CN114195943A - Carbomer thickening agent capable of being quickly wetted and dispersed and preparation method thereof - Google Patents
Carbomer thickening agent capable of being quickly wetted and dispersed and preparation method thereof Download PDFInfo
- Publication number
- CN114195943A CN114195943A CN202111549017.9A CN202111549017A CN114195943A CN 114195943 A CN114195943 A CN 114195943A CN 202111549017 A CN202111549017 A CN 202111549017A CN 114195943 A CN114195943 A CN 114195943A
- Authority
- CN
- China
- Prior art keywords
- carbomer
- layer component
- carbon
- inner layer
- mass
- 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
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- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229920002125 Sokalan® Polymers 0.000 title claims abstract description 97
- 229960001631 carbomer Drugs 0.000 title claims abstract description 93
- 239000002562 thickening agent Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- -1 acrylic ester Chemical class 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000002904 solvent Substances 0.000 claims description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 31
- 239000003999 initiator Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 20
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 19
- 239000003431 cross linking reagent Substances 0.000 claims description 19
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 15
- 150000003254 radicals Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 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 8
- 125000005599 alkyl carboxylate group Chemical group 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 4
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- 125000005907 alkyl ester group Chemical group 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229950011392 sorbitan stearate Drugs 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003759 ester based solvent Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 claims description 3
- 229940082004 sodium laurate Drugs 0.000 claims description 3
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 claims description 2
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 claims description 2
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 claims description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-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
- FKOKUHFZNIUSLW-UHFFFAOYSA-N 2-Hydroxypropyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(C)O FKOKUHFZNIUSLW-UHFFFAOYSA-N 0.000 claims description 2
- FKMHSNTVILORFA-UHFFFAOYSA-N 2-[2-(2-dodecoxyethoxy)ethoxy]ethanol Chemical compound CCCCCCCCCCCCOCCOCCOCCO FKMHSNTVILORFA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical group [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 229940091181 aconitic acid Drugs 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 150000001734 carboxylic acid salts Chemical class 0.000 claims description 2
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001869 inorganic persulfate Inorganic materials 0.000 claims description 2
- 229940057905 laureth-3 Drugs 0.000 claims description 2
- 229910001416 lithium ion Chemical group 0.000 claims description 2
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 229940114930 potassium stearate Drugs 0.000 claims description 2
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 claims description 2
- 229940093625 propylene glycol monostearate Drugs 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 229940080350 sodium stearate Drugs 0.000 claims description 2
- ATZHWSYYKQKSSY-UHFFFAOYSA-N tetradecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)=C ATZHWSYYKQKSSY-UHFFFAOYSA-N 0.000 claims description 2
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- 229940085654 trideceth-5 Drugs 0.000 claims description 2
- 150000001451 organic peroxides Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 39
- 150000003839 salts Chemical class 0.000 abstract description 5
- 238000007334 copolymerization reaction Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 55
- 238000009736 wetting Methods 0.000 description 33
- 239000000047 product Substances 0.000 description 19
- 230000008719 thickening Effects 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000009472 formulation Methods 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229940059574 pentaerithrityl Drugs 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000004909 Moisturizer Substances 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000001333 moisturizer Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000004970 Chain extender Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 230000000474 nursing effect Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- JHSWSKVODYPNDV-UHFFFAOYSA-N 2,2-bis(prop-2-enoxymethyl)propane-1,3-diol Chemical compound C=CCOCC(CO)(CO)COCC=C JHSWSKVODYPNDV-UHFFFAOYSA-N 0.000 description 2
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 2
- RMTFNDVZYPHUEF-XZBKPIIZSA-N 3-O-methyl-D-glucose Chemical compound O=C[C@H](O)[C@@H](OC)[C@H](O)[C@H](O)CO RMTFNDVZYPHUEF-XZBKPIIZSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- 239000004908 Emulsion polymer Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 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 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000000546 pharmaceutical excipient Substances 0.000 description 2
- 229960005323 phenoxyethanol Drugs 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- TYMYJUHDFROXOO-UHFFFAOYSA-N 1,3-bis(prop-2-enoxy)-2,2-bis(prop-2-enoxymethyl)propane Chemical compound C=CCOCC(COCC=C)(COCC=C)COCC=C TYMYJUHDFROXOO-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 1
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000205585 Aquilegia canadensis Species 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- GORMSINSWZJIKL-UHFFFAOYSA-N [3-(2-ethylhexanoyloxy)-2,2-dimethylpropyl] 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OCC(C)(C)COC(=O)C(CC)CCCC GORMSINSWZJIKL-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethyl cyclohexane Natural products CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- AEIJTFQOBWATKX-UHFFFAOYSA-N octane-1,2-diol Chemical compound CCCCCCC(O)CO AEIJTFQOBWATKX-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/10—General cosmetic use
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/48—Thickener, Thickening system
Abstract
The invention discloses a carbomer thickening agent capable of being quickly wetted and dispersed and a preparation method thereof. The carbomer thickener is composed of an inner layer and an outer layer, wherein the outer layer is formed by long-chain organic salt surfactant which is distributed on the surface of the carbomer in polymerization, and when the carbomer thickener is added into water, the surface of the carbomer can quickly absorb water and be wetted; the inlayer is obtained with strong polarity monomer and acrylic ester monomer copolymerization, provides the inside passageway that absorbs water of carbomer structure, can make the hydrone get into fast for carbomer can be quick after adding the aquatic absorb water moist.
Description
Technical Field
The invention relates to the field of preparation of high polymer materials, and particularly relates to a novel carbomer thickening agent with a rapid wetting and dispersing function and a preparation method thereof.
