CN109957062A - High cross-linked acrylic acid lipin polymer and preparation method thereof and purposes as thickener - Google Patents
High cross-linked acrylic acid lipin polymer and preparation method thereof and purposes as thickener Download PDFInfo
- Publication number
- CN109957062A CN109957062A CN201711403768.3A CN201711403768A CN109957062A CN 109957062 A CN109957062 A CN 109957062A CN 201711403768 A CN201711403768 A CN 201711403768A CN 109957062 A CN109957062 A CN 109957062A
- Authority
- CN
- China
- Prior art keywords
- acrylic acid
- variety
- methyl
- high cross
- linked acrylic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002562 thickening agent Substances 0.000 title claims abstract description 31
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229920000642 polymer Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 39
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000004132 cross linking Methods 0.000 claims abstract description 33
- -1 C1-C4 hydroxyalkyl acrylate Chemical compound 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 13
- 150000003254 radicals Chemical class 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 229920000570 polyether Polymers 0.000 claims abstract description 8
- 238000012673 precipitation polymerization Methods 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000003973 paint Substances 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000539 dimer Substances 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 claims description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 2
- JHSWSKVODYPNDV-UHFFFAOYSA-N 2,2-bis(prop-2-enoxymethyl)propane-1,3-diol Chemical compound C=CCOCC(CO)(CO)COCC=C JHSWSKVODYPNDV-UHFFFAOYSA-N 0.000 claims description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 2
- LZDXRPVSAKWYDH-UHFFFAOYSA-N 2-ethyl-2-(prop-2-enoxymethyl)propane-1,3-diol Chemical compound CCC(CO)(CO)COCC=C LZDXRPVSAKWYDH-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 229940091181 aconitic acid Drugs 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000006266 etherification reaction Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 150000001451 organic peroxides Chemical class 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 2
- TYMYJUHDFROXOO-UHFFFAOYSA-N 1,3-bis(prop-2-enoxy)-2,2-bis(prop-2-enoxymethyl)propane Chemical compound C=CCOCC(COCC=C)(COCC=C)COCC=C TYMYJUHDFROXOO-UHFFFAOYSA-N 0.000 claims 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims 1
- 239000007983 Tris buffer Substances 0.000 claims 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims 1
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 21
- 230000008719 thickening Effects 0.000 abstract description 11
- 239000003292 glue Substances 0.000 description 14
- 230000001681 protective effect Effects 0.000 description 14
- 239000001913 cellulose Substances 0.000 description 13
- 229920002678 cellulose Polymers 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 3
- 102100026735 Coagulation factor VIII Human genes 0.000 description 3
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007761 roller coating Methods 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 1
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 1
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 description 1
- 238000001792 White test Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000002087 whitening effect Effects 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/29—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for multicolour effects
Landscapes
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Abstract
The present invention relates to a kind of high cross-linked acrylic acid lipin polymer and preparation method thereof and as the purposes of thickener, the copolymer is obtained by the precipitation polymerization that the free radical of the monomer composition in a solvent including following monomer causes: a) the first monomer component of 10-80wt% is selected from one of olefinic list unsaturated monomer containing at least one carboxylic acid group or a variety of；B) the second olefinic list unsaturated monomer component of 89.9-15wt%, one of C1-C4 hydroxyalkyl acrylate of straight chain or branching selected from (methyl) acrylic acid or a variety of；C) cross-linking component of 0.01-5wt%, selected from the polyalkenyl polyethers at least two polymerizable ethylenical unsaturated double bonds.High cross-linked acrylic acid lipin polymer of the invention shows for example high thickening efficiency of excellent performance, good Miscibility and storage stability in multi-color.
Description
Technical field
Water is used for the present invention relates to a kind of high cross-linked acrylic acid lipin polymer and preparation method thereof and as thickener
The purposes of property multi-color system, substituted cellulose class thickener, thickener of the invention (rheology modifier) can dissolve in water
Or swelling, transparency liquid is formed, while forming interactive construction in the protective glue of colorful system, the color grain in multi-color is made to keep steady
It is fixed, improve the water-whitening resistance energy of multi-color.
