CN106750255B - A kind of preparation method and applications of anionic and nonionic type reactive emulsifier - Google Patents
A kind of preparation method and applications of anionic and nonionic type reactive emulsifier Download PDFInfo
- Publication number
- CN106750255B CN106750255B CN201611216316.XA CN201611216316A CN106750255B CN 106750255 B CN106750255 B CN 106750255B CN 201611216316 A CN201611216316 A CN 201611216316A CN 106750255 B CN106750255 B CN 106750255B
- Authority
- CN
- China
- Prior art keywords
- anionic
- reactive emulsifier
- nonionic type
- type reactive
- polyoxyethylene ether
- 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.)
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- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 88
- 125000000129 anionic group Chemical group 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 42
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 42
- 150000003333 secondary alcohols Chemical class 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000003513 alkali Substances 0.000 claims description 19
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 17
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 17
- 239000011976 maleic acid Substances 0.000 claims description 17
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims 4
- 150000001340 alkali metals Chemical class 0.000 claims 4
- 235000021419 vinegar Nutrition 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 36
- 239000002245 particle Substances 0.000 abstract description 10
- 239000006185 dispersion Substances 0.000 abstract description 4
- 238000009736 wetting Methods 0.000 abstract description 4
- NJVOHKFLBKQLIZ-UHFFFAOYSA-N (2-ethenylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C=C NJVOHKFLBKQLIZ-UHFFFAOYSA-N 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- -1 hydroxypropyl sodium alkyl sulfonate Chemical class 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 150000002689 maleic acids Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 235000011118 potassium hydroxide Nutrition 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 229940087291 tridecyl alcohol Drugs 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000006071 cream Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 125000000746 allylic group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 2
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- 150000000211 1-dodecanols Chemical class 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241001432959 Chernes Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical class CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229940097037 decylene glycol Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 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
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000002020 sage Nutrition 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 235000011091 sodium acetates Nutrition 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
-
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Abstract
The invention discloses a kind of preparation method and applications of anionic and nonionic type reactive emulsifier.The structural formula of the anionic and nonionic type reactive emulsifier is as follows:Wherein
Description
Technical field
The present invention relates to a kind of preparation method and applications of anionic and nonionic type reactive emulsifier, belong to polymer emulsion
The field of middle emulsifier.
Background technique
Emulsifier is one of the main component in emulsion polymerization systems, plays decisive role to the performance of polymer.It passes
The emulsifier of system is adsorbed in emulsion particle surface by physical action, when temperature change, imposing shearing force or electrolyte being added, cream
The stability of liquid can change or even be demulsified；Emulsifier can migrate to film coated surface and form one layer of non-ization in film forming procedure
The hydrophilic emulsifying agent layer for learning bonding, will lead to film water absorption and swelling once encounteing water or be affected with dump, and cause frosting, whiting, gloss decline
The defects of, reduce coating film gloss, rate of film build and water resistance.
In emulsion polymerization, reactive emulsifier is bonded in the way of covalent bond by the double bond functional group in molecule
Polymer particle surface becomes a part of polymer, avoids emulsifier from desorption on polymer particle or in latex film
Migration, greatly reduce the hydrophilic radical of latex film surface, not only effectively solve water paint ink system in emulsifier in base
Expect surface and surface of pigments competitive Adsorption problem, and increase substantially emulsion intercalation method, coating film gloss, rate of drying,
Filming performance and water-resistance property of coating.It is dry in order to improve film using that can be greatly reduced in ordinary emulsion in water paint ink
Dry speed and a large amount of volatility low-carbon alcohols, ethers, esters quick dry agent and the coalescing agent added, so that printing be greatly reduced
Ink VOC emission.In addition, most reactive emulsifiers are linked in polymer segment by participating in reaction, high degree
Reduce using existing for free form, using APEO class emulsifier be representative, difficult to degrade conventional emulsifier in water body environment
Discharge reduces water body COD content, reduces environmental pollution and the generation of foam, reduces wastewater treatment difficulty, increases waste water circulation
Utilization rate.
Since polymerisable emulsifier is used for emulsion polymerization for the first time by Greene et al., many scholars and research institution exist
This respect has done many researchs.According to the difference of reactive group, reactive emulsifier is divided into allylic, phenylethylene, third
Acrylamide, maleic acid esters etc..Model sage, which forces, makees reactive emulsifier with hydroxypropyl sodium alkyl sulfonate (SAHS), has synthesized bullet
Property acrylic acid ester emulsion, the results showed that the PA lotion of SAHS modified synthesis is more stable and viscosity is lower.Chern etc. will be reactive newborn
Agent sodium dodecyl allyl base Succinate sodium sulfonate is for adding on a small quantity in the semi-continuous emulsion polymerizing of butyl acrylate
In the case of electrolyte, more stable polymer emulsion can be obtained；It wears obviously with 2- acrylamide-2-methylpro panesulfonic acid sodium
(APMS) solid content height is successfully prepared using styrene and butyl acrylate as comonomer for a kind of polymerisable emulsifier
Up to 50% styrene-acrylic emulsion, and the properties such as the electrolyte resistance of lotion, pH stability, mechanical stability are all preferable；Deng
Sword such as utilizes maleic anhydride to polymerize as a kind of reactive emulsifier for pure-acrylic emulsion with the single-esterification product of lauryl alcohol
In, compared with conventional emulsifier, shear strength, water resistance, transparency, pollution resistance of film etc. all have clear improvement.Pich etc.
It is prepared for a kind of fluorine-containing reactive emulsifier first, obtains a kind of fluorine-containing cream after it is copolymerized with styrene, butyl acrylate
Liquid, the emulsion intercalation method and film forming are preferable, and the corrosion resistance of film, the transparency, glossiness are also fine；It closes in recent years
It is more in the research of maleic diester type reactive emulsifier.Xu Jian etc. has synthesized maleic anhydride list decylene glycol ester first, so
Carry out reacting under alkaline condition with 2,3- epoxypropyltrimethylchloride chloride afterwards generate a kind of maleic diester type sun from
Sub- emulsifier can significantly reduce the surface tension of water, and have lower critical micelle concentration (0.2-0.6mmol.L-1)。He
Etc. having synthesized a kind of diester-type reactive emulsifier maleic anhydride decylene glycol ester sulfopropyl sodium salt (M-12), it to be used for styrene, third
The ultrasonic radiation polymerization reaction of olefin(e) acid butyl ester.With the increase of M-12 dosage, emulsion particle diameter gradually becomes smaller and is distributed and broadens, simultaneously
Since emulsifier is chemically bound in the surface of emulsion particle securely, gained emulsion intercalation method is preferable.
Reactivity and bonding rate