CN100523019C - Alkali thickening type rheological modifier and its preparing method - Google Patents
Alkali thickening type rheological modifier and its preparing method Download PDFInfo
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- CN100523019C CN100523019C CNB2006100219300A CN200610021930A CN100523019C CN 100523019 C CN100523019 C CN 100523019C CN B2006100219300 A CNB2006100219300 A CN B2006100219300A CN 200610021930 A CN200610021930 A CN 200610021930A CN 100523019 C CN100523019 C CN 100523019C
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- 239000006254 rheological additive Substances 0.000 title claims abstract description 33
- 239000003513 alkali Substances 0.000 title claims abstract description 12
- 230000008719 thickening Effects 0.000 title claims description 21
- 238000000034 method Methods 0.000 title description 4
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- -1 polyoxyethylene chain Polymers 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 150000002430 hydrocarbons Chemical group 0.000 claims description 14
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- 239000012986 chain transfer agent Substances 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 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 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical group CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- JQRRFDWXQOQICD-UHFFFAOYSA-N biphenylen-1-ylboronic acid Chemical compound C12=CC=CC=C2C2=C1C=CC=C2B(O)O JQRRFDWXQOQICD-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 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
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- HAMGRBXTJNITHG-UHFFFAOYSA-N methyl isocyanate Chemical compound CN=C=O HAMGRBXTJNITHG-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-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
- 239000008096 xylene Substances 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims 2
- 230000000379 polymerizing effect Effects 0.000 claims 2
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 claims 1
- 239000003607 modifier Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 35
- 239000000243 solution Substances 0.000 abstract description 34
- 229920000642 polymer Polymers 0.000 abstract description 20
- 239000000843 powder Substances 0.000 abstract description 14
- 239000011259 mixed solution Substances 0.000 abstract description 11
- 229920005862 polyol Polymers 0.000 abstract description 8
- 150000003077 polyols Chemical class 0.000 abstract description 8
- 239000004094 surface-active agent Substances 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000010008 shearing Methods 0.000 abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 238000003756 stirring Methods 0.000 description 21
- 238000010992 reflux Methods 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000002562 thickening agent Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 239000000017 hydrogel Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 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 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 229940086737 allyl sucrose Drugs 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- KKQBNQXZNTVMBZ-UHFFFAOYSA-N docosa-1,3,5,7,9,11-hexaen-1-ol Chemical compound CCCCCCCCCCC=CC=CC=CC=CC=CC=CO KKQBNQXZNTVMBZ-UHFFFAOYSA-N 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- GOAHRBQLKIZLKG-UHFFFAOYSA-N 1-tert-butylperoxybutane Chemical compound CCCCOOC(C)(C)C GOAHRBQLKIZLKG-UHFFFAOYSA-N 0.000 description 1
- RFIMISVNSAUMBU-UHFFFAOYSA-N 2-(hydroxymethyl)-2-(prop-2-enoxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC=C RFIMISVNSAUMBU-UHFFFAOYSA-N 0.000 description 1
- ZACVGCNKGYYQHA-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOC(=O)OCC(CC)CCCC ZACVGCNKGYYQHA-UHFFFAOYSA-N 0.000 description 1
- ZJCZFAAXZODMQT-UHFFFAOYSA-N 2-methylpentadecane-2-thiol Chemical compound CCCCCCCCCCCCCC(C)(C)S ZJCZFAAXZODMQT-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 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 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical group [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 235000019476 oil-water mixture Nutrition 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GSECCTDWEGTEBD-UHFFFAOYSA-N tert-butylperoxycyclohexane Chemical compound CC(C)(C)OOC1CCCCC1 GSECCTDWEGTEBD-UHFFFAOYSA-N 0.000 description 1
- CSKKAINPUYTTRW-UHFFFAOYSA-N tetradecoxycarbonyloxy tetradecyl carbonate Chemical compound CCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCC CSKKAINPUYTTRW-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The alkali thickened rheological modifier is prepared with unsaturated carboxylic acid with C-C double bond, macro monomer containing C-C double bond, long C-H chain and PVC chain, initiator, cross-linking agent, chain transferring agent, etc and through polymerization in organic solvent. Introducing the reactive macro monomer can result in smooth polymerization process to produce dense polymer powder easy to disperse in water; and adding alkali to neutralize can raise the viscosity and improve the rheological property of the solution fast. The polymer will not be contaminated by surfactant and attacked by microbe. This kind of rheological modifier can raise the viscosity of mixed solution of water and/or polyol at low shearing rate and endow solution with excellent shearing and thinning performance.