Background technique
Raising with the fast development and people of Architectural Paint in China industry to finishing requirements, water-water multi-color by
More and more concerns.Multicolor finish can replace the stone materials such as granite as exterior coating, reduce the exploitation to lithotome, right
Environment plays a protective role, while avoiding bring danger due to falling off for lithotome, with " environmental protection, graceful, energy conservation "
Feature meets the demand of development.In addition, the complete Water-borne modification of water-in-water multicolor coating, VOC content is low, and can be according to people
Demand configuration different colours and size color grain, different marmorean floral designs effects can be obtained in spraying.Just because of upper
The superiority and creativeness that aqueous colorful paint highlights in coating industry are stated, therefore is recognized by more and more insiders
Can, the scope of application in China is also increasing.
Aqueous colorful paint be it is a kind of be dispersed in water dispersion medium containing film forming matter, be made of colored spherolite water-borne dispersions
Water-soluble colorful coating；The coating is mainly made of dispersed phase, protection sol solution and continuous phase three parts.Water-water multi-color
There are many systems for dispersed phase, and current most popular system is cellulose ether/speciality viscous systems.Cellulose thickener is made
For the important component of this system, to the color tablets of multicolor finish, the performances such as storage have important influence.The skill of colorful water paint
Art key is the stability that ideal colored particle is formed and is suspended in continuous phase.Protective glue is chemical synthesis hectorite,
The diametrically round shape nano particle of 30nm, thickness 1nm, sheet surfaces have negative electrical charge, and edge is positively charged.Ideal crystal structure
It is clipped between two layers of 4 tetrahedral silicon atoms for 6 octahedral magnesium ions.
Cellulose thickener and the mechanism of protective glue crosslinking may on the one hand be hydroxyl in cellulose thickener with
Hydroxyl in protective glue particle surface hexagonal hole forms hydrogen bond；On the other hand since protective glue surface has negative electricity, meeting and hydroxyl
Based polar group forms dipolar interaction.
Although cellulose thickener can be very good to have an effect with protective glue, it is ensured that suspension of the color tablets in continuous phase
Stability and morphology retentivity, but cellulose thickener will cause multi-color film forming water-fast white effect it is poor.Meanwhile cellulose family
Thickener easily causes the infection of bacterium due to its polysaccharide class formation, causes the long enzyme of paint film, influences paint film appearance effect.
EP13836 describes the copolymer containing following components: (1) acrylic acid and/or methyl-prop of 20-69.5 weight %
Olefin(e) acid；(2) 0.5-25 weight %'s has formula CH2=C (R)-C (O)-O- (CH2CH2O)n-RoMonomer, wherein R is H or CH3,
N is at least 2, RoIt is C8-C30Alkyl, alkylaryl or multi-ring alkyl；(3) at least at least one acrylic acid C of 30 weight %1-
C4Arrcostab and/or methacrylic acid C1-C4Arrcostab, and the polyenoid unsaturated monomer of (4) 0-0.1 weight %, wherein (1) (2)
(3) and the total amount of (4) is 100%.
US4692502, which is disclosed, forms catalyst and at least one selected from anion, cation and both sexes examination in free radical
Polymerizeing unsaturated carboxyl group-containing monomer (such as acrylic acid) and optional comonomer in the presence of the ionic surfactant of agent
Method.
In addition, United States Patent (USP) US7816441 discloses low molecular weight addition polymers A of the molecular weight less than 100,000 dalton
The purposes as dispersing aid in the aqueous emulsion or suspension polymerisation that free radical causes, it by 0.1% to 40wt% at least
A kind of C3-C30Alkene, 40% to the 99.9wt% unsaturated C of at least one olefinic3-C6Monocarboxylic acid, 0% to 50wt% extremely
A kind of few unsaturated C of olefinic4-C12Dicarboxylic acids and/or the ethylenically unsaturated dicarboxylic list alkyl ester or two as obtained by carboxylic acid acid
Carboxylic acid anhydrides, 0% to 30wt% other at least one olefinic unsaturated compounds that can be copolymerized with aforementioned monomer are with copolymerized form group
At.
The above patent is all the method for synthetic thickening agent, but its raw material for using or technique, and some is on thickening efficiency
Face existing defects, the complete and stabilization that effective structure cannot be formed with protective glue and then protect color tablets in multi-color having.Nothing
Method meets the application in multi-color.
