CN115466346A - Preparation method of polymer thickener in polar solvent - Google Patents
Preparation method of polymer thickener in polar solvent Download PDFInfo
- Publication number
- CN115466346A CN115466346A CN202211197616.3A CN202211197616A CN115466346A CN 115466346 A CN115466346 A CN 115466346A CN 202211197616 A CN202211197616 A CN 202211197616A CN 115466346 A CN115466346 A CN 115466346A
- Authority
- CN
- China
- Prior art keywords
- mass
- solvent
- polar
- polymer thickener
- polar solvent
- 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.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 63
- 239000002562 thickening agent Substances 0.000 title claims abstract description 38
- 239000002798 polar solvent Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 239000000047 product Substances 0.000 claims abstract description 60
- 239000000178 monomer Substances 0.000 claims abstract description 38
- 239000012046 mixed solvent Substances 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000003999 initiator Substances 0.000 claims abstract description 19
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- 238000009826 distribution Methods 0.000 claims abstract description 16
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- -1 salt ions Chemical class 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 11
- 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 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 229940086737 allyl sucrose Drugs 0.000 claims description 5
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 4
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
- 239000001923 methylcellulose Substances 0.000 claims description 4
- 235000010981 methylcellulose Nutrition 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229950006451 sorbitan laurate Drugs 0.000 claims description 4
- 235000011067 sorbitan monolaureate Nutrition 0.000 claims description 4
- 229950011392 sorbitan stearate Drugs 0.000 claims description 4
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 claims description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 239000001593 sorbitan monooleate Substances 0.000 claims description 3
- 235000011069 sorbitan monooleate Nutrition 0.000 claims description 3
- 229940035049 sorbitan monooleate Drugs 0.000 claims description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-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
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-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
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- 239000012454 non-polar solvent Substances 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 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
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- HFUSECPXGUISGB-UHFFFAOYSA-N benzoyl benzenecarboperoxoate;2-tert-butylperoxy-2-methylpropane Chemical compound CC(C)(C)OOC(C)(C)C.C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 HFUSECPXGUISGB-UHFFFAOYSA-N 0.000 claims 1
- OEDAJYOQELMMFC-UHFFFAOYSA-N octadecanoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CCCCCCCCCCCCCCCCCC(O)=O OEDAJYOQELMMFC-UHFFFAOYSA-N 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 14
- 230000008719 thickening Effects 0.000 abstract description 9
- 238000010998 test method Methods 0.000 description 35
- 239000000243 solution Substances 0.000 description 29
- 238000012360 testing method Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 10
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 6
- 229920002521 macromolecule Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- ZWLQACFYTXLLEJ-UHFFFAOYSA-N butan-1-ol;methanol Chemical compound OC.CCCCO ZWLQACFYTXLLEJ-UHFFFAOYSA-N 0.000 description 4
- 230000015784 hyperosmotic salinity response Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- AINBZKYUNWUTRE-UHFFFAOYSA-N ethanol;propan-2-ol Chemical compound CCO.CC(C)O AINBZKYUNWUTRE-UHFFFAOYSA-N 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- ZMQBBPRAZLACCW-UHFFFAOYSA-N acetic acid;dichloromethane Chemical compound ClCCl.CC(O)=O ZMQBBPRAZLACCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RTEXIPZMMDUXMR-UHFFFAOYSA-N benzene;ethyl acetate Chemical compound CCOC(C)=O.C1=CC=CC=C1 RTEXIPZMMDUXMR-UHFFFAOYSA-N 0.000 description 1
- XHWUYHQNLYFFDO-UHFFFAOYSA-N butyl acetate;toluene Chemical compound CC1=CC=CC=C1.CCCCOC(C)=O XHWUYHQNLYFFDO-UHFFFAOYSA-N 0.000 description 1
- 229960001631 carbomer Drugs 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- MAAQWJCOOBQJRP-UHFFFAOYSA-N cyclohexane;propanoic acid Chemical compound CCC(O)=O.C1CCCCC1 MAAQWJCOOBQJRP-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- BHBKJSBTRATHKT-UHFFFAOYSA-N hexane;methyl acetate Chemical compound COC(C)=O.CCCCCC BHBKJSBTRATHKT-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PHZDEABCWBMSDT-UHFFFAOYSA-N n,n-dimethylformamide;hexane Chemical compound CN(C)C=O.CCCCCC PHZDEABCWBMSDT-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
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
- 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
- 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
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of a polymer thickener in a polar solvent, which comprises the following step of sectional dropwise adding process: s1, adding a mixed solvent of a polar organic solvent and a nonpolar organic solvent, an alpha, beta-unsaturated monomer, a hydrophobic monomer and a dispersing agent into a reaction vessel in a nitrogen environment; s2, dropwise adding an initiator after the solution obtained in the step S1 is stable in reaction; s3, after the dropwise addition in the step S2 is finished, dropwise adding a cross-linking agent; s4, after the dropwise adding is finished, heating and maintaining the temperature until the particle size of the precipitate is 20-50 mu m, finishing the reaction, filtering and drying to obtain a product; the preparation method of the polymer thickener in the polar solvent has the advantages that the polymer has uniform particle size distribution, can be rapidly dispersed and thickened in various polar solvents, has excellent light transmittance, and can still keep good thickening property and light transmittance in the presence of salt ions.