Background
With the increasing aging of the Chinese population and the increasing awareness of people on the demand of personal care products, the demand for the carbomer thickener applied and widely used in the field is increasing year by year. The hand sanitizer without washing is an effective sterilization means for isolating viruses and protecting people, and the market acceptance is greatly improved. The thickening material used in the leave-in hand sanitizer is a carbomer thickener.
The traditional thickener for aqueous systems is mainly water-soluble macromolecule, the molecular structure is completely hydrophilic, and the thickener does not contain hydrophobic structures, such as cellulose (HEC) and acrylic thickener (ASE), and the thickener achieves the purpose of thickening the aqueous phase by forming hydrogen bonds with water molecules in the system.
The polyurethane thickener is a thickener developed in the 80 th 20 th century and is a water-soluble oligomer containing hydrophobic groups. The main structure of the thickening agent is a hydrophilic main component, the hydrophilic main component is a hydrophilic polymer chain, and the hydrophilic polymer chain and the hydrophobic group are connected together through covalent bonds to form the associative thickening agent. In aqueous systems, the hydrophilic portion of such thickeners ensures the dissolution or dispersion of the thickener molecules in water by forming hydrogen bonds with water; in an aqueous system, a hydrophobic part on the thickening agent is bridged to emulsion, solid particles and micelles which can form hydrophobic association in the aqueous system to form a spatial three-dimensional network structure, so that the thickening of the aqueous system is realized. Such thickeners can be classified as hydrophobic alkali swellable thickeners (HASE) and polyurethane associative thickeners (HEUR) and other types of associative thickeners. The aqueous system added with HEUR has more excellent leveling property, excellent film fullness and high film-forming gloss, thereby being widely applied.
Carbomer is homopolymerized or heteropolymerized high polymer of acrylic acid, and is a very important rheology control agent, and the carbomer after neutralization is an excellent gel substrate, has excellent thickening, suspending and emulsifying effects, has good compatibility with other auxiliary materials, is mostly used as an adhesive, a pharmaceutic adjuvant and a nutrient additive, and is particularly widely applied to emulsion, cream and gel.
CN103755861 discloses a carbomer, which is mainly prepared by polymerizing acrylic acid in a mixed solvent of water and tert-butyl alcohol using a water soluble initiator to obtain powdered carbomer. According to the method, a more compatible green and friendly water phase reaction system is provided by adding tert-butyl alcohol, so that the carbomer with high quality and performance is obtained.
CN101633718A discloses a comb-shaped polyurethane associative thickener, a preparation method and application thereof. In the patent, a chain extender containing a hydrophobic long chain is synthesized, and the hydrophobic chain segment is increased by introducing the chain extender into a thickener molecule, so that the thickening effect is improved. However, the synthesis process of the chain extender is complicated.
EP1765900 describes thickeners based on aqueous preparations of nonionic water-dispersible or water-soluble polyurethanes having a special structure. The particular structure of these polymers is achieved by the presence of allophanate linkages, which are generated by the use of an excess of isocyanate. As component (a) hydrophilic polyols having at least 2 OH groups can be used, which may additionally contain ether groups.
CN105037606 discloses a carbomer resin, which comprises the following raw materials in parts by weight: 10-110 parts of carboxylic acid monomer, 0.01-1.5 parts of cross-linking agent and 10-1000 parts of water; 0.01-5.0 parts of other additives; wherein, the carboxylic acid monomer is monomer carboxylic acid with alkenyl double bond; the cross-linking agent is a monomer with more than two double bonds; the other auxiliary agents are one or more of fatty alcohol sodium benzenesulfonate, fatty alcohol sodium sulfate, fatty alcohol-polyoxyethylene ether and sulfate thereof, hydrogen peroxide, persulfate, EDTA and salts thereof.
CN 108299608 describes an alkali swelling associative thickener, which is prepared from the following components in percentage by mass: 10 to 15 percent of methacrylic acid, 15 to 20 percent of ethyl acrylate, 0.1 to 5 percent of polyurea crosslinking monomer, 0.1 to 3 percent of hydrophobic association monomer, 0.5 to 2 percent of anionic surfactant, 0.2 to 0.1 percent of nonionic surfactant and 0.1 to 1 percent of initiator. And is prepared by emulsion polymerization. The thickener is not easily affected by the amount of residual solvent, dispersant and other assistants in the water-based system and the ion concentration of the system, and has good stability.
CN103483491 discloses a method for preparing powdered carbomer, which is mainly characterized in that in a mixed solvent of ethyl acetate and cyclohexane, an oil-soluble initiator is adopted to carry out polymerization of acrylic acid to obtain a white powdered polyacrylic acid powder, and the white powdered polyacrylic acid powder has a good thickening effect in the fields of water phase and personal care.
US20190002613 describes a hydrophobically modified alkali swellable emulsion polymer useful as a rheology modifier. More particularly, this invention relates to hydrophobically modified alkali-swellable emulsion polymers containing residues of polyunsaturated amphiphilic macromonomers. In one aspect, the disclosed polymers are useful for thickening surfactant-containing aqueous compositions while providing excellent rheological properties, clarity, and the ability to stably suspend insoluble and particulate materials for extended periods of time for compositions containing them.
US3912921 discloses a substance obtained by copolymerizing acrylic acid and acrylic ester (alkyl group having 10 to 30 carbon atoms) by radical polymerization in a solvent system to obtain a mixture of polymer and solvent, and finally by separating, washing, drying and the like processes to obtain a powdery acrylic ester copolymer which can obtain a good thickening effect in water.