Description
Technical Field
The invention relates to a rheology modifier and a preparation method thereof, in particular to an alkali thickening rheology modifier which is used for improving the rheological property of water, polyhydric alcohol and mixed solution of the polyhydric alcohol and the water and can effectively improve the viscosity of the mixed solution at a low shear rate and a preparation method thereof.
Background
In order to change the rheology and viscosity of water, polyols and mixed solutions of polyols and water, it is often necessary to add a rheology modifier (conventionally referred to as a thickener) to the system. Among the commonly used rheology modifiers, natural products include guar gum, xanthan gum, and the like; the artificial synthesized products include polyacrylic acid, polyacrylamide and the like. The following is a brief description of the basic thickening rheology modifiers and their synthesis which have been disclosed so far in the patent literature:
U.S. Pat. No. 6,433,061 discloses a crosslinked polymer synthesized from a chain transfer agent containing a hydrophobic chain of an unsaturated carboxylic acid having a carbon-carbon double bond, dodecylmercaptan, etc., a steric stabilizer, allyl sucrose ether as a crosslinking agent, and an acrylate having a long carbon chain as a hydrophobic monomer, for increasing the viscosity of an aqueous solution containing an electrolyte. This patent technology uses allyl sucrose ether as cross-linking agent to improve the thickening ability, but this cross-linking agent made of sucrose is apt to be attacked by bacteria in water, produce and go mouldy, destroy the product quality; in addition, the technology of the patent also adopts steric type surfactants as dispersion stabilizers, and the surfactants can remain in subsequent products and possibly bring limitations to the use of final products.
CN 1424335 discloses a preparation method of an acrylate thickener. It is carried out in supercritical carbon dioxide by using monomer, emulsifier, initiator, etc. as raw material. Because the reaction pressure is high, the safety risk of actual operation is increased.
CN 1415658 discloses a preparation method of an associative thickener containing fluorocarbon hydrophobic groups. The thickening agent is a polymer synthesized by acrylic acid or methacrylic acid, fluorine-containing acrylate or methacrylate and a bifunctional crosslinking agent. The fluorine-containing acrylate is expensive, which results in high cost of the polymer.
US 6437068 discloses a water soluble or water swellable polymer synthesized from acrylamidoalkylsulfonic acid salts, N-vinylamide monomers and a cross-linking agent in t-butanol. US 6645476 discloses a polymer synthesized from acrylamidoalkylsulfonic acid salts and macromonomers containing carbon-carbon double bonds, long hydrocarbon chains and polyoxyethylene chains. The two polymer monomers are neutralized during the synthesis process, so that the obtained product can be directly thickened in water, and the uniform mixing of other materials in the system is not facilitated.
Disclosure of Invention
The invention aims to provide an alkali thickening rheology modifier capable of effectively improving the rheological property and viscosity of water, polyalcohol and a mixed solution of the polyalcohol and the water and a preparation method thereof. The rheology modifier not only can effectively improve the viscosity and the shear thinning performance of water, polyol and mixed solution of the polyol and the water at a low shear rate, but also can increase the adhesive force of the solution on an inclined surface. When the water-soluble polymer is used in an oil-water mixed system and a liquid-solid mixed system, the stability of an oil-water mixture can be improved, and the suspension stability of solids in a solution is improved.
The purpose of the invention is realized by adopting the following technical scheme:
an alkali thickening rheology modifier is characterized by comprising the following components which are polymerized in an organic solvent according to the weight ratio:
50-95 parts of unsaturated carboxylic acid containing carbon-carbon double bond
1-40 parts of macromonomer containing carbon-carbon double bond, long hydrocarbon chain and polyoxyethylene chain
0.1-2 parts of initiator
0.01-5 parts of cross-linking agent
0.05-4 parts of chain transfer agent
Wherein, the preferable range values of the components are as follows:
60-90 parts of unsaturated carboxylic acid containing carbon-carbon double bonds,
5-30 parts of macromonomer containing carbon-carbon double bond, long hydrocarbon chain and polyoxyethylene chain
0.5-1 part of initiator
0.1-2 parts of cross-linking agent
0.1-2 parts of chain transfer agent
The organic solvent includes: petroleum ether, mineral spirits, ethyl acetate, butyl acetate, isobutyl acetate, toluene, xylene, benzene, cyclohexane, decalin, n-octane, isooctane, and mixtures of these solvents.