Description
Technical Field
The invention relates to the field of new material preparation and thickening agents, in particular to a preparation method of a polymer thickening agent in a polar solvent.
Background
In the current thickener market, alpha, beta-unsaturated carboxylic acid polymers, especially polyacrylic acid homopolymers or polyacrylic acid (polyacrylate) copolymers have good thickening property and improved thixotropy and stability of a coagulation system, and are widely applied to the fields of daily chemicals, medical sanitation, personal care products and the like. Such polymeric thickeners are generally prepared by free radical precipitation polymerization or suspension polymerization processes using α, β -unsaturated carboxylic acids, α, β -unsaturated amides or α, β -unsaturated carboxylic acid esters as monomers.
However, the structure of the alpha, beta-unsaturated carboxylic acid polymer generally contains carboxylic acid groups and has strong hydrophilic ability, if the alpha, beta-unsaturated carboxylic acid polymer is directly, continuously and quickly put into a system to be dispersed for stirring, the alpha, beta-unsaturated carboxylic acid polymer is quickly combined with a solvent in the system to be dispersed to form a solvent protective film, the polymer is coated in a block shape, so that the inner part of the polymer product is prevented from being soaked, the dispersion speed of the thickening agent completely depends on the penetration speed of the solvent into the protective film, and the quick dispersion of the thickening agent cannot be realized. Although dispersion of the polymer can be accelerated industrially by increasing the mechanical shear rate, the polymer dispersion is destroyed by the action of the homogenizer at high shear rates, resulting in permanent viscosity loss. Meanwhile, the use of industrial high-speed homogenizers and blenders will undoubtedly increase the cost.
On the other hand, the thickening mechanism of the alpha, beta-unsaturated carboxylic acid polymer thickener is neutralization thickening, namely, neutralization is carried out on the thickener by using an alkaline substance, so that polymer macromolecules are ionized, negative charges are generated along the main chain of the polymer, and the like charges repel each other, so that the polymer molecules are greatly stretched and spread to reach a reticular expansion structure, and the solution viscosity is increased sharply. This results in a low resistance of such polymer thickening to salt ions in the solution, and the viscosity and light transmittance of the thickened solution are significantly reduced in the presence of the salt ions.
Meanwhile, the research and application of the alpha, beta-unsaturated carboxylic acid polymer thickener are mainly carried out by taking water as a dispersion system, and the research and application of other polar solvents are less. Currently, the demand for personal care products such as alcohol gels is rapidly increasing under the influence of global new crown epidemics. Meanwhile, in the field of industrial production, the need for thickening and emulsifying of solvents with different polarities such as isopropanol, butanol and the like also exists.
Patent CN01817899.5 discloses a rheology modified copolymer, which adopts hydrophobic monomer and molecular weight regulator to achieve the salt tolerance improvement of the product, but it cannot achieve the uniform improvement of light transmittance and viscosity under the condition of salt.
Patent CN10191022A discloses an acrylic acid/alkyl methacrylate copolymer, which uses hydrophobic monomer and cross-linking agent to achieve salt tolerance of the product, and can maintain higher viscosity under the condition of high sodium chloride concentration, but it cannot achieve uniform improvement of light transmittance and viscosity.
Patent CN104861104B discloses a quick wetting carboxylic acid copolymer thickener, which adopts a step-by-step feeding process, wherein the salt tolerance of the product is improved by step-by-step dropping of monomers and cross-linking agents, and the product can keep better viscosity and light transmittance under the condition of higher sodium chloride concentration, but the product cannot achieve the effect of thickening in polar solvents such as methanol, ethanol, isopropanol and the like, and the step-by-step feeding process does not use a particle size analyzer to measure the size of the precipitated product on line, and meanwhile, the step-by-step dropping time is uncertain, and the experimental repeatability is poor.