The thickener products described in the above patents can be used in aqueous systems for a variety of applications. The polyurethane thickening agents invented by CN101633718A and EP1765900 have low thickening efficiency and are difficult to meet the application requirements of most personal care or home care; the alkali swelling thickener disclosed by CN 108299608 and US20190002613 can be applied to some nursing fields, but has the problems of large addition amount and sticky hand feeling; the carbomer thickening agents invented in CN103755861, CN105037606, CN103483491 and US3912921 can meet the requirements of partial nursing fields, but have the problems of long dispersion wetting time, low thickening efficiency and complex process.
The invention discloses a preparation method and application of a carbomer thickening agent with a rapid wetting and dispersing function on the basis of the prior patent. The carbomer thickener has the function of quick wetting and dispersing, wherein the quick wetting and dispersing means that the wetting time of 1 percent of the carbomer thickener added into water is less than or equal to 10 minutes, so that the use efficiency of the carbomer is greatly improved. The carbomer thickener disclosed by the invention is mainly structurally characterized by consisting of an inner layer and an outer layer. The outer layer is embedded on the surface of the outer layer polymer by adopting a long-chain organic salt surfactant, and the surface can be quickly wetted by adding water; the inner layer is obtained by copolymerizing a strong polar monomer and an acrylate monomer, provides a water absorption channel in the carbomer structure, and can enable water molecules to rapidly enter. Meanwhile, the long-chain acrylate monomer is added in the copolymerization, so that the ion resistance and the thickening efficiency of the carbomer thickener are effectively improved.
Disclosure of Invention
Aiming at the problems of the existing carbomer thickening agent, the invention aims to provide the carbomer thickening agent capable of being quickly wetted and dispersed and a preparation method thereof.
In order to achieve one aspect of the above object, the technical solution of the present invention is as follows:
a carbomer thickener capable of being rapidly wetted and dispersed is obtained by initiating a reaction in a first solvent from raw materials comprising an inner layer component and an outer layer component through a radical initiator:
a) the inner layer component is obtained by initiating reaction of a reaction system containing a second solvent and comprising the following reaction components through a free radical initiator:
ai) 80 to 98% by mass, based on the total mass of the inner layer components, of at least one unsaturated carboxylic acid containing a polymerizable carbon-carbon double bond and a carboxyl group;
aii) 0.1 to 15% by mass, based on the total mass of the inner layer components, of at least one unsaturated olefinic monomer containing a polymerizable carbon-carbon double bond and at least one polar structure, other than an unsaturated carboxylic acid;
aiii) 1-12% by mass of the total mass of the inner layer component of at least one (meth) acrylate monomer having the following general structural formula I:
wherein R is1Is hydrogen or methyl, R2Is an alkyl structure containing 1 to 30 carbon atoms;
aiv) 0.01 to 5% by mass, based on the total mass of the inner layer components, of at least one crosslinking agent containing at least two unsaturated carbon-carbon double bonds;
b) an outer layer component comprising:
bi) from 90 to 99.5% by mass, based on the total mass of the outer layer components, of at least one unsaturated carboxylic acid containing a polymerizable carbon-carbon double bond and a carboxyl group;
bii) 0.01 to 5% by mass, based on the total mass of the outer layer components, of at least one crosslinking agent containing at least two unsaturated carbon-carbon double bonds;
biii) 0.1 to 5% based on the total mass of the outer layer components of at least one surfactant of a long-chain alkyl carboxylate having the following general structural formula II:
wherein R is3Is an alkyl structure containing 6-20 carbon atoms, and M is sodium ion, potassium ion or lithium ion;
wherein the mass fraction of the inner layer component is 70-95%, such as 75%, 85% or 88%, preferably 80-90%, and the mass fraction of the outer layer component is 5-30%, such as 12%, 15% or 25%, preferably 10-20%, based on the total mass of the raw materials.
Carbomer is homopolymerized or heteropolymerized high polymer of acrylic acid, and is a very important rheology control agent, and the carbomer after neutralization is an excellent gel substrate, has excellent thickening, suspending and emulsifying effects, has good compatibility with other auxiliary materials, is mostly used as an adhesive, a pharmaceutic adjuvant and a nutrient additive, and is particularly widely applied to emulsion, cream and gel. The rapid wetting and dispersing function in the invention means that when 1 mass percent of carbomer is added into water, the wetting time is less than or equal to 10 minutes, and the wetting is completed, namely that no white powder solid exists on the surface layer of the water. The carbomer structure is mainly composed of an inner layer and an outer layer, the long-chain organic salt surfactant adopted in the outer layer is distributed on the surface of the carbomer in polymerization, and the surface of the carbomer can quickly absorb water and be wetted when being added into water; the inlayer obtains with strong polarity monomer and acrylic ester monomer copolymerization, provides the inside passageway that absorbs water of carbomer structure, can make the hydrone get into fast to make carbomer can be quick after adding the aquatic absorb water moist.
In one embodiment of the present invention, the at least one unsaturated carboxylic acid containing a polymerizable carbon-carbon double bond and a carboxyl group is one or more of acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, crotonic acid and aconitic acid, preferably acrylic acid and/or methacrylic acid. In one embodiment of the invention, such monomers are used in the inner layer component in a proportion of 80 to 98%, such as 82%, 86%, 88%, 92%, 94% or 96%, preferably 85 to 95.5%, of the total mass of the inner layer component; in the outer layer component, such monomers are used in a proportion of 90 to 99.5%, such as 92%, 94%, 96% or 98%, preferably 95 to 99% by weight of the total mass of the outer layer component.