Summary of the invention
In view of above-mentioned problems of the prior art, the present inventor uses at least two polymerizable ethylenical unsaturated double bonds
Polyalkenyl polyethers be cross-linking component, with the olefinic list unsaturated monomer of carboxylic acid group and the straight chain or branch of (methyl) acrylic acid
The hydroxyalkyl acrylate of change obtains the powder acrylic acid esters co-polymer of high crosslinking by the precipitation polymerization mode in dicyandiamide solution
Thickener；In addition, have the additional amount of patent substantially between 0-0.5% in terms of the cross-linking component additional amount of thickener, and
The additional amount of cross-linking component of the invention preferably from about 1% or even higher, the degree of cross linking with higher can provide more in system
Firm tridimensional network, it is ensured that product viscosity and stability.This thickener is due to introducing the multichain containing unsaturated double-bond
Alkenyl polyether type crosslinking agent can effectively promote " flexibility " of cross-linking efficiency and polymer molecular chain between polymer molecule, Ke Yirang
Hydroxyl and protective glue above the straight chain of (methyl) acrylic acid or the hydroxyalkyl acrylate of branching preferably crosslink effect, play
The similar effect of cellulose thickener, while the olefinic list unsaturated monomer of carboxylic acid group plays the role of thickening, Neng Gou
It is met the requirements in terms of thickening efficiency and multi-color color tablets stability, simultaneously because the excellent compatibility of such thickener and resin,
Enable multi-color that there is good water-whitening resistance.
The purpose of the present invention is to provide a kind of high cross-linked acrylic acid lipin polymers, by making to include such as in a solvent
The precipitation polymerization that the free radical of the monomer composition of lower monomer causes obtains:
A) 10-80wt%, preferably 20-70wt%, the first of more preferable 30-60wt%, further preferred 40-55wt% are single
Body component is selected from one of olefinic list unsaturated monomer containing at least one carboxylic acid group or a variety of；
B) 89.9-15wt%, preferably 79%-29wt%, more preferable 69%-29wt%, further preferred 59-44wt%'s
Second olefinic list unsaturated monomer component is selected from the straight chain of (methyl) acrylic acid or the C1-C4 hydroxyalkyl acrylate of branching
It is one or more；
C) 0.01-5wt%, preferably 0.1-3wt%, more preferable 0.3-2wt%, the friendship of further preferred 0.5-1.5wt%
Join component, selected from the polyalkenyl polyethers at least two polymerizable ethylenical unsaturated double bonds.
Above-mentioned wt% is counted on the basis of the gross mass of all three classes monomers.
Olefinic list unsaturated monomer containing at least one carboxylic acid group can be selected from acrylic acid, methacrylic acid, clothing health
Acid, fumaric acid, crotonic acid, aconitic acid or one of maleic acid and its salt are a variety of.
The straight chain of (methyl) acrylic acid or the C1-C4 hydroxyalkyl acrylate of branching can selected from (methyl) acrylate,
(methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid -4- hydroxy butyl ester but one of or it is a variety of.
Polyalkenyl polyethers at least two polymerizable ethylenical unsaturated double bonds include but is not limited to allyl alcohol with
The etherification product of the polyalcohol of straight chain or branching with 2-15 carbon atom, wherein the polyalcohol can be selected from sucrose, season
One of penta tetrol, dipentaerythritol, trimethylolpropane and its dimer, triethylol propane and its dimer are more
Kind, such as the polyallyl ether of pentaerythrite, including pentaerythritol diallyl ether, pentaerythritol triallyl ether and season penta
Tetrol tetraallyl ether；The polyallyl ether of trimethylolpropane, including trimethylolpropane allyl ether and trihydroxy methyl
Propane triallyl ether etc..
Term " (methyl) acrylic acid " used herein refers to including acrylic acid and methacrylic acid.Similarly, make here
Term " (methyl) alkyl acrylate " refers to including alkyl acrylate and alkyl methacrylate.
Height synthesized by the present invention crosslinking acrylic acid esters co-polymer cross-linking component for generate have partly or
The polymer for the three-dimensional network being substantially crosslinked.It includes the polyalkenyls at least two polymerizable ethylenical unsaturated double bonds
Polyethers or two or more combinations thereof.Amount ofthe cross-linking monomer preferred 0.1wt%-3wt%, more preferable 0.3wt%-
2wt%, further preferred 0.5wt%-1.5wt%.Amount ofthe cross-linking monomer is too big, and synthesized thickener is difficult in the later period
Swelling stretching, extension, causes thickening efficiency low；Amount ofthe cross-linking monomer is too small, and the 3 D stereo reticular structure that synthetic thickening agent is formed is not
It is enough abundant, the movement of system free molecular flow cannot be effectively limited, causes product viscosity relatively low.
