己烷和20000g环己酮,配成固含量0.75%的涂料助剂。
实施例6
(1)采用“准一步法”,以8.94g二羟甲基丙酸为单体、2.98g三羟甲基丙烷为中心核,0.04g对甲苯磺酸为催化剂,在氮气保护下,搅拌、加热到140℃反应2h,然后停止充氮气,减压到130mmHg反应2h。然后加入17.88g二羟甲基丙酸和0.09g对甲苯磺酸,在氮气保护下,140℃反应2h,之后减压到130mmHg MPa反应2h,再加入35.76g二羟甲基丙酸和0.18g对甲苯磺酸,在氮气保护下,140℃反应2h,之后减压到130mmHg反应2h,冷却至室温,再将产物溶解于丙酮中,然后用正己烷沉淀,过滤后经80℃/130mmHg真空干燥24h后,获得58.873g(收率89.8%)羟端基脂肪族超支化聚酯G3-HBPE;
(2)在氮气保护下,将所得羟端基超支化聚酯G3-HBPE 0.723g放入三颈烧瓶,加入甲苯4ml,在氮气氛下加入18ml(1.0mol/L)正丁基锂,90℃陈化2小时。用10ml正己烷沉淀、清洗3次,获得不含游离Li+离子的超支化大分子引发剂;(3)在氮气保护下,向所得超支化大分子引发剂中加6.96g促进剂DMF(环硅氧烷的3wt%),加入177.6g DMC和54.4g甲基苯基混合环体,在140℃下反应8小时,获得超支化聚酯-聚硅氧烷嵌段大分子活性种;
(4)在氮气保护下,加入1984.5g无水无氧的环己烷、50g丙烯酸乙酯、60g丙烯酸丙酯、100g丙烯酸丁酯、25g甲基丙烯酸羟乙酯、72.02g丙烯酸、84g甲基丙烯酸三氟乙酯和38.5g丙烯酸十三氟辛酯的混合物,在90℃下聚合2h后,降至室温,加入800g质量百分比为5%盐酸的甲醇溶液终止反应。
(5)在130mmHg/60℃下减压4h,脱除溶剂、低分子和未参与聚合反应的单体,获得转化率93.5%的一种新型超支化嵌段高分子共聚物672.29g,其固含量92.0%。应用例6
将实施例6所得产品加入300g乙二醇单甲醚、200g乙二醇乙醚醋酸酯和202.16g乙二醇二甲醚,配成固含量45%的涂料助剂。
实施例7
(1)采用“准一步法”,以8.94g二羟甲基丙酸为单体、2.98g三羟甲基丙烷为中心核,0.04g对甲苯磺酸为催化剂,在氮气保护下,搅拌、加热到140℃反应2h,然后停止充氮气,减压到130mmHg反应2h。然后加入17.88g二羟甲基丙酸和0.09g对甲苯磺酸,在氮气保护下,140℃反应2h,之后减压到130mmHg反应2h,再加入35.76g二羟甲基丙酸和0.18g对甲苯磺酸,在氮气保护下,140℃反应2h,之后减压到130mmHg反应2h;还加入71.52g二羟甲基丙酸和0.36g对甲苯磺酸,在氮气保护下,140℃反应2h,之后减压到130mmHg反应2h;冷却至室温,再将产物溶解于丙酮中,然后用正己烷沉淀,过滤后经80℃/130mmHg真空干燥24h后,获得118.574g(收率86.5%)羟端基脂肪族超支化聚酯G4-HBPE;(2)在氮气保护下,将所得羟端基超支化聚酯G4-HBPE 1.446g放入三颈烧瓶,加入甲苯5ml,在氮气氛下加入24ml(1.0mol/L)正丁基锂,110℃陈化0.5小时。用10ml正己烷清洗3次,获得不含游离Li+离子的超支化大分子引发剂;
(3)在氮气保护下,向所得超支化大分子引发剂中加6.96g促进剂DMSO(环硅氧烷的5wt%),加入200g DMC和35g D3F,在140℃下反应6小时,获得超支化聚酯-聚硅氧烷嵌段大分子活性种;
(4)在氮气保护下,加入886g无水无氧的甲苯、200g甲基丙烯酸甲酯、150g丙烯酸丁酯、25g甲基丙烯酸羟乙酯、72.02g丙烯酸、84g甲基丙烯酸三氟乙酯和120g丙烯酸十三氟辛酯的混合物,在90℃下聚合4h后,降至室温,加入600g质量百分比为5%盐酸的甲醇溶液终止反应。
(5)在130mmHg/60℃下减压4h,脱除溶剂、低分子和未参与聚合反应的单体,获得转化率93.8%的一种新型超支化嵌段高分子共聚物888.84g,其固含量93.5%。应用例7
将实施例7所得产品加入100g三甲苯、119.25g乙二醇乙醚醋酸酯配成固含量75%的涂料助剂。
比较例
应用类型PU亮光白面漆,对比例为在树脂市售1503添加进口BYK样品作为助剂,添加量:0.05-0.2%。