In one embodiment of the invention, the unsaturated olefinic monomer containing at least one polymerizable carbon-carbon double bond and at least one polar structure other than an unsaturated carboxylic acid is one or more of a polymerizable carboxylic acid salt, hydroxy (meth) acrylate and 2-acrylamido-2-methylpropanesulfonic acid, preferably one or more of hydroxyethyl (meth) acrylate, sodium (meth) acrylate, hydroxypropyl (meth) acrylate and 2-acrylamido-2-methylpropanesulfonic acid. Such monomers are used in an amount of 0.1 to 15%, such as 0.5%, 2%, 4%, 8% or 10%, preferably 1 to 5% by weight of the total mass of the inner layer components. The introduction of the monomer in the polymerization of the inner layer component is beneficial to increasing the transparency of a thickened system, and is also beneficial to forming a capillary channel for water permeation and increasing the wetting rate of carbomer.
In one embodiment of the present invention, in the structural formula I of the (meth) acrylate monomer, R1Is methyl, R2The long chain alkyl structure containing 10 to 20, such as 12, 15 or 18 carbon atoms can be a straight chain or branched chain type long chain alkyl structure. Researches find that the long-chain alkyl structure of the carbomer can be more favorable for improving the thickening effect and the ion resistance of a system, and improving the use efficiency and the application range of the carbomer. In the present invention, the (meth) acrylate monomer is used in an amount of 1 to 12%, such as 2%, 5% or 10%, preferably 3 to 8%, based on the total mass of the inner layer component. Preferably, the at least one (meth) acrylate monomer is one or more of lauryl methacrylate, myristyl methacrylate, cetyl methacrylate and stearyl methacrylate.
In a preferred embodiment of the invention, the at least one crosslinking agent containing at least two unsaturated carbon-carbon double bonds is a multifunctional acrylate having at least two polymerizable ethylenically unsaturated double bonds (e.g. a (meth) acrylate compound of a linear or branched polyol having 2 to 20 carbon atoms), or a polyalkenyl polyether having at least two polymerizable ethylenically unsaturated double bonds (e.g. an etherification product of allyl alcohol with a linear or branched polyol having 2 to 15 carbon atoms), or a combination of both. Wherein the polyhydric alcohol is selected from one or more of sucrose, pentaerythritol, dipentaerythritol, trimethylolpropane and a dimer thereof, and trimethylolpropane and a dimer thereof. In the invention, the use of the cross-linking agent can effectively establish a three-dimensional network structure, reduce the free water of the whole system and improve the viscosity and the stability of the system.
The (meth) acrylate-based compound as the crosslinking agent may be selected from, for example, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and one or more of tetramethylolmethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and the like.
Polyalkenyl polyethers as crosslinking agents include polyallyl ethers having a functionality of 2 to 4 per molecule, such as one or more of pentaerythritol diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, and the like.
Of course, other types of crosslinking agents such as silicon crosslinking agents, zinc oxide crosslinking agents, divinyl benzene, methylene bisacrylamide, and the like may also be used in the present invention.
In the inner layer component, the crosslinking agent is used in an amount of 0.01 to 5%, such as 0.05%, 0.2%, 1% or 4%, preferably 0.1 to 3%, more preferably 0.5 to 2% of the total mass of the inner layer component.
In the outer layer component, the cross-linking agent is used in an amount of 0.01 to 5%, such as 0.05%, 0.2%, 1% or 4%, preferably 0.1 to 3%, more preferably 0.5 to 2% of the total mass of the outer layer component.
In one embodiment of the present invention, the surfactant of the long-chain alkyl carboxylate has the general structural formula II in which R is3Preferably 10 to 20, such as 12, 15 or 18 carbon atoms, and may be a linear or branched long chain alkyl structure. The surfactant of the long-chain alkyl carboxylate may be one or a combination of sodium laurate, potassium laurate, sodium stearate, potassium stearate, and lithium stearate. In the outer layer structure, researches find that the introduction of the long-chain alkyl carboxylate can form a water absorbing medium on the outer layer of the carbomer, so that the water absorbing capacity of a system can be effectively improved, and the wetting and dispersing efficiency of the carbomer is further promoted.
In one embodiment of the present invention, the first and second solvents may be the same or different hydrocarbon solvents and/or alkyl ester solvents, wherein the hydrocarbon solvents used include, but are not limited to, n-hexane, cyclohexane, n-heptane, cycloheptane, n-decane, and mixtures thereof; wherein the alkyl ester solvents used include, but are not limited to, ethyl acetate, butyl acetate, ethyl propionate, butyl propionate, and mixtures thereof; preferably, the first and second solvents are a mixture of cyclohexane and ethyl acetate, which not only facilitates polymerization of the inner and outer layers of the thickener of the present invention, but also cyclohexane and ethyl acetate are solvents with lower boiling points and lower toxicity, which can be removed to a very low level in the carbomer at a later stage. When the carbomer produced by the solvent is used in the field of personal care or home care, the irritation to a human body can be reduced, and the use experience of the product is improved.
In one embodiment of the invention, the first solvent is a mixture of cyclohexane and ethyl acetate in a mass ratio of 1:2 to 1:4, such as 1:2.5, 1:3, 1:3.3 or 1: 3.8. Researches find that during outer layer component polymerization, the content of ethyl acetate serving as a solvent is increased, the enrichment of the outer layer long-chain alkyl carboxylate on the surface is facilitated, and the water absorption of carbomer initial wetting is increased. The second solvent is a mixture of cyclohexane and ethyl acetate in a mass ratio of 2:1 to 1:1, such as 1.2:1, 1.5:1 or 1.7: 1. Researches find that under the condition that cyclohexane is not less than ethyl acetate, polar monomers different from carboxylic acid and long-chain alkyl acrylate monomers are copolymerized with unsaturated carboxylic acid monomers more uniformly, and the thickening efficiency of a system and a channel for quick wetting are improved.