Olefinic list unsaturated monomer component being introduced on thickener containing at least one carboxylic acid group can be in alkali
Carboxylic acids salt is quickly generated under, and the carboxylate radical on main chain stretches main chain effectively by mutually exclusive, so with water shape
Hydration layer is formed at hydrogen bond, promotes the viscosity of whole system.
Olefinic list unsaturated monomer mass fraction preferred 20%-70%, preferably 30%- containing at least one carboxylic acid group
60%, most preferably 40%-55%；Olefinic list unsaturated monomer content containing at least one carboxylic acid group is too low, thickener
Thickening efficiency is relatively low, and the olefinic list unsaturated monomer content of carboxylic acid group is high, and product polymerization stability is poor and is crosslinked with protective glue
Degree is low, influences multi-color color tablets quality and stability.
Hydroxyl above the straight chain of (methyl) acrylic acid or the C1-C4 hydroxyalkyl acrylate of branching can the thickening of like fibrous element class
Hydroxyl above agent forms effective crosslinked action in protective glue, it is ensured that the stabilization of whole system color grain.And due to its entirety
Structure and dispersed phase emulsion compatibility are good, can promote the water-whitening resistance energy of system very well.The straight chain of (methyl) acrylic acid or branching
C1-C4 hydroxyalkyl acrylate mass fraction preferred 80%-20%, preferably 70%-30%, most preferably 60%-45%；(methyl) third
The too high levels of the C1-C4 hydroxyalkyl acrylate of the straight chain or branching of olefin(e) acid can reduce thickener to the thickening efficiency of system, (first
Base) acrylic acid straight chain or branching the low crosslinked action that can be reduced with protective glue of C1-C4 hydroxy alkyl ester content, make multi-color
Color grain stability reduce.
The acrylic acid esters co-polymer of the crosslinking of height synthesized by the present invention, the precipitating caused by free radical in a solvent are poly-
Conjunction obtains.Selected solvent is preferably selected from one of hydro carbons, esters or a variety of, used in hydro carbons include but is not limited to
N-hexane, hexamethylene, normal heptane, cycloheptane, n-decane and its mixture；Esters used in it include but is not limited to acetic acid second
Ester, butyl acetate, ethyl propionate, butyl propionate and its mixture.
The acrylic acid esters co-polymer of the crosslinking of height synthesized by the present invention, the precipitating caused by free radical in a solvent are poly-
Conjunction obtains.Radical type initiator selected by its method polymerizeing includes at least one be organic peroxide class compound,
Azo compound, inorganic peroxysulfate class compound and hydrogen peroxide class or optional its composition, radical type initiator
Including but not limited to azodiisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, dilauroyl peroxide, ammonium persulfate, over cure
Sour sodium, hydrogen peroxide.
The equal Dalton molecular weight of number about 1 × 10 of acrylic acid esters co-polymer thickener of the invention6-1×107Between, tool
There is higher molecular weight, requirement of the system to viscosity can be met.
Invention further provides the preparation method of the acrylic acid esters co-polymer of above-mentioned high crosslinking, this method include with
Lower step::
E. solvent, the olefinic list unsaturated monomer containing at least one carboxylic acid group, (methyl) propylene are added in a reservoir
The straight chain of acid or the C1-C4 hydroxyalkyl acrylate and cross-linking component of branching, are passed through nitrogen, open stirring；
F. initiator is added into container, is reacted；
G. it to fully reacting, then adds part initiator and eliminates residual monomer, then cool down filtering and discharging；
H. filtering product is cleaned and is dried, obtain required powder product.
The present invention restriction not stringent to reaction temperature, can choose 40-130 DEG C, preferably 50-110 DEG C, more preferably
It 60-100 DEG C, selects optimal reaction temperature that can effectively promote reaction rate, shortens the reaction time, while reducing by-product
It generates, improves the quality of product.The dosage of initiator can be the 0.01-0.5wt% of three kinds of monomer dosage summations, preferably
The initiator amount added in 0.05-0.15wt%, step g for example can be the initiator amount added for the first time in step f
1/2~1/5.Initiator as described above include but is not limited to azodiisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide,
One of dilauroyl peroxide, ammonium persulfate, sodium peroxydisulfate, hydrogen peroxide are a variety of.