Disclosure of Invention
The invention aims to provide a preparation method of a polymer thickener in a polar solvent, and the technical scheme adopted for realizing the aim of the invention is as follows: the method comprises the following process steps of sectional dripping:
s1, adding a mixed solvent of a polar organic solvent and a non-polar organic solvent, an alpha, beta-unsaturated monomer, a hydrophobic monomer and a dispersant into a reaction vessel in a nitrogen environment;
s2, dropwise adding an initiator after the solution obtained in the step S1 is stable in reaction;
s3, after the dropwise addition in the step S2 is finished, dropwise adding a cross-linking agent;
s4, after the dropwise addition is finished, heating and maintaining the temperature until the particle size distribution of the precipitate is 20-50 mu m, finishing the reaction, filtering and drying to obtain a product;
further, in step S1, the polar solvent is one or more of acetic acid, propionic acid, N-dimethyl sulfoxide, methyl acetate, ethyl acetate and butyl acetate, preferably acetic acid and/or ethyl acetate; the mass of the polar organic solvent is 20-80% of that of the mixed solvent, and preferably 35-65%.
Further, in the step S1, the nonpolar solvent is one or more of benzene, toluene, hexane, cyclohexane and dichloromethane, and preferably dichloromethane and/or cyclohexane; the mass of the nonpolar organic solvent is 20-80% of the mass of the mixed solvent, and preferably 35-65%.
Further, in the step S1, the α, β -unsaturated monomer is one or more of methacrylic acid, acrylic acid, crotonic acid, maleic acid, acrylamide and methacrylamide, and is preferably acrylic acid and/or acrylamide; the mass of the alpha, beta-unsaturated monomer is 1-50% of that of the mixed solvent, and preferably 5-30%.
Further, in step S1, the hydrophobic monomer is one or more of methyl methacrylate, methyl acrylate, isobutyl acrylate, tert-butyl acrylate, lauryl acrylate and stearic acrylate, preferably methyl methacrylate and/or stearic acrylate; the mass of the hydrophobic monomer is 1-30% of that of the mixed solvent, and preferably 5-20%.
Further, in the step S1, the dispersant is one or more of sorbitan laurate, sorbitan monooleate, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan stearate, methyl cellulose and hydroxyethyl cellulose, and is preferably polyoxyethylene sorbitan stearate and/or methyl cellulose; the mass of the dispersant is 0.5-10% of the total mass of the monomers, and preferably 1-5%.
Specifically, the total mass of the monomers is the sum of the mass of the alpha, beta-unsaturated monomer and the mass of the hydrophobic monomer.
Further, the reaction temperature in the step S1 is 50-80 ℃, preferably 55-75 ℃, and the reaction time is 2h.
Further, in the step S2, the initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide tert-butyl ester and methyl ethyl ketone peroxide, and preferably azobisisobutyronitrile and/or benzoyl peroxide; the mass of the initiator is 0.05-5% of the total mass of the monomers, preferably 0.1-2%, and the mass concentration of the initiator solution is 0.5-5%, preferably 0.8-3%.
Further, in the step S3, the crosslinking agent is one or more of allyl sucrose ether, triallyl isocyanurate, ethylene glycol dimethacrylate and pentaerythritol triallyl ether, and is preferably ethylene glycol dimethacrylate and/or pentaerythritol triallyl ether; the mass of the cross-linking agent is 0.1-5% of the total mass of the monomers, preferably 0.2-3%, and the mass concentration of the cross-linking agent solution is 0.5-5%, preferably 1-3%.
Further, in the steps S2 and S3, the reaction temperature is 50-80 ℃, preferably 55-75 ℃, and the time for dripping the initiator and the cross-linking agent is 2 hours respectively.
Further, in the step S4, the temperature is raised after the completion of the dropwise addition, and the reaction temperature after the temperature rise is 60 to 90 ℃, preferably 70 to 85 ℃.
Further, the polar solvent thickened by the polymer thickener is one or a mixture of water, methanol, ethanol, isopropanol and n-butanol in any proportion; preferably water and/or ethanol, and in the case of water and ethanol, they are mixed in any proportion.
According to the invention, by introducing the hydrophobic monomer, the hydrophilicity of the alpha, beta-unsaturated carboxylic acid polymer is reduced, the hydration of the polymer in a solvent is reduced, an external polar solvent can permeate into the particles, the rapid wetting is realized, the dispersion time is obviously reduced, and meanwhile, the associative thickening capability of the polymer is increased to a certain extent by introducing the hydrophobic monomer, so that the polymer has the electrolyte resistance capability.
In addition, by using a segmented dropwise adding process, firstly, raising the reaction temperature of a reaction solvent, a monomer and a dispersing agent, fully stirring, and after the reaction solvent, the monomer and the dispersing agent are stabilized, dropwise adding an initiator into the system, wherein the purpose is to control the decomposition rate of the initiator and slowly initiate the initiator, so that the reaction rate is controlled, a polymer product with relatively uniform molecular weight distribution is obtained, the uniform particle size distribution is characterized by online particle size measurement, and the reaction is determined to be finished when the particle size reaches 20-50 mu m; it should be noted that, if the traditional process is used, the step-by-step dripping is not adopted, the particle size distribution of the product is 50-500 μm, and the particle size distribution is very wide; and by using a step-by-step dripping process, the particle size distribution of the product is 20-50 mu m when the reaction lasts for 2 hours, and the reaction is stopped at the moment, so that the particle size distribution of the product can be determined.