表1是应用例1-4制成涂料的实际使用对照表,除光泽是用光泽仪测得外,其余项打分按照满分3分,2.0分合格,2.5分优秀。如表1所示,本发明产品作为涂料助剂具有较好的消泡性,板面更平整,丰满度较好,快速流平、板干后手感和清晰度相当。
表1
对应项目 | 应用例1 | 应用例2 | 应用例3 | 应用例4 | 进口BYK样品 |
消泡 | 2.5 | 2.5-3 | 2.0-2.5 | 2.0-2.5 | 2.0-2.5 |
施工稳泡 | 2.5 | 2.5 | 2.0 | 2.0 | 2.0 |
瞬间流平 | 2.0-2.5 | 2.5 | 2.5 | 2.5 | 2.5 |
光泽° | 99 | 99 | 99 | 98 | 97 |
板面平整度 | 2.5 | 2.5 | 2.5 | 2.5 | 2.0-2.5 |
清晰度 | 2.0 | 2.5 | 2.5 | 2.0 | 2.0-2.5 |
丰满度 | 2.0-2.5 | 2.5 | 2.0 | 2.5 | 2.0 |
手感 | 2-2.5 | 2.5稍差 | 2.5 | 2.5 | 2.5 |
Claims (8)
1.一种超支化嵌段高分子共聚物的制备方法,其特征在于,所述的制备方法为以下步骤:
(1)以二羟甲基丙酸、三羟甲基丙烷通过自缩聚反应合成羟端基脂肪族超支化聚酯;
(2)在氮气保护下,将所得羟端基超支化聚酯与金属有机锂在甲苯中反应,获得超支化大分子引发剂;
(3)将所得的超支化大分子引发剂与环硅氧烷在促进剂中进行开环聚合反应,得到超支化聚酯-聚硅氧烷嵌段大分子活性种;
所述促进剂选自DMF、DMAC、DMSO中的一种或几种,使用量为环硅氧烷质量的0.5~7.0wt%;
(4)然后与由丙烯酸、丙烯酸酯类单体和含氟丙烯酸酯类单体组成的混合单体在有机溶剂中进行共聚合反应,然后加入醇类与盐酸混合物来终止反应,得到初产物;
所述丙烯酸酯类单体选自甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、丙烯酸羟乙酯、丙烯酸羟丙酯中的一种或几种;
所述含氟丙烯酸酯类单体为丙烯酸六氟丁酯、甲基丙烯酸六氟丁酯、甲基丙烯酸三氟乙酯、甲基丙烯酸十二氟庚酯、丙烯酸十二氟庚酯、丙烯酸十三氟辛酯和甲基丙烯酸十三氟辛酯中的一种或者几种;
(5)将初产物减压脱除溶剂、低分子和未参与聚合反应的单体,得到超支化嵌段高分子共聚物。
2.根据权利要求1所述的一种超支化嵌段高分子共聚物的制备方法,其特征在于,步骤(2)中金属有机锂选自丁基锂、乙基锂、戊基锂、苯基锂、甲基锂中的一种或几种,其中,有机锂与羟端基脂肪族超支化聚酯用量按照有机锂与羟端基脂肪族超支化聚酯中羟基的摩尔比1 ~1.5:1。
3.根据权利要求1所述的一种超支化嵌段高分子共聚物的制备方法,其特征在于,步骤(3)环硅氧烷用量按照环硅氧烷与金属锂离子摩尔比10~500:1。
4.根据权利要求1所述的一种超支化嵌段高分子共聚物的制备方法,其特征在于,混合单体中丙烯酸为混合单体物质的量的1~60%,丙烯酸和丙烯酸酯类单体占混合单体物质的量的5-95%,含氟丙烯酸酯类单体的量为其余量。
5.根据权利要求1所述的一种超支化嵌段高分子共聚物的制备方法,其特征在于,步骤(4)中有机溶剂选自甲苯、二甲苯、四氢呋喃、正己烷、环己烷中的一种或几种,使用量为混合单体质量的0.5-6倍;终止反应所用的醇类为甲醇、乙醇、异丙醇、正丁醇、叔丁醇中的一种或几种,使用量为混合单体质量的0.5-3倍。
6.一种如权利要求1所述的超支化嵌段高分子共聚物的制备方法制备得到的超支化嵌段高分子共聚物在作为涂料助剂上的应用。
7.根据权利要求6所述的一种超支化嵌段高分子共聚物的应用,其特征在于,将超支化嵌段高分子共聚物在溶剂中制成固含量为0.75-95%的涂料助剂。
8.根据权利要求7所述的一种超支化嵌段高分子共聚物的应用,其特征在于,所述溶剂选自甲苯、二甲苯、三甲苯、正己烷、环己烷、环己酮、石油醚、丙二醇甲醚醋酸酯、乙二醇乙醚醋酸酯、乙二醇单甲醚、乙二醇二甲醚、乙酸乙酯、乙酸丁酯、二价酸酯高沸点环保溶剂中的一种或几种。
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