Present invention product obtained is mainly used in aqueous colorful paint, and substituted cellulose class thickener is played and protected
Glue forms the effect of crosslinking, guarantees the suspension and stability of dispersed phase color grain in multi-color.
A further object of the present invention is to be to provide above-mentioned high cross-linked acrylic acid lipin polymer as aqueous colorful paint body
Be the purposes of thickener, this thickener (auxiliary rheological agents) can effectively promote the viscosity of system, while can in multi-color
Protective glue crosslinks effect, it is ensured that the color tablets integrity and stability of multi-color dispersed phase.
The positive effect of the present invention is:
1) acrylic acid esters co-polymer of high crosslinking of the invention may replace the thickener of cellulose family in multi-color, introduce
Polyalkenyl polyether-type crosslinking agent containing unsaturated double-bond can effectively promote cross-linking efficiency and polymer between polymer molecule
" flexibility " of strand, can allow hydroxyl above the straight chain of (methyl) acrylic acid or the hydroxyalkyl acrylate of branching and protective glue more
Good crosslinks effect, guarantees the suspension and stability of dispersed phase color grain in multi-color.
2) acrylic acid esters co-polymer and dispersed phase resin compatible of high crosslinking of the invention are good, colorful after film forming
Surface compact is painted, the water-whitening resistance energy of paint film can be effectively improved.
3) acrylic acid esters co-polymer of high crosslinking of the invention shows such as high thickening of excellent performance in multi-color
Efficiency, good Miscibility and storage stability etc..
Specific embodiment
For the better implementation present invention, the present invention will be further explained with reference to the examples below, but embodiment is simultaneously
It is not limitation of the present invention.
Listed monomer and component are used for the embodiment of the present invention in following table.
Embodiment 1
A kind of acrylic acid esters co-polymer of high crosslinking, synthesizing formula composition such as table 1:
Table 1
| Raw material | Quality/g |
| AA | 40 |
| HEMA | 40 |
| TMPDE | 0.82 |
| Hypermer B246 | 0.16 |
| AIBN | 0.08 |
| BPO | 0.08 |
| Hexamethylene | 160 |
| N-hexane | 160 |
| Ethyl acetate | 400 |
Its step are as follows for the acrylic acid esters co-polymer being crosslinked using the height of this formula synthesis:
1) hexamethylene 160g, n-hexane 160g and ethyl acetate 400g are added in four-hole boiling flask, connect condenser pipe, opens
Stirring is opened, is uniformly mixed；
2) by 40g monomer AA, 40g monomer HEMA, 0.82g crosslinking agent TMPDE, 0.16g stabilizer Hypermer B246 with
And 0.08g initiator A IBN and 0.04g initiator B PO is added in four-hole boiling flask, to be triggered dose is completely dissolved, and is passed through nitrogen bubbling
20-30 minutes；
3) heating water bath is warming up to 75 DEG C, reacts 3 hours, improves temperature to 90 DEG C, then react 2 hours.At this temperature
0.04g initiator B PO is added, then is reacted 1 hour, fully reacting, cooling processing is started；
4) the obtained product of step 3 is filtered, washed, dried and ground, obtain white powdery solid C1；
5) obtained sample 1.5g is added in 300g deionized water, 0.7g neutralizer AMP-95 is added, uses JSF-
550 stirring dispersion machines are mixed, and are mixed 30 minutes, and (25 DEG C) of constant temperature processing are carried out to it, obtain sample A1.
Embodiment 2
A kind of acrylic acid esters co-polymer of high crosslinking, synthesizing formula composition such as table 2:
Table 2
The synthesis step and embodiment 1 of embodiment 2 are similar, and details are not described herein, according to this obtained products C 2 of formula and
Sample A2.
Embodiment 3
A kind of acrylic acid esters co-polymer of high crosslinking, synthesizing formula composition such as table 3:
Table 3
| Raw material | Quality/g |
| AA | 25 |
| MAA | 15 |
| HEMA | 30 |
| Triallyl sucrose ether | 0.3 |
| TMPDE | 0.4 |
| Hypermer B246 | 0.14 |
| AIBN | 0.07 |
| BPO | 0.07 |
| Hexamethylene | 150 |
| N-hexane | 150 |
| Ethyl acetate | 330 |
The synthesis step and embodiment 1 of embodiment 3 are similar, and details are not described herein, according to this obtained products C 3 of formula and
Sample A3.