And finally, dropwise adding a cross-linking agent after the dropwise adding of the initiator is finished, so that the uniform polymer macromolecule chain is subjected to three-dimensional cross-linking, and the characterization is carried out by a scanning electron microscope to verify that the polymer macromolecule chain has a spatial three-dimensional structure.
If the cross-linking agent is firstly dripped and then the initiator is dripped, the method is not different from the method of directly mixing the monomer and the cross-linking agent and then dripping the initiator, therefore, the initiator is firstly dripped to cause free radicals to appear in the reaction, chain reaction is started, the cross-linking agent is dripped after the dripping of the initiator is finished, the free radicals still exist in the reaction system, and the macromolecule is cross-linked under the condition that the reaction activity still exists.
And because the molecular weight of the polymer obtained by free radical polymerization is often very large and cannot be characterized by using a conventional method, but the molecular weight is related to the particle size distribution, the invention determines whether the product finally meets the requirement by determining the particle size.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the method for preparing the polar solvent polymer thickener, the hydrophobic monomer is introduced, so that the dispersion time of the copolymer thickener in a polar dispersion system is greatly shortened, and the production cost is saved; the associative thickening capacity of the polymer is increased to a certain extent, so that the polymer has the capacity of resisting electrolyte;
(2) The method of the polar solvent polymer thickener adopts a sectional dripping process to obtain a polymer product with controllable particle size and uniform distribution; the light transmittance of the thickening agent in a polar solvent is improved, the molecular weight of the polymer is increased, and the viscosity in the polar solvent is further increased;
(3) The method for preparing the polar solvent polymer thickener can realize rapid dispersion in different polar solvents such as water, methanol, ethanol, isopropanol, n-butanol and the like, keeps better viscosity and light transmittance and has certain universality.
Drawings
FIG. 1 is the three-dimensional structure of the product of example 1 of the invention after swelling in water;
FIG. 2 is the three-dimensional structure of the product of example 1 of the present invention after swelling in 75% ethanol-water;
FIG. 3 is a three-dimensional structure of the product of example 1 of the present invention after swelling in 50% methanol-n-butanol.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, were all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
First, the test criteria of the embodiments of the present invention are explained: the viscosity of the corresponding thickening agent in 0.5% aqueous solution with the concentration of 4.0 multiplied by 10 is required to be tested according to the light industry standard QB/T4530-2013 carbomer resin of the people's republic of China 4 -6.0×10 4 The corresponding light transmittance should reach more than or equal to 85 percent.
Test method 1:0.5% by mass of polar solvent Dispersion time test
497.5g of solvent with different polarity is accurately weighed into a 1000mL beaker, and 2.5g of polymer product is quickly and uniformly sprinkled on the surface of the solvent in a standing state, and timing is started at the same time, and is ended after the polymer product is completely settled. Here, the polar solvent is water, methanol, ethanol, isopropanol, n-butanol, 50% methanol-water solution, 50% ethanol-water solution, 75% ethanol-water solution, 50% methanol-n-butanol mixed solution, 90% ethanol-isopropanol mixed solution (the percentages are mass fractions), respectively.
The test method 2:0.5% mass concentration polar solution viscosity test
497.5g of a solvent of different polarity is accurately weighed into a 1000mL beaker, 2.5g of the polymer product is sprinkled rapidly and uniformly on the surface of the solvent in a standing state, and after the polymer product has completely settled down, 4.0g of triethanolamine is added to the solution to neutralize the polymer. Here, the polar solvent is water, methanol, ethanol, isopropanol, n-butanol, 50% methanol-water solution, 50% ethanol-water solution, 75% ethanol-water solution, 50% methanol-n-butanol mixed solution, 90% ethanol-isopropanol mixed solution (all mass fractions). The solution was then transferred to a centrifuge tube and centrifuged at 5000rpm for 30min for defoaming treatment. After centrifugation the solution was transferred to a beaker and the viscosity of the solution was measured using a BrookfieldDV2TRV type rotational viscometer at 20 rpm.
Test method 3:0.5% mass concentration polar solution light transmittance test
The centrifuged solution obtained in test method 2 was placed in a 5mL UV spectrophotometer cell, and the transmittance at 420nm was measured using a Shimadzu UV-1800 UV spectrophotometer with each solvent as a reference.