The carbomer thickener with the function of quick wetting and dispersing is obtained through precipitation polymerization reaction initiated by free radicals in a solvent. The free radical initiator is one or more of organic peroxide compounds, azo compounds, inorganic persulfate compounds and hydrogen peroxide; preferably, the radical initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, lauroyl peroxide, ammonium persulfate, sodium persulfate and hydrogen peroxide.
In the present invention, the initiator may be used in an amount of 0.05 to 1% by weight, such as 0.1%, 0.4% or 0.6%, preferably 0.2 to 0.7% by weight, based on the total weight of the monomers.
In order to achieve another aspect of the above objects, the present invention also provides a method for preparing the above carbomer thickener capable of being rapidly dispersed and wetted, comprising the steps of:
I) adding reaction components for preparing the inner layer component into a second solvent in proportion and uniformly mixing;
II) heating the reaction system obtained in the step I) to 50-80 ℃, such as 55 ℃, 58 ℃, 60 ℃, 65 ℃, 69 ℃, 71 ℃ or 75 ℃, adding the free radical initiator, and carrying out polymerization reaction to obtain the inner layer component;
III) mixing the free radical initiator and the outer layer component with the inner layer component obtained in the step II) in a first solvent at 50-80 ℃, such as 55 ℃, 58 ℃, 60 ℃, 65 ℃, 69 ℃, 71 ℃ or 75 ℃, carrying out polymerization reaction, cooling after the reaction, filtering, separating, washing and drying to obtain the carbomer thickener.
In one embodiment of the present invention, in step I), a dispersant is further added to the reaction system obtained by mixing; preferably, the dispersant is added in an amount of 0.2 to 3%, such as 1% or 1.5%, preferably 0.5 to 2% of the total mass of the inner layer components.
In one embodiment of the present invention, in step III), the radical initiator and the outer layer component are diluted in advance and then mixed with the inner layer component, wherein a dispersant is further added to the diluted outer layer component; preferably, the dispersant is added in an amount of 0.01 to 1%, such as 0.05%, 0.2% or 0.5%, preferably 0.1 to 0.6% of the total mass of the outer layer components.
In one embodiment of the invention, the dispersant is one or more of propylene glycol monostearate, sorbitan stearate, polyoxyethylene (2EO) oleyl ether, isomeric trideceth-5 and laureth-3. The introduction of the dispersing agent can effectively improve and reduce the viscosity of a polymerization system and improve the polymerization efficiency.
It is understood by those skilled in the art that dilution of the reaction mass prior to addition of the reaction mass facilitates better mixing of the reaction mass after addition, and that dilution of the reaction mass with a solvent is well known in the art, although if the solvent used is a mixture, it is understood by those skilled in the art that pre-dilution with one or more components of the solvent may be used, provided that the final solvent composition is maintained.
In one embodiment of the preparation method of the present invention, the preparation method employs the steps of:
1) adding a mixture of cyclohexane and ethyl acetate serving as a second solvent into the reactor 1, adding a dispersing agent, uniformly mixing, and introducing nitrogen for replacement;
2) uniformly mixing reaction components for preparing the inner layer component, adding the mixture into the reactor 1, uniformly mixing, and continuously introducing nitrogen for replacement;
3) heating the temperature of the reactor 1 to 50-80 ℃, adding an initiator, and starting a polymerization reaction; after the reaction is finished, cooling to room temperature;
4) optionally, adding a proper amount of ethyl acetate into the reactor 1 to adjust the solvent ratio, so as to form a mixture of cyclohexane and ethyl acetate as a first solvent in the reaction kettle 1 subsequently;
5) diluting unsaturated carboxylic acid, a cross-linking agent and a surfactant contained in the outer layer component in a reactor 2 by part of a first solvent or ethyl acetate and uniformly mixing;
6) adding an initiator and a part of first solvent or ethyl acetate for dilution into a reactor 3, and uniformly mixing;
7) after the temperature of the reactor 1 rises to 50-80 ℃, the monomers in the reactor 2 and the initiator in the reactor 3 are gradually added to start polymerization reaction;
8) after the reaction is finished, the reactor 1 is cooled to room temperature, and the synthesized polymerization product is filtered, washed and dried to obtain the carbomer thickening agent capable of being quickly wetted and dispersed.
In the steps, the reaction temperature is 50-80 ℃ to promote the reaction rate, shorten the reaction time, be beneficial to reducing the generation of byproducts and improve the quality of products.
In the polymerization process, protective gas such as nitrogen is preferably introduced, so that the side reaction is favorably reduced, and the phase of the carbomer is improved.
Compared with the prior art, the invention has the following advantages:
the carbomer thickener is formed by polymerizing an inner layer component firstly and then forming an inner layer component and an outer layer component by polymerizing the inner layer component, so that the inner layer component and the outer layer component are formed, the outer layer adopts a long-chain organic salt surfactant which is distributed on the surface of carbomer in polymerization, and the surface of carbomer can quickly absorb water and be wetted when being added into water; the inlayer obtains with strong polarity monomer and acrylic ester monomer copolymerization, provides the inside passageway that absorbs water of carbomer structure, can make the hydrone get into fast to make carbomer can be quick after adding the aquatic absorb water moist.
When the carbomer is used, the carbomer can be quickly wetted and dispersed in water, so that the using process that the traditional carbomer needs to be activated overnight is greatly optimized, and the production efficiency is improved. Meanwhile, the carbomer disclosed by the invention has good thickening efficiency and ion resistance, and can basically meet all the requirements of the carbomer. The carbomer disclosed by the invention can keep high transparency in an aqueous solution system or a transparent nursing formula system, and the use experience of a product is improved.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the examples.