The dosage of the organic solvent is 2-20 times of the total weight of the component monomers, and is usually more 3-10 times.
The unsaturated carboxylic acid containing carbon-carbon double bonds is composed of one or more than one monobasic acid or polybasic acid containing 3-13 carbon atoms.
These unsaturated carboxylic acids containing a carbon-carbon double bond include: acrylic acid, methacrylic acid, α -cyanoacrylic acid, crotonic acid, butenedioic acid, itaconic acid, and the like. The carboxylic acid herein also includes maleic anhydride which can be hydrolyzed into a carboxylic acid, and the like.
In particular, the unsaturated carboxylic acid containing a carbon-carbon double bond is preferably acrylic acid, methacrylic acid or a mixture of both in an arbitrary ratio.
The molecular structure of the macromonomer containing carbon-carbon double bond, long hydrocarbon chain and polyoxyethylene chain is A-B-C, A, B, C groups are connected through chemical bonds, wherein
The structure of the A group is:
R1——
R1is a hydrocarbon chain containing 8 to 30 carbon atoms.
The structure of the B group is:
m is 1 to 60
The structure of the C group is:
the structure formed by the reaction of the monomer containing the carbon-carbon double bond and carrying the active group and the polyoxyethylene with a long carbon-carbon chain at one end, namely the structure formed by the reaction of the unsaturated carboxylic acid containing the carbon-carbon double bond or the anhydride, the acyl halide and the ester thereof, and the isocyanate containing the carbon-carbon double bond and the hydroxyl at the tail end of the polyoxyethylene.
Wherein,
the monomer containing carbon-carbon double bond and having active group is: (meth) acrylic acid, (meth) acryloyl halide, (meth) acrylic anhydride, maleic anhydride, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isopropyl (meth) acrylate, and the like, which react with a hydroxyl group-and long-hydrocarbon chain-containing polyoxyethylene to form an ester macromonomer.
The isocyanate monomer containing carbon-carbon double bonds is as follows: 1. 1-dimethyl-3-isopropenylphenyl methyl isocyanate, 2-ethyl methacrylate and the like, which react with polyoxyethylene containing hydroxyl and a long hydrocarbon chain through an isocyanate group to form a macromonomer with a carbamate chemical structure.
The initiator initiates polymerization reaction by decomposing to form free radicals, and comprises the following components: dilauroyl peroxide, ditetradecyl peroxydicarbonate, bis (2-ethylhexyl) peroxydicarbonate, azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, 1-bis (t-butylperoxy) cyclohexane, 2-bis (t-butylperoxy) butane.
The chain transfer agent of the present invention contains a group that readily reacts with a free radical, including: carbon tetrachloride, carbon tetrabromide, isopropanol, n-butylmercaptan, specific mercaptan, dodecylmercaptan, hexadecylmercaptan, octadecylmercaptan, etc. The chain transfer agents can regulate and control the molecular weight of the polymer and also have a certain regulating effect on the viscosity of the polymer after neutralization.
The crosslinking agent molecule of the invention contains a plurality of vinyl groups, and comprises: trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, triallylisocyanurate, divinylbenzene, trimethylolpropane diallyl ether, pentaerythritol allyl ether, and the like. Mainly used for improving the molecular structure of the polymer and adjusting the molecular weight.
The preparation method of the alkali thickening rheology modifier comprises the following process steps:
A. synthesis of macromonomers containing carbon-carbon double bonds, long hydrocarbon chains and polyoxyethylene chains
Adding 0.1 mol of polyoxyethylene containing hydroxyl and long hydrocarbon chain into a three-neck flask provided with a stirring device and a distilling device, replacing 3-6 times with nitrogen, removing oxygen in the system, heating to 100-110 ℃, decompressing and vacuumizing for 30 minutes to remove water in the system, and then cooling to 50-70 ℃. And (3) removing a distillation device, installing a reflux condenser tube and a dropping funnel, then adding 1-3 drops of catalyst and 0.005-0.03 g of polymerization inhibitor, dropwise adding 1.0-1.1 mol of monomer containing carbon-carbon double bonds and having active groups from the dropping funnel under stirring, heating to 80 ℃, carrying out heat preservation reaction for 2 hours, cooling to normal temperature, and then discharging to obtain the macromonomer.