Test method 4: salt tolerance test in 0.5% aqueous solution
497.5g of 0.9% saline solution was accurately weighed into a 1000mL beaker, 2.5g of the polymer product was quickly and uniformly sprinkled on the surface of the solvent in a static state, and 4.0g of triethanolamine was added to neutralize the polymer after the polymer product was completely settled. The solution was then transferred to a centrifuge tube and centrifuged at 5000rpm for 30min for defoaming treatment. After centrifugation the solution was transferred to a beaker and the viscosity of the solution was measured using a Brookfield DV2TRV type rotational viscometer at 20 rpm. The centrifuged solution was placed in a 5mL UV spectrophotometer and the transmittance at 420nm was measured using a Shimadzu UV-1800 UV spectrophotometer with 0.9% saline as a reference.
Test method 5: scanning electron microscope
The product of example 1 was prepared as described in test method 1 in aqueous solution, 75% ethanol-water solution and 50% methanol-n-butanol solution and stirred at 80 ℃ to fully swell the thickener. The solution is then freeze-dried to give a macromolecular thickener powder with fully swollen molecular weight and frozen segments. Scanning electron microscope shooting is carried out on the obtained product, and the results are respectively shown in fig. 1, fig. 2 and fig. 3.
Example 1
1000g of an acetic acid-dichloromethane mixed solvent (mass ratio: 35. Then 1.0g of azobisisoheptonitrile was accurately weighed, dissolved in 19g of the mixed solvent and added dropwise to the reaction system for 2 hours, with the reaction temperature maintained at 50 ℃. Accurately weighing 1.0g of ethylene glycol dimethacrylate, dissolving the ethylene glycol dimethacrylate in 19g of mixed solvent, dropwise adding the mixture into a reaction system for 2 hours, and maintaining the reaction temperature at 50 ℃. After the end of the dropwise addition, the reaction temperature was raised to 60 ℃ and the reaction was continued for 2 hours, the particle size distribution of the polymer being 20-50 μm as measured with a Mettler Toledo Easy Viewer400 on-line particle sizer. After the reaction was complete, the product was filtered, the solid collected, dried in vacuo, weighed, and the yield was 95.7%. The resulting product was tested as described in test method 1 and the results are shown in table 1. The resulting products were subjected to the tests described in test method 2 and test method 3, respectively, and the results are shown in table 2. The resulting product was tested as described in test method 4 and the results are shown in table 3.
Example 2
500g of propionic acid-cyclohexane mixed solvent (mass ratio 65. Then 0.2g of benzoyl peroxide tert-butyl ester is accurately weighed and dissolved in 39.8g of mixed solvent and is dropwise added into the reaction system for 2 hours, and the reaction temperature is maintained at 80 ℃. Accurately weighing 0.4g of allyl sucrose ether, dissolving in 79.6g of mixed solvent, dropwise adding into the reaction system for 2 hours, and maintaining the reaction temperature at 80 ℃. After the end of the dropwise addition, the reaction temperature was raised to 90 ℃ and the reaction was continued for 2 hours, the particle size distribution of the polymer was measured at 20 to 50 μm using a Mettler Toledo Easy Viewer400 on-line particle sizer. After the reaction was complete, the product was filtered, the solid collected, dried in vacuo, weighed, and the yield was 94.1%. The resulting product was tested as described in test method 1 and the results are shown in table 1. The resulting products were subjected to the tests described in test method 2 and test method 3, respectively, and the results are shown in table 2. The resulting product was tested as described in test method 4 and the results are shown in table 3.
Example 3
A2000 mL four-necked flask was sequentially charged with 1000g of N, N-dimethylformamide-hexane mixed solvent (mass ratio: 40: 60), 50g of maleic acid, 50g of acrylamide, 100g of t-butyl acrylate, and 2g of sorbitan monooleate, mechanically stirred under nitrogen protection, slowly heated to 70 ℃ and kept warm for 2 hours. Then 1.0g of benzoyl peroxide is accurately weighed and dissolved in 19g of mixed solvent and is dripped into the reaction system for 2 hours, and the reaction temperature is maintained at 70 ℃. Accurately weighing 2.0g of pentaerythritol triallyl ether, dissolving the pentaerythritol triallyl ether in 19g of mixed solvent, dropwise adding the mixed solvent into a reaction system for 2 hours, and maintaining the reaction temperature at 70 ℃. After the end of the dropwise addition, the reaction temperature was raised to 80 ℃ and the reaction was continued for 2 hours, the particle size distribution of the polymer being 20-50 μm as measured by a Mettler Toledo Easy Viewer400 on-line particle sizer. After the reaction was complete, the product was filtered, the solid collected, dried in vacuo, weighed, and the yield 93.9%. The product obtained was tested as described in example 1 and the results are shown in table 1. The resulting product was tested as described in test method 1 and the results are shown in table 1. The resulting products were subjected to the tests described in test method 2 and test method 3, respectively, and the results are shown in table 2. The resulting product was tested as described in test method 4 and the results are shown in table 3.