The commercially available products, powdered carbomer B1 and powdered carbomer B2, were selected as controls and tested in comparison to the products made in the examples below in different application formulations.
The selected powder CARBOMER B1 is TC-CARBOMER FD 2010 of Guangzhou Tiancigao New materials, Inc., B1 is acrylic acid (ester)/C10-30 alkanol acrylate cross-linked polymer, and the powder CARBOMER is sold in domestic markets and has high acceptance, and the main parameters are as follows:
the carbomer thickener B2 selected was Carbopol Ultrez 20 from Luborun, Inc., and B2 was hydrophobically modified highly crosslinked polyacrylic acid. The product has high market acceptance, and the main parameters are as follows:
example 1
A carbomer thickener C1 with a rapid wetting and dispersing function is prepared, and the synthetic formula comprises the following components:
TABLE 1
The carbomer thickener with the function of quick wetting and dispersing, which is synthesized by adopting the formula, comprises the following steps:
1) adding 252g of cyclohexane and 148.2g of ethyl acetate into 1500ml of a four-neck flask (reactor 1) with a mechanical stirrer and a nitrogen inlet, adding 0.6g of sorbitan stearate, uniformly mixing, introducing nitrogen for replacing for more than 30min, and replacing the oxygen content in the system to be less than 1 x 10-7 mg/L;
2) adding 92g of acrylic acid, 1g of potassium acrylate, 6g of lauryl methacrylate and 1g of trimethylolpropane diallyl ether into a four-neck flask, uniformly mixing, and continuously introducing nitrogen to replace oxygen;
3) heating the reaction temperature to 58 ℃, adding 0.2g of azobisisobutyronitrile into the four-neck flask, starting a polymerization reaction, reacting for 7 hours till the reaction is complete, and cooling to room temperature;
4) in a 500ml three-necked flask (reactor 2), 24.55g of acrylic acid, 0.3g of pentaerythritol diallyl ether, 0.15g of sodium laurate, 0.05g of sorbitan stearate and 255.8g of ethyl acetate were added, and mixed uniformly under a nitrogen atmosphere for use;
5) 0.05g of azobisisobutyronitrile and 100g of ethyl acetate are added into a 250ml three-neck flask (reactor 3) and mixed evenly for standby under nitrogen atmosphere;
6) after the temperature of the reactor 1 rises to 60 ℃, simultaneously dropwise adding monomers and an initiator in the reactor 2 and the reactor 3, measuring the dropwise adding time for 4 hours, starting polymerization reaction, and completely preserving heat for 2 hours until the reaction is finished;
7) the reaction solution in reactor 1 was cooled to room temperature and filtered through a suction funnel, while the mixture was stirred with a stirred mixture of 300g cyclohexane and ethyl acetate in a ratio of 1:2, and finally, putting the mixture into an oven at 95 ℃ for drying for 24 hours to obtain the carbomer thickener C1 with the function of quick wetting and dispersing.
Example 2
The carbomer thickener C2 with the function of quick wetting and dispersing is prepared, and the synthetic formula comprises the following components:
TABLE 2
The synthesis procedure of example 2 was the same as that of example 1 except that the reaction temperature in steps 3) and 6) of example 2 was 69 deg.C, and no further description was made herein, and carbomer thickener C2 having a fast wetting and dispersing function was obtained according to this formulation.
Example 3
The carbomer thickener C3 with the function of quick wetting and dispersing is prepared, and the synthetic formula comprises the following components:
TABLE 3
The synthesis procedure of example 3 was the same as that of example 1 except that the reaction temperature in steps 3) and 6) of example 3 was 50 ℃ and no further description was made herein, and carbomer thickener C3 having a fast wetting and dispersing function was obtained according to this formulation.
Example 4
The carbomer thickener C4 with the function of quick wetting and dispersing is prepared, and the synthetic formula comprises the following components:
TABLE 4
The synthesis procedure of example 4 was the same as that of example 1 except that the reaction temperature in steps 3) and 6) of example 4 was 80 ℃ and no further description was made herein, and carbomer thickener C4 having a fast wetting and dispersing function was obtained according to this formulation.
Example 5
The carbomer thickener C5 with the function of quick wetting and dispersing is prepared, and the synthetic formula comprises the following components:
TABLE 5
The synthesis procedure of example 5 was the same as that of example 1 except that the reaction temperature in steps 3) and 6) of example 5 was 71 deg.C, and no further description was made herein, and carbomer thickener C5 having a fast wetting and dispersing function was obtained according to this formulation.
Examples 5-6 below are examples using the above described thickeners for leave-on hand cleanser systems, and are comparative to commercially available thickeners B1, B2. The items and methods to be tested are as follows:
1) thickening efficiency, namely adding the same amount of thickening agent into the system, and inspecting the viscosity of the system at 20rpm at 20 ℃ and the unit cp;
2) and (3) transparency test: measured using a yuniko 7200 spectrophotometer, 100% being most preferred;
3) the storage stability is that the prepared finished paint is put into a 50 ℃ oven and is placed for 14 days, and the change of the appearance state of the system is inspected; and (3) judging standard: the storage stability was good at 5 points, not good at 1 point;
4) wetting time test: putting 200g of deionized water in a 500ml vertical lifting bottle, uniformly spreading, naturally wetting until the upper white part disappears, and recording the time;
5) skin feel test: 20 female subjects with the habit of using the color cosmetic products are selected, and the age range is 20-45 years. After the subjects applied the products provided by the invention examples C1-C5 and the comparative examples B1 and B2 after sequentially cleaning the face, refreshing the skin water and caring the skin milk, the freshness of the products was evaluated in a sensory manner, and the scoring criteria were as follows:
no greasy feeling, and the refreshing degree is very satisfactory from 9 to 10 minutes,
has a slightly greasy feeling of 7-8 minutes,
has a greasy feeling of 4-6 points,
has obvious greasy feeling of 1-3 points,
the amount of the oil-based resin composition is 0 point,
an average score is calculated.