The polymerization inhibitor can be selected from hydroquinone, p-hydroxyanisole, 2, 6-di-tert-butyl-p-cresol and the like.
The catalyst is stannous diisooctoate, dibutyltin dilaurate and the like.
B. Synthesis of alkaline thickening rheology modifier
Adding 100 ml of organic solvent into a 250 ml three-neck flask provided with a stirring device, a reflux condenser tube, a dropping funnel and a nitrogen protection device according to the weight ratio, then uniformly mixing and dissolving 4 g of the macromonomer prepared in the step A, 16 g of unsaturated carboxylic acid containing carbon-carbon double bonds, 40 ml of the rest organic solvent, 0.1 g of chain transfer agent and 0.1 g of cross-linking agent to prepare a mixed monomer solution, adding 20 ml of the mixed monomer solution into the three-neck flask, purging with nitrogen for 5 minutes to remove oxygen, and then starting heating to reflux. When the system is refluxed, 0.2 g of initiator is added, and the polymerization exotherms begin after about 2 to 3 minutes, and the system becomes cloudy at the same time. And after 5 minutes of the start of the polymerization reaction, dropwise adding the rest of the mixed monomer solution from the dropping funnel, continuously keeping refluxing for 2 hours after the dropwise adding is finished, then cooling and filtering, and drying the filter cake to obtain a white powder product.
The polymerization temperature of the invention is 40-110 ℃, and generally more 50-90 ℃.
The molecular main chain of the alkali thickening type rheology modifier is polymerized by a carbon-carbon double bond structure of (methyl) acrylic acid and a macromonomer, and the side chain is composed of an alkyl alcohol polyoxyethylene chain. When this polymer is thickened after neutralization with alkali in water, the polymer backbone is rapidly stretched in water due to the electrostatic repulsion of the carboxyl groups on the polymer backbone; meanwhile, hydrophobic chains on the branched chains are mutually associated to form physical crosslinking points, so that the polymer solution at low shear rate shows high viscosity. At higher shear rates, the physical crosslinks formed by the hydrophobic associations are broken and the viscosity of the polymer solution shows a tendency to decrease rapidly. Thus, at very low levels (less than 1%), the polymer is effective in increasing the viscosity of the water, polyol and water mixture and also in increasing the shear thinning properties of these solutions.
The invention has the advantages that:
1. the invention is polymerized in normal pressure environment, and the operation is simple and easy.
2. The invention does not contain expensive fluorine-containing acrylate, thereby reducing the cost of the polymer.
3. The polymer with special rheological property synthesized by the invention contains long hydrocarbon hydrophobic chains, and the viscosity or the rheological property of the system can be changed at any time by regulating the pH value of the system in a solution containing the polymer.
4. The invention introduces the macromonomer containing carbon-carbon double bond, long hydrocarbon chain and polyoxyethylene chain, so the polymerization process has stable reaction, the product is loose powder which is easy to disperse in water, and after being neutralized by adding alkali, the viscosity can be rapidly improved, and the rheological property of the solution can be improved.
5. The invention does not add other surface active agent as dispersion stabilizer in the process of synthesizing the polymer, so the polymerization product is not polluted by other surface active agent. And the rheology modifier can effectively improve the viscosity of water, polyol or a mixed solution of the polyol and the water at a low shear rate under a very low concentration, and endow the solution with good shear thinning performance.
Detailed Description
EXAMPLE 1 Synthesis of macromonomer
100 g of docosahexenol polyoxyethylene ether (21) is added into a 250 ml three-neck flask provided with a stirring device and a distilling device, nitrogen is used for replacing 4 times, oxygen in the system is removed, the temperature is raised to 100-110 ℃, vacuum is carried out under reduced pressure for 30 minutes, water in the system is removed, and then the temperature is lowered to 65 ℃. And (3) removing a distillation device, installing a reflux condenser tube and a dropping funnel, then adding 1 drop of dibutyltin dilaurate and 0.01 gram of p-hydroxyanisole, dropwise adding 16.7 grams of 1, 1-dimethyl-3-isopropenyl phenyl methyl isocyanate from the dropping funnel after stirring, heating to 80 ℃ after dropwise adding, carrying out heat preservation reaction for 2 hours, cooling, and discharging to obtain the macromonomer.