Example 4
1000g of ethyl acetate-benzene mixed solvent (mass ratio: 50. Then, 0.1g of azobisisobutyronitrile was accurately weighed and dissolved in 9.9g of the mixed solvent and added dropwise to the reaction system over 2 hours, and the reaction temperature was maintained at 60 ℃. Accurately weighing 2.0g of triallyl isocyanurate, dissolving the triallyl isocyanurate in 19g of mixed solvent, dropwise adding the solution into a reaction system for 2 hours, and maintaining the reaction temperature at 60 ℃. After the end of the dropwise addition, the reaction temperature was raised to 70 ℃ and the reaction was continued for 2 hours, and the polymer particle size distribution was measured at 20 to 50 μm using a Mettler Toledo Easy Viewer400 on-line particle sizer. After the reaction was complete, the product was filtered, the solid collected, dried in vacuo, weighed, and the yield was 94.0%. The resulting product was tested as described in example 1 and the results are shown in table 1. The resulting product was tested as described in test method 1 and the results are shown in table 1. The resulting products were subjected to the tests described in test method 2 and test method 3, respectively, and the results are shown in table 2. The resulting product was tested as described in test method 4 and the results are shown in table 3.
Example 5
A2000 mL four-necked flask was charged with 1000g of a butyl acetate-toluene mixed solvent (mass ratio 65. 1.5g of azobisisobutyronitrile was then accurately weighed, dissolved in 28.5g of the mixed solvent and added dropwise to the reaction system over 2 hours, the reaction temperature was maintained at 60 ℃. Accurately weighing 1.5g of triallyl isocyanurate, dissolving the triallyl isocyanurate in 28.5g of mixed solvent, dropwise adding the solution into a reaction system for 2 hours, and maintaining the reaction temperature at 60 ℃. After the end of the dropwise addition, the reaction temperature was raised to 70 ℃ and the reaction was continued for 2 hours, the particle size distribution of the polymer being 20-50 μm as measured by a Mettler Toledo Easy Viewer400 on-line particle sizer. After the reaction was complete, the product was filtered, the solid collected, dried in vacuo, weighed, and the yield was 95.0%. The resulting product was tested as described in example 1 and the results are shown in table 1. The resulting product was tested as described in test method 1 and the results are shown in table 1. The resulting products were subjected to the tests described in test method 2 and test method 3, respectively, and the results are shown in table 2. The resulting product was tested as described in test method 4 and the results are shown in table 3.
Example 6
Into a 2000mL four-necked flask were sequentially added 1000g of a methyl acetate-hexane mixed solvent (mass ratio 50. Then, 4.0g of methyl ethyl ketone peroxide was accurately weighed and dissolved in 76g of the mixed solvent and added dropwise to the reaction system over 2 hours with the reaction temperature maintained at 80 ℃. Accurately weighing 2.0g of allyl sucrose ether, dissolving the allyl sucrose ether in 38g of mixed solvent, dropwise adding the mixture into a reaction system for 2 hours, and maintaining the reaction temperature at 80 ℃. After the end of the dropwise addition, the reaction temperature was raised to 90 ℃ and the reaction was continued for 2 hours, the particle size distribution of the polymer being 20-50 μm as measured with a Mettler Toledo Easy Viewer400 on-line particle sizer. After the reaction was complete, the product was filtered, the solid collected, dried in vacuo and weighed, yielding 93.5%. The resulting product was tested as described in example 1 and the results are shown in table 1. The resulting product was tested as described in test method 1 and the results are shown in table 1. The resulting products were subjected to the tests described in test method 2 and test method 3, respectively, and the results are shown in table 2. The resulting product was tested as described in test method 4 and the results are shown in table 3.
Table 1 different products test method 1 test results
Table 2 different products test method 2 and test method 3 test results
Table 3 different products test method 4 test results
| Viscosity (cP) | Light transmittance (%) | |
| Example 1 | 48200 | 94.9 |
| Example 2 | 47200 | 94.6 |
| Example 3 | 48600 | 93.5 |
| Example 4 | 49200 | 93.1 |
| Example 5 | 48000 | 94.0 |
| Example 6 | 51000 | 93.3 |
In summary, the thickeners prepared in examples 1 to 6 can achieve fast dispersion (less than 300 seconds) in different polar solvents such as water, methanol, ethanol, isopropanol, n-butanol, and the like, and maintain good viscosity and light transmittance, and all preparations meet the standard range, and have certain universality.