Embodiment 4
A kind of acrylic acid esters co-polymer of high crosslinking, synthesizing formula composition such as table 4:
Table 4
The synthesis step and embodiment 1 of embodiment 4 are similar, and details are not described herein, according to this obtained products C 4 of formula and
Sample A4.
Embodiment 5
A kind of acrylic acid esters co-polymer of high crosslinking, synthesizing formula composition such as table 5:
Table 5
| Raw material | Quality/g |
| MAA | 45 |
| HPMA | 35 |
| Triallyl sucrose ether | 0.8 |
| Hypermer B246 | 0.16 |
| AIBN | 0.08 |
| LPO | 0.08 |
| Hexamethylene | 180 |
| N-hexane | 190 |
| Ethyl acetate | 350 |
The synthesis step and embodiment 1 of embodiment 5 are similar, and details are not described herein, according to this obtained products C 5 of formula and
Sample A5.
Comparative example 1
A kind of acrylic acid esters co-polymer of high crosslinking, synthesizing formula composition such as table 6:
Table 6
The synthesis step and embodiment 1 of comparative example 1 are similar, and details are not described herein, according to this obtained products C 6 of formula and
Sample A6.
By cellulose250 according to the method for embodiment 1, is dissolved into deionized water, obtained sample
Entitled B1.Respectively to above five samples, with it is rich strangle fly No. 4 rotor 12rpm measurements of DV-II (RV) viscosimeter wherein, low cut
Viscosity is cut, flies CAP2000+ type cone and plate viscometer with rich Le and measures its shear viscosity, obtained data are as follows:
Table 7
As can be seen from the above data, the acrylic acid esters co-polymer for the high crosslinking that the present invention synthesizes is imitated in the thickening of water phase
Rate is higher than cellulose thickener and other crosslinker component products.
Embodiment 6
The acrylic acid esters co-polymer of the high crosslinking of above embodiments synthesis is tested in multi-color using formula, is surveyed
The main performance and test method of examination are as follows:
1) water-white test: priming is applied together in 150x70mmCCA plate with banister brush, is placed under standard environment and conserves for 24 hours；
Together with roller roller coating mass-tone paint, dry 6h under standard environment, then roller coating mass-tone paint is together, is placed under standard environment
Drying overnight；With multicolor finish spray gun even application multicolor finish, quantity for spray is 0.45-0.53g/ plate；Template is placed in standard
Under environment it is dry for 24 hours after, immersion for 24 hours, observes the degree of whitening of template, give a mark by degree is whitened from 1 to 5,1 point be it is worst, 5 points
It is best.The standard environment occurred herein is 23 ± 2 DEG C of temperature, humidity 50%
Environment.
2) particle shape is observed: particle shape give a mark from 1 to 5,1 point to be worst, 5 points be it is best, 1 point of particle easily at
Paste, 5 points of particle adhesion, easily at graininess.
3) stability test: after prepared multi-color is conserved 1 month under standard environment, the change of its KU value is tested
Change.
The formula composition of dispersed phase is as follows:
Table 8
The step of dispersed phase prepared using this formula, is as follows:
1) by portions of de-ionized water, defoaming agent, cellulose or this patent polymer, pH adjusting agent, dispersing agent, mould inhibitor,
Fungicide, antifreezing agent mixing, is stirred until homogeneous state；
2) pigments and fillers, high speed dispersion to fineness≤50 μm are slow added into；
3) anionic emulsion, remaining deionized water, coalescing agent, protection sol solution is added, is uniformly mixed；
4) mill base is added, is uniformly mixed and obtains dispersed phase.
Above 7 samples are counted with the viscosity for the dispersed phase that the test of IV type of stormer viscosity meter STM- is prepared respectively
According to as follows:
Table 9
| Sample number into spectrum | B1 | A1 | A2 | A3 | A4 | A5 | A6 |
| Middle cut and paste degree/KU | 101 | 119 | 120 | 119 | 122 | 121 | 105 |
Embodiment 7
The formula composition of dispersed phase is as follows:
Table 10
The preparation steps and Application Example 7 of embodiment 8 are similar, and details are not described herein.