Example 2 Synthesis of base thickening rheology modifier
100 ml of benzene is added into a 250 ml three-neck flask provided with a stirring device, a reflux condenser tube, a dropping funnel and a nitrogen protection device, 4 g of the macromonomer in example 1 is taken and uniformly mixed and dissolved with 16 g of acrylic acid, 40 ml of benzene, 0.1 g of octadecyl mercaptan and 0.1 g of divinylbenzene to prepare a mixed monomer solution, 20 ml of the mixed monomer solution is added into the three-neck flask, nitrogen is used for purging for 5 minutes to remove oxygen, and then heating is started until reflux. When the system was refluxed, 0.2 g of dibenzoyl peroxide was added and after a few minutes the exothermic polymerization started and the system became cloudy at the same time. And 5 minutes after the polymerization reaction starts, dropwise adding the mixed monomer solution, and finishing dropwise adding within about 20-30 minutes. After the dropwise addition, the reflux is kept for 2 hours, then cooling and suction filtration are carried out, and the filter cake is dried to obtain 19.1 g of white powder.
Example 3 viscosity of base thickening rheology modifier in aqueous solution
0.4 g of the white powder from example 2 was dispersed in 320 g of deionized water under stirring, neutralized with triethanolamine at a stirring rate of 300 rpm, thoroughly stirred until the thickener had formed a hydrogel in the deionized water, adjusted to pH 7.5 with triethanolamine to form a 0.125% strength solution, and then measured for viscosity using BrookFIELLV-DVIII viscometer # 2 spindle. The viscosity measured at 25 degrees celsius was: 6298 centipoise to 0.3rpm, 2129 centipoise to 3rpm, 665 centipoise to 30 rpm.
EXAMPLE 4 Synthesis of macromonomer
100 g of docosahexenol polyoxyethylene ether (21) is added into a 250 ml three-neck flask provided with a stirring device and a distilling device, nitrogen is used for replacing 4 times, oxygen in the system is removed, the temperature is raised to 100-110 ℃, vacuum is carried out under reduced pressure for 30 minutes, water in the system is removed, and then the temperature is lowered to 70 ℃. And (3) removing a distillation device, installing a reflux condenser tube and a dropping funnel, then adding 0.01 g of p-hydroxyanisole, dropwise adding 9.5 g of methacryloyl chloride from the dropping funnel under stirring, heating to 80 ℃ after dropwise addition, carrying out heat preservation reaction for 2 hours, and then cooling and discharging.
Example 5 Synthesis of base thickening rheology modifier
100 ml of benzene is added into a 250 ml three-neck flask provided with a stirring device, a reflux condenser tube, a dropping funnel and a nitrogen protection device, 4 g of macromonomer prepared by the implementation 4 is taken to be uniformly mixed and dissolved with 16 g of acrylic acid, 40 ml of benzene, 0.1 g of octadecyl mercaptan and 0.1 g of divinylbenzene to prepare a mixed monomer solution, 20 ml of the mixed monomer solution is added into the three-neck flask, nitrogen is used for purging for 5 minutes to remove oxygen, and then heating is started until reflux. When the system was refluxed, 0.2 g of dibenzoyl peroxide was added and after a few minutes the exothermic polymerization started and the system became cloudy at the same time. And 5 minutes after the polymerization reaction starts, dropwise adding the mixed monomer solution, and finishing dropwise adding within about 20-30 minutes. After the dropwise addition, the reflux is kept for 2 hours, then cooling and suction filtration are carried out, and the filter cake is dried to obtain 18.5 g of white powder.
Example 6 viscosity of base thickening rheology modifier in aqueous solution
0.4 g of the white powder from example 5 was dispersed in 100 g of deionized water under stirring, neutralized with triethanolamine at a stirring rate of 300 rpm, thoroughly stirred until the thickener had formed a hydrogel in the deionized water, adjusted to pH 7.5 with triethanolamine to give a 0.4% strength solution, and then measured for viscosity using BrookFIELLV-DVIII viscometer # 3 spindle. The viscosity measured at 25 degrees celsius was: 127972 cps to 0.3rpm, 16196 cps to 3rpm, 2650 cps to 30 rpm.