From the results of fig. 1, 2 and 3, it is shown that the polymer macromolecule has a distinct three-dimensional cross-linked structure, and the structure is regular, and a clear and distinct reticular three-dimensional structure exists, which confirms that the thickener macromolecule prepared by the present invention has a three-dimensional cross-linked structure after being sufficiently swelled in the polar solvent.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (12)
1. A preparation method of a polymer thickener in a polar solvent is characterized by comprising the following step of sectional dropwise adding process:
s1, adding a mixed solvent of a polar organic solvent and a nonpolar organic solvent, an alpha, beta-unsaturated monomer, a hydrophobic monomer and a dispersing agent into a reaction vessel in a nitrogen environment;
s2, dropwise adding an initiator after the solution obtained in the step S1 is reacted stably;
s3, after the dropwise addition in the step S2 is finished, dropwise adding a cross-linking agent;
s4, after the dropwise addition is finished, heating and maintaining the temperature until the particle size distribution of the precipitate is 20-50 mu m, finishing the reaction, filtering and drying to obtain a product;
wherein the polar solvent is one or more of acetic acid, propionic acid, N-dimethyl sulfoxide, methyl acetate, ethyl acetate or butyl acetate, and the mass of the polar organic solvent is 20-80% of that of the mixed solvent; the nonpolar solvent is one or more of benzene, toluene, hexane, cyclohexane or dichloromethane, and the mass of the nonpolar organic solvent is 20-80% of that of the mixed solvent; the alpha, beta-unsaturated monomer is one or more of methacrylic acid, acrylic acid, crotonic acid, maleic acid, acrylamide or methacrylamide, and the mass of the alpha, beta-unsaturated monomer is 1-50% of that of the mixed solvent; the hydrophobic monomer is one or more of methyl methacrylate, methyl acrylate, isobutyl acrylate, tert-butyl acrylate, lauryl acrylate or stearic acrylate, and the mass of the hydrophobic monomer is 1-30% of that of the mixed solvent; the dispersing agent is one or more of sorbitan laurate, sorbitan monooleate, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan stearate, methyl cellulose or hydroxyethyl cellulose, and the mass of the dispersing agent is 0.5-10% of the total mass of the monomers.
2. The method for preparing a polymer thickener in polar solvent according to claim 1, wherein the polar solvent is acetic acid and/or ethyl acetate in the step S1; the mass of the polar organic solvent is 35-65% of the mass of the mixed solvent.
3. The method for preparing a polymer thickener in polar solvent according to claim 1, wherein the non-polar organic solvent is dichloromethane and/or cyclohexane; the mass of the nonpolar organic solvent is 35-65% of the mass of the mixed solvent.
4. The method for preparing a polymer thickener in a polar solvent according to claim 1, wherein the α, β -unsaturated monomer is acrylic acid and/or acrylamide in the step S1; the mass of the alpha, beta-unsaturated monomer accounts for 5-30% of the mass of the mixed solvent.
5. The method for preparing a polymer thickener in polar solvent according to claim 1, wherein the hydrophobic monomer is methyl methacrylate and/or acrylic acid stearate in the step S1; the mass of the hydrophobic monomer is 5-20% of that of the mixed solvent.
6. The method for preparing a polymer thickener in a polar solvent according to claim 1, wherein the dispersant is polyoxyethylene sorbitan stearate and/or methylcellulose in the step S1; the mass of the dispersing agent is 1-5% of the total mass of the monomers.
7. The method for preparing a polymer thickener in a polar solvent as claimed in claim 1, wherein the reaction temperature in the step S1 is 50 to 80 ℃ and the reaction time is 2 hours.
8. The method of claim 1, wherein in the step S2, the initiator is one or more selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide-t-butyl peroxide, methyl ethyl ketone peroxide; the mass of the initiator is 0.05-5% of the total mass of the monomers, and the mass concentration of the initiator solution is 0.5-5%.
9. The method for preparing the polymer thickener in the polar solvent as claimed in claim 1, wherein the cross-linking agent in the step S3 is one or more of allyl sucrose ether, triallyl isocyanurate, ethylene glycol dimethacrylate, pentaerythritol triallyl ether; the mass of the cross-linking agent is 0.1-5% of the total mass of the monomers, and the mass concentration of the cross-linking agent solution is 0.5-5%.
10. The method for preparing a polymer thickener in a polar solvent according to claim 1, wherein the reaction temperature is 50 to 80 ℃ and the time for adding the initiator and the crosslinking agent is 2 hours each in the steps S2 and S3.
11. The method for preparing a polymer thickener in a polar solvent as claimed in claim 1, wherein the reaction temperature is increased to 60 to 90 ℃ after the completion of the dropping in the step S4.