Above 7 samples are counted with the viscosity for the dispersed phase that the test of IV type of stormer viscosity meter STM- is prepared respectively
According to as follows:
Table 11
| Sample number into spectrum | B1 | A1 | A2 | A3 | A4 | A5 | A6 |
| Middle cut and paste degree/KU | 95 | 114 | 115 | 114 | 116 | 115 | 101 |
Embodiment 9
The formula composition of dispersed phase is as follows:
Table 12
The preparation steps and Application Example 6 of embodiment 8 are similar, and details are not described herein.
Above 7 samples are counted with the viscosity for the dispersed phase that the test of IV type of stormer viscosity meter STM- is prepared respectively
According to as follows:
Table 12
| Sample number into spectrum | B1 | A1 | A2 | A3 | A4 | A5 | A6 |
| Middle cut and paste degree/KU | 101 | 119 | 120 | 119 | 122 | 121 | 106 |
Embodiment 9
The formula composition of dispersed phase is as follows:
Table 14
The preparation steps and Application Example 6 of embodiment 9 are similar, and details are not described herein.
Above 7 samples are counted with the viscosity for the dispersed phase that the test of IV type of stormer viscosity meter STM- is prepared respectively
According to as follows:
Table 15
| Sample number into spectrum | B1 | A1 | A2 | A3 | A4 | A5 | A6 |
| Middle cut and paste degree/KU | 105 | 124 | 125 | 124 | 126 | 125 | 112 |
Embodiment 10
Multi-color is prepared, the comprehensive evaluating of performance is carried out.
Water-soluble colorful coating, including dispersed phase, protection sol solution and continuous phase, the mass ratio between three are as follows: 30:30:
40。
1, the preparation of sol solution is protected
7 parts of S482 are added in 93 parts of deionized waters, is dispersed to is completely dissolved to colourless transparent solution under high velocity agitation,
It is spare.
2, the preparation of dispersed phase
It is derived from the prepared dispersed phase of Application Example 1 and is slowly added into mill base in the final step of preparation, adjust to pre-
The color first designed is mixed to uniform state, spare.
3, the preparation of continuous phase
Continuous phase is prepared in accordance with the following steps: by above-mentioned deionized water, lotion, coalescing agent, defoaming agent, fungicide prevents
Mould dose, antifreezing agent mixes, and moderate-speed mixer to uniform state is spare.
4, it is granulated
Dispersed phase and 30 parts of protection sol solutions after 30 parts are mixed colours mix, and feed the mixture into Granulation Equipments,
The mixture that dispersed phase color spot is suspended in protection sol solution is obtained, it is spare.
5, continuous phase is added
40 parts are continuously added in granulation mixture, in the case where stirring at low speed, addition thickener (A401)
0.57 part, complete the preparation of multi-color.
Dispersed phase particles are observed with the viscosity of the dispersed phase of stormer viscosity measurement trial to above 7 samples respectively
State, it is as follows to obtain data:
Table 16
| Sample number into spectrum | B1 | A1 | A2 | A3 | A4 | A5 | A6 |
| Middle cut and paste degree/KU | 74 | 79 | 80 | 79 | 81 | 80 | 77 |
| Dispersed phase particles state | 3 | 5 | 4 | 5 | 4 | 5 | 4 |
| It is water-white | 2 | 4 | 5 | 4 | 5 | 5 | 3 |
| Stability (KU changing value) | 10 | 6 | 6 | 6 | 6 | 5 | 8 |
According to the acrylic acid esters co-polymer of high crosslinking prepared by the method for this patent, shown in aqueous colorful Qi Zhongzhong
For example high thickening efficiency of excellent performance, water-whitening resistance energy, good Miscibility and storage stability etc..
Above-described embodiment is the preferable implementation method of the present invention, but the present invention is not limited by above-mentioned implementation method, other
It is any to should be equivalent displacement side without departing from change made under Spirit Essence and principle of the invention, modification, simplified, replacement
Formula is included within the scope of the present invention.