Example 7 viscosity of base thickening rheology modifier in a mixture of ethylene glycol and aqueous solution
0.2 g of the white powder is dispersed in 50 g of deionized water under stirring, 50 g of ethylene glycol is added and stirred uniformly, the white powder is neutralized by triethanolamine at a stirring speed of 300 r/min, the white powder is stirred sufficiently until the thickener forms a gel in the deionized water, the pH value is adjusted to 7.2 by the triethanolamine to prepare a solution with the concentration of 0.2%, and then the viscosity is measured by a BrookFIELL LV-DVIII viscometer # 2 spindle. The viscosity measured at 25 degrees celsius was: 6998 centipoise-0.3 rpm, 1709 centipoise-3 rpm, 503 centipoise-30 rpm
EXAMPLE 8 Synthesis of base thickening rheology modifier
30 ml of ethyl acetate and 70 ml of cyclohexane are added into a 250 ml three-neck flask provided with a stirring device, a reflux condenser tube, a dropping funnel and a nitrogen protection device. 4 g of the macromonomer obtained in example 1 was mixed with 16 g of acrylic acid, 12 ml of ethyl acetate, 28 ml of cyclohexane, 0.05 g of stearyl mercaptan, and 0.1 g of divinylbenzene and dissolved uniformly to prepare a mixed monomer solution. 0.1 g of ditetradecyperoxydicarbonate was mixed with 3 ml of ethyl acetate and 7 ml of cyclohexane to prepare an initiator solution. 20 ml of the mixed monomer solution was added to a three-necked flask, stirred and purged with nitrogen for 5 minutes to remove oxygen, and then heating was started to 45 ℃. Ditetradecyperoxydicarbonate, 0.3 g, is added and after a few minutes the exothermic polymerization begins and the system becomes cloudy at the same time. And (3) after 5 minutes of the polymerization reaction, dropwise adding the mixed monomer solution, dropwise adding the initiator mixed solution by using a constant flow pump, wherein the dropwise adding of the mixed monomer solution is finished after about 20-30 minutes, and the adding of the initiator mixed solution is finished after 2-3 minutes. After the dropwise addition, the reaction is continued for 2 hours under heat preservation, then cooling and suction filtration are carried out, and the filter cake is dried to obtain 17.5 g of white powder.
Example 9 viscosity of base thickening rheology modifier in aqueous solution
0.4 g of the white powder from example 8 was dispersed in 100 g of deionized water under stirring, neutralized with triethanolamine at a stirring rate of 300 rpm, thoroughly stirred until the thickener had formed a hydrogel in the deionized water, adjusted to pH 7.5 with triethanolamine to give a 0.4% strength solution, and then measured for viscosity using BrookFIELLV-DVIII viscometer # 3 spindle. The viscosity was measured at 25 ℃ to be 81938 cps-0.3 rpm, 13924 cps-3 rpm, 2640 cps-30 rpm.
Example 10 Synthesis of base thickening rheology modifier
30 ml of butyl acetate and 70 ml of decalin are added into a 250 ml three-neck flask provided with a stirring device, a reflux condenser tube, a dropping funnel and a nitrogen protection device. 4 g of the macromonomer obtained in example 1 was mixed with 16 g of acrylic acid, 12 ml of butyl acetate, 28 ml of decalin, 0.05 g of stearyl mercaptan and 0.1 g of divinylbenzene and dissolved uniformly to prepare a mixed monomer solution. An initiator solution was prepared by mixing 0.1 g of 2, 2-di (t-butylperoxy) butane with 3 ml of butyl acetate and 7 ml of decalin. 20 ml of the mixed monomer solution was added to a three-necked flask, stirred and purged with nitrogen for 5 minutes to remove oxygen, and then heating was started to 100 ℃. 0.2 g of 2, 2-di (tert-butylperoxy) butane was added, and after a few minutes the exothermic polymerization started and the system became cloudy at the same time. And (3) after 5 minutes of the polymerization reaction, dropwise adding the mixed monomer solution, dropwise adding the initiator mixed solution by using a constant flow pump, wherein the dropwise adding of the mixed monomer solution is finished after about 20 to 30 minutes, and the adding of the initiator mixed solution is finished after 2 to 3 minutes. After the dropwise addition, the reaction is continued for 2 hours under heat preservation, then cooling and suction filtration are carried out, and the filter cake is dried to obtain 16.5 g of white powder.