12. The method for preparing the polymer thickener in polar solvent as claimed in claim 1, wherein the polar solvent thickened by the polymer thickener is one or a mixture of water, methanol, ethanol, isopropanol and n-butanol in any proportion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211197616.3A CN115466346B (en) | 2022-09-29 | 2022-09-29 | Preparation method of polymer thickener in polar solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211197616.3A CN115466346B (en) | 2022-09-29 | 2022-09-29 | Preparation method of polymer thickener in polar solvent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115466346A true CN115466346A (en) | 2022-12-13 |
| CN115466346B CN115466346B (en) | 2024-05-07 |
Family
ID=84335849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211197616.3A Active CN115466346B (en) | 2022-09-29 | 2022-09-29 | Preparation method of polymer thickener in polar solvent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115466346B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112538132A (en) * | 2020-12-08 | 2021-03-23 | 南京紫鸿生物科技有限公司 | Preparation method of thickening polymer suitable for alcohol system |
| CN112876596A (en) * | 2021-01-06 | 2021-06-01 | 广州市东雄化工有限公司 | Solution type alcohol disinfection gel thickening agent and preparation method thereof |
| CN114276492A (en) * | 2022-01-19 | 2022-04-05 | 广东星狮能源科技有限公司 | Anti-ultraviolet thickening agent, preparation method thereof and disinfection washing-free hand rubbing gel |
-
2022
- 2022-09-29 CN CN202211197616.3A patent/CN115466346B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112538132A (en) * | 2020-12-08 | 2021-03-23 | 南京紫鸿生物科技有限公司 | Preparation method of thickening polymer suitable for alcohol system |
| CN112876596A (en) * | 2021-01-06 | 2021-06-01 | 广州市东雄化工有限公司 | Solution type alcohol disinfection gel thickening agent and preparation method thereof |
| CN114276492A (en) * | 2022-01-19 | 2022-04-05 | 广东星狮能源科技有限公司 | Anti-ultraviolet thickening agent, preparation method thereof and disinfection washing-free hand rubbing gel |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115466346B (en) | 2024-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR920009613B1 (en) | Process for making hard or fixed based permeable hollow particle dispersions | |
| US5663258A (en) | Strongly swellable, moderately crosslinked copolymers of vinylpyrrolidone and vinyl acetate | |
| Legros et al. | pH and redox responsive hydrogels and nanogels made from poly (2-ethyl-2-oxazoline) | |
| NO158811B (en) | WATER-ABSORBING POLYMER MIXTURE BASED ON A WATER SOLUBLE POLYMER OF A VINYL LACTAM AND A WATER SOLUBLE COPOLYMER. | |
| CN105777992B (en) | A kind of environmental response type nano-cellulose graft copolymer of alcoxyl etherificate and preparation method thereof | |
| WO2014050795A1 (en) | Polyvinyl acetal microparticles for water-based dispersion | |
| CN111825798B (en) | Preparation method of high-molecular ultraviolet light absorber | |
| US4209435A (en) | Dispersion preparation | |
| Jansen et al. | Modification of polyetherurethane for biomedical application by radiation‐induced grafting. I. Grafting procedure, determination of mechanical properties, and chemical modification of grafted films | |
| CN109535345B (en) | Method for preparing polymer based on semi-continuous feeding method | |
| Zeng et al. | Uncontrolled polymerization that occurred during photoinitiated RAFT dispersion polymerization of acrylic monomers promotes the formation of uniform raspberry-like polymer particles | |
| Falireas et al. | Synthesis, aqueous solution behavior and self-assembly of a dual pH/thermo-responsive fluorinated diblock terpolymer | |
| CN115466346B (en) | Preparation method of polymer thickener in polar solvent | |
| JP3054447B2 (en) | Method for producing water-soluble polymer fine particles | |
| US6599979B2 (en) | Carboxylated polymer composition | |
| WO2005026225A1 (en) | Process of making monodisperse, spherical, controlled-size micrometer polymer particles | |
| CN105860104A (en) | Temperature-sensitive self-repairing hydrogel and preparation method and application thereof | |
| JP3128628B2 (en) | Method for producing high polymerization degree polyacrylic acid | |
| CN116284540B (en) | High-light-transmittance high-viscosity polyacrylic acid thickener and preparation method thereof | |
| CN1300221C (en) | Process for preparing rapidly responsive pH sensitive hydrogel | |
| CN114716627A (en) | High-molecular UV absorbent for outdoor non-woven fabric and preparation method thereof | |
| John et al. | Cardanyl acrylate/methacrylate based cross‐linked copolymers as novel supports: Synthesis and characterization | |
| Pan et al. | Influence of preparation conditions on the properties of keratin-based polymer hydrogel | |
| EP0024164A1 (en) | Preparation of non-cross-linked polymers, moulding process therefor and contact lenses produced by the process | |
| US5061761A (en) | Polyvinyl ester macromonomer and its uses |
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 |