6) Moisture retention test: in the humidity environment of 40-50%, the subjects applied the products provided by the invention examples C1-C5 and the comparative examples B1 and B2 after sequentially cleaning the face, refreshing the skin water and caring the skin milk, kept for 30min, and then tested the humidity of the applied part by using a skin moisture tester, and the data is recorded.
Example 6
In the personal care area, skin moisturizer formulations show a comparison of carbomer thickeners C1-C5 synthesized in examples 1-5 of the present invention with fast moisturizing and dispersing function and the commercial products B1, B2.
TABLE 6
The preparation method of the skin moisturizer formula comprises the following steps:
1) 89.4g of deionized water was added to a 250ml beaker and heated to 85 ℃;
2) adding 1g of methyl glucose sesquistearate and 0.3g of dimethyl silicone oil into a beaker while stirring, and mixing uniformly;
3) reducing the temperature of the mixed solution in the beaker to 60 ℃, adding 1g of methyl glucose polyether-20 and 3g of neopentyl glycol diethyl hexanoate while stirring, and uniformly mixing;
4) cooling the beaker mixture to room temperature, keeping stirring, adding 0.3g of honeysuckle extract, 0.02g of BHT, 0.02g of disodium ethylene diamine tetraacetate, 0.5g of phenoxyethanol and 0.35g of carbomer into the beaker mixture, and uniformly mixing;
5) homogenizing the beaker mixed solution for 30min by a homogenizer at the rotation speed of 20000rpm to ensure that the mixture is more uniform;
6) slowly adding 18% sodium hydroxide solution into the beaker mixed solution, changing the rotation speed along with the increase of the viscosity to uniformly neutralize the whole, and adjusting the pH value to 5.2-5.8.
In this formulation, comparative examples synthesized carbomer thickeners C1-C5 and commercially available products B1, B2 with fast wetting and dispersing function, giving the following table results:
TABLE 7
As can be seen from Table 7, the carbomer thickener with the rapid wetting and dispersing function disclosed by the invention has excellent viscosity, relatively fast wetting time, good stability, relatively good skin feeling experience and excellent moisture retention in a skin moisturizer formula, and can meet the actual needs of the skin moisturizer.
Example 7
The synthetic carbomer thickener with fast wetting and dispersing function C1-C5 of the present invention was tested against the commercial products B1, B2 in a skin mask formulation.
The formula of the skin mask is as follows:
TABLE 8
The preparation method of the skin mask formula comprises the following steps:
1) 59.96g of deionized water were added to a 250ml beaker and heated to 70 ℃;
2) adding 5g of polydimethylsiloxane and 1g of PEG-10-dimethyl siloxane into the beaker while stirring, and uniformly mixing;
3) reducing the temperature of the mixed solution in the beaker to 50 ℃, adding 1.2g of butanediol, 0.6g of glycerol, 1g of kaolin and 0.2g of carbomer while stirring, and uniformly mixing;
4) reducing the temperature of the beaker mixed solution to room temperature, and homogenizing the beaker mixed solution for 30min by a homogenizer at the rotation speed of 20000rpm to ensure that the beaker mixed solution is mixed more uniformly;
5) keeping stirring, slowly adding 30g of polyurethane-35 & polyurethane-11, 0.1g of EDTA-2Na and 0.4g of phenoxyethanol & caprylyl glycol into the beaker mixed solution, uniformly mixing, adding 0.54g of triethanolamine in a metering manner, changing the rotating speed along with the increase of viscosity to uniformly neutralize the whole, and adjusting the pH value to 5.2-5.5.
In this formulation, comparative examples carbomer thickeners C1-C5 and commercially available products B1, B2 having fast wetting and dispersing function were synthesized to give the following table results:
TABLE 9
As can be seen from Table 9, the carbomer thickener having a fast wetting and dispersing function, C1-C5, and the commercial products B1 and B2 of the present invention also have good thickening efficiency in skin mask formulations without affecting transparency and storage stability.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, simplifications, substitutions and equivalents which do not depart from the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A carbomer thickener capable of being rapidly wetted and dispersed is obtained by initiating a reaction in a first solvent from raw materials comprising an inner layer component and an outer layer component through a radical initiator:
a) the inner layer component is obtained by initiating reaction of a reaction system containing a second solvent and comprising the following reaction components through a free radical initiator:
ai) 80 to 98% by mass, based on the total mass of the inner layer components, of at least one unsaturated carboxylic acid containing a polymerizable carbon-carbon double bond and a carboxyl group;
aii) 0.1 to 15% by mass, based on the total mass of the inner layer components, of at least one unsaturated olefinic monomer containing a polymerizable carbon-carbon double bond and at least one polar structure, other than an unsaturated carboxylic acid;
aiii) 1-12% by mass of the total mass of the inner layer component of at least one (meth) acrylate monomer having the following general structural formula I:
wherein R is1Is hydrogen or methyl, R2Is an alkyl structure containing 1 to 30 carbon atoms;
aiv) 0.01 to 5% by mass, based on the total mass of the inner layer components, of at least one crosslinking agent containing at least two unsaturated carbon-carbon double bonds;
b) an outer layer component comprising:
bi) from 90 to 99.5% by mass, based on the total mass of the outer layer components, of at least one unsaturated carboxylic acid containing a polymerizable carbon-carbon double bond and a carboxyl group;
bii) 0.01 to 5% by mass, based on the total mass of the outer layer components, of at least one crosslinking agent containing at least two unsaturated carbon-carbon double bonds;
biii) 0.1 to 5% based on the total mass of the outer layer components of at least one surfactant of a long-chain alkyl carboxylate having the following general structural formula II:
wherein R is3Is an alkyl structure containing 6-20 carbon atoms, and M is sodium ion, potassium ion or lithium ion;
wherein the mass fraction of the inner layer component is 70-95% and the mass fraction of the outer layer component is 5-30% of the total mass of the raw materials.