Claims (9)
1. a kind of high cross-linked acrylic acid lipin polymer passes through the freedom of the monomer composition in a solvent including following monomer
The precipitation polymerization that base class initiator causes obtains:
A) 10-80wt%, preferably 20-70wt%, the first monomer group of more preferable 30-60wt%, further preferred 40-55wt%
Point, it is selected from one of olefinic list unsaturated monomer containing at least one carboxylic acid group or a variety of；
B) 89.9-15wt%, preferably 79%-29wt%, more preferable 69%-29wt%, the second of further preferred 59-44wt%
Olefinic list unsaturated monomer component, one of straight chain or the C1-C4 hydroxyalkyl acrylate of branching selected from (methyl) acrylic acid
Or it is a variety of；
C) 0.01-5wt%, preferably 0.1-3wt%, the crosslinking group of more preferable 0.3-2wt%, further preferred 0.5-1.5wt%
Point, it is selected from the polyalkenyl polyethers at least two polymerizable ethylenical unsaturated double bonds,
The wt% is counted on the basis of the gross mass of all three classes monomers.
2. high cross-linked acrylic acid lipin polymer according to claim 1, wherein the alkene containing at least one carboxylic acid group
Belong to single unsaturated monomer be selected from acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid or maleic acid and its
One of salt is a variety of.
3. high cross-linked acrylic acid lipin polymer according to claim 1 or 2, wherein the straight chain of (methyl) acrylic acid or
The C1-C4 hydroxyalkyl acrylate of branching is selected from (methyl) acrylate, (methyl) hydroxy-ethyl acrylate, (methyl) acrylic acid hydroxyl
One of propyl ester, (methyl) acrylic acid -4- hydroxy butyl ester are a variety of.
4. high cross-linked acrylic acid lipin polymer according to any one of claim 1-3, wherein can at least two
Polymerize ethylenical unsaturated double bonds polyalkenyl polyethers be selected from allyl alcohol with 2-15 carbon atom straight chain or branching
The etherification product of polyalcohol, wherein the polyalcohol be selected from sucrose, pentaerythrite, dipentaerythritol, trimethylolpropane and its
One of dimer, triethylol propane and its dimer are a variety of, such as selected from pentaerythritol diallyl ether, Ji Wusi
Alcohol triallyl ether, pentae-rythritol tetraallyl ether, trimethylolpropane allyl ether and trimethylolpropane tris allyl
Ether.
5. high cross-linked acrylic acid lipin polymer described in any one of -4 according to claim 1, wherein solvent be selected from hydro carbons,
One of esters are a variety of, and hydro carbons is preferably selected from one of n-hexane, hexamethylene, normal heptane, cycloheptane, n-decane or more
Kind；Esters are selected from one of ethyl acetate, butyl acetate, ethyl propionate, butyl propionate or a variety of.
6. high cross-linked acrylic acid lipin polymer according to any one of claims 1-5, wherein radical type initiator
Selected from one of organic peroxide class compound, azo compound, inorganic peroxysulfate class compound and hydrogen peroxide or
It is a variety of, it is preferably selected from azodiisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, dilauroyl peroxide, ammonium persulfate, mistake
One of sodium sulphate, hydrogen peroxide are a variety of.
7. the preparation method of high cross-linked acrylic acid lipin polymer of any of claims 1-6, this method include with
Lower step:
A. solvent, olefinic list unsaturated monomer containing at least one carboxylic acid group, (methyl) acrylic acid are added in a reservoir
Straight chain or the C1-C4 hydroxyalkyl acrylate and cross-linking component of branching are passed through nitrogen, open stirring；
B. initiator is added into container, is reacted；
C. it to fully reacting, then adds part initiator and eliminates residual monomer, then cool down filtering and discharging；
D. filtering product is cleaned and is dried, obtain required powder product.
8. preparation method according to claim 7, wherein the reaction temperature of step b is 40-130 DEG C, preferably 50-110
DEG C, more preferable 60-100 DEG C.
9. high cross-linked acrylic acid lipin polymer of any of claims 1-6 is used as aqueous colorful paint system thickener
Purposes.
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| CN113072832A (en) * | 2020-01-06 | 2021-07-06 | 万华化学集团股份有限公司 | Combined rheology modifier and preparation method and application thereof |
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| CN116075532A (en) * | 2020-09-07 | 2023-05-05 | 爱森集团 | Use of copolymers obtained by precipitation polymerization in hydroalcoholic compositions |
| CN114195943A (en) * | 2021-12-17 | 2022-03-18 | 万华化学集团股份有限公司 | Carbomer thickening agent capable of being quickly wetted and dispersed and preparation method thereof |
| CN114195943B (en) * | 2021-12-17 | 2023-12-19 | 万华化学集团股份有限公司 | Carbomer thickener capable of being rapidly wetted and dispersed and preparation method thereof |
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