Example 11 viscosity of base thickening rheology modifier in aqueous solution
0.5 g of the white powder from example 10 was dispersed in 100 g of deionized water under stirring, neutralized with triethanolamine at a stirring rate of 300 rpm, thoroughly stirred until the thickener had formed a hydrogel in the deionized water, adjusted to pH 7.5 with triethanolamine to give a 0.5% strength solution, and then measured for viscosity using BrookFIELLV-DVIII viscometer # 3 spindle. The viscosity measured at 25 degrees celsius was: 52846 cP to 0.3rpm, 8942 cP to 3rpm, 1782 cP to 30 rpm.
Claims (8)
1. An alkali thickening rheology modifier is characterized in that the modifier is prepared by polymerizing the following components in an organic solvent according to the weight ratio:
50-95 parts of unsaturated carboxylic acid containing carbon-carbon double bond
1-40 parts of macromonomer containing carbon-carbon double bond, long hydrocarbon chain and polyoxyethylene chain
0.1-2 parts of initiator
0.01-5 parts of cross-linking agent
0.05-4 parts of chain transfer agent
Wherein the organic solvent is: petroleum ether, solvent oil, ethyl acetate, butyl acetate, isobutyl acetate, toluene, xylene, benzene, cyclohexane, decalin, n-octane, isooctane or a mixture of the solvents, wherein the dosage of the organic solvent is 2-20 times of the total weight of the component monomers;
the macromonomer containing carbon-carbon double bond, long hydrocarbon chain and polyoxyethylene chain has a molecular structure of A-B-C, and A, B, C groups are connected through chemical bonds, wherein
The structure of the A group is:
R1—
R1is a hydrocarbon chain containing 8-30 carbon atoms;
the structure of the B group is:
m is 1-60;
the structure of the C group is:
a structure formed by reacting unsaturated carboxylic acids containing a carbon-carbon double bond or their anhydrides, acid halides, esters, or isocyanates containing a carbon-carbon double bond with a hydroxyl group at the end of polyoxyethylene.
2. The alkali-thickening rheology modifier of claim 1, which is prepared by polymerizing the following components in an organic solvent according to the weight ratio:
60-90 parts of unsaturated carboxylic acid containing carbon-carbon double bonds,
5-30 parts of macromonomer containing carbon-carbon double bond, long hydrocarbon chain and polyoxyethylene chain
0.5-1 part of initiator
0.1-2 parts of cross-linking agent
0.1-2 parts of a chain transfer agent.
3. An alkali-thickening rheology modifier according to claim 1 or 2 characterised in that the unsaturated carboxylic acid containing a carbon-carbon double bond is comprised of one or more of acrylic acid, methacrylic acid, α -cyanoacrylic acid, crotonic acid, butenedioic acid or itaconic acid.
4. The alkaline thickening rheology modifier of claim 3 wherein said unsaturated carboxylic acid containing carbon-carbon double bonds is acrylic acid, methacrylic acid or a mixture thereof in any proportion.
5. The alkali-thickening rheology modifier according to claim 1, characterized in that said unsaturated carboxylic acid containing a carbon-carbon double bond or their anhydride, acid halide, ester is: (meth) acrylic acid, (meth) acryloyl halide, (meth) acrylic anhydride, maleic anhydride, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, or isopropyl (meth) acrylate.
6. The alkali-thickening rheology modifier of claim 1 wherein said isocyanate monomer containing a carbon-carbon double bond is: 1. 1-dimethyl-3-isopropenylphenyl methyl isocyanate or methacrylic acid-2-isocyanatoethyl ester.
7. An alkali-thickening rheology modifier according to claim 1 or 2, characterised in that said cross-linking agent is selected from trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, triallylisocyanurate, divinylbenzene, trimethylolpropane diallyl ether or pentaerythritol polyallyl ether.
8. The alkali-thickening rheology modifier of claim 1 or 2, wherein the polymerization temperature is from 40 to 110 ℃.
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