2. The carbomer thickener of claim 1, wherein said at least one unsaturated carboxylic acid comprising a polymerizable carbon-carbon double bond and a carboxyl group is one or more of acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, crotonic acid and aconitic acid.
3. Carbomer thickener according to claim 1 or 2, characterized in that said unsaturated olefinic monomer containing at least one polymerizable carbon-carbon double bond and at least one polar structure, different from an unsaturated carboxylic acid, is one or more of a polymerizable carboxylic acid salt, hydroxy (meth) acrylate and 2-acrylamido-2-methylpropanesulfonic acid, preferably one or more of hydroxyethyl (meth) acrylate, sodium (meth) acrylate, hydroxypropyl (meth) acrylate and 2-acrylamido-2-methylpropanesulfonic acid.
4. Carbomer thickener according to any of the claims 1 to 3, wherein in said general structural formula I, R1Is methyl, R2An alkyl structure containing 10 to 20 carbon atoms; preferably, the at least one (meth) acrylate monomer is one or more of lauryl methacrylate, myristyl methacrylate, cetyl methacrylate and stearyl methacrylate.
5. Carbomer thickener according to any of the claims 1 to 4, wherein in said general structural formula II R3Preferably an alkyl structure of 10 to 20 carbon atoms; preferably, the surfactant of the long-chain alkyl carboxylate is one or more of sodium laurate, potassium laurate, sodium stearate, potassium stearate, and lithium stearate.
6. Carbomer thickener according to any of the claims 1 to 5, wherein said at least one crosslinking agent containing at least two unsaturated carbon-carbon double bonds is one or more of a multifunctional acrylate having at least two polymerizable ethylenically unsaturated double bonds and a polyalkenyl polyether having at least two polymerizable ethylenically unsaturated double bonds.
7. Carbomer thickener according to any of the claims 1 to 6, wherein said first and second solvents are hydrocarbon solvents and/or alkyl ester solvents, wherein said hydrocarbon solvents are one or more of n-hexane, cyclohexane, n-heptane, cycloheptane and n-decane; the alkyl ester solvent is one or more of ethyl acetate, butyl acetate, ethyl propionate and butyl propionate; preferably, the first and second solvents are a mixture of cyclohexane and ethyl acetate;
further preferably, the first solvent is a mixture of cyclohexane and ethyl acetate in a mass ratio of 1:2-1:4, and the second solvent is a mixture of cyclohexane and ethyl acetate in a mass ratio of 2:1-1: 1.
8. Carbomer thickener according to any of the claims 1 to 7, wherein said free radical type initiator is one or more of organic peroxide based compounds, azo based compounds, inorganic persulfate based compounds and hydrogen peroxide; preferably, the radical initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, lauroyl peroxide, ammonium persulfate, sodium persulfate and hydrogen peroxide.
9. The carbomer thickener according to any one of claims 1 to 8, wherein in the reaction components for preparing said inner layer component, said at least one unsaturated carboxylic acid containing a polymerizable carbon-carbon double bond and a carboxyl group is used in an amount of from 85 to 95.5%, said at least one unsaturated ethylenic monomer other than an unsaturated carboxylic acid containing a polymerizable carbon-carbon double bond and at least one polar structure is used in an amount of from 1 to 5%, said at least one (meth) acrylate monomer is used in an amount of from 3 to 8%, and said at least one crosslinking agent containing at least two unsaturated carbon-carbon double bonds is used in an amount of from 0.1 to 3%, based on the total mass of said inner layer component;
the content of the at least one unsaturated carboxylic acid containing polymerizable carbon-carbon double bonds and carboxyl groups in the outer layer component is 95-99%, the content of the at least one surfactant of long-chain alkyl carboxylate is 0.5-3%, and the content of the at least one cross-linking agent containing at least two unsaturated carbon-carbon double bonds is 0.1-3%;
preferably, the mass fraction of the inner layer component accounts for 80-90% and the mass fraction of the outer layer component accounts for 10-20% of the total mass of the raw materials.
10. The method of preparing the carbomer thickener of any one of claims 1 to 9, wherein said method comprises the steps of:
I) adding reaction components for preparing the inner layer component into a second solvent in proportion and uniformly mixing;
II) heating the reaction system obtained in the step I) to 50-80 ℃, adding the free radical initiator, and carrying out polymerization reaction to obtain the inner layer component;
III) mixing the free radical initiator and the outer layer component with the inner layer component obtained in the step II) in a first solvent at 50-80 ℃, carrying out polymerization reaction, cooling after the reaction, filtering, separating, washing and drying to obtain a carbomer thickening agent;
preferably, in the step I), a dispersant is further added into the reaction system obtained by mixing; in the step III), the free radical initiator and the outer layer component are pre-diluted and then mixed with the inner layer component, wherein a dispersing agent is further added into the diluted outer layer component;
further preferably, the dispersant is one or more of propylene glycol monostearate, sorbitan stearate, polyoxyethylene (2EO) oleyl ether, isomeric trideceth-5 and laureth-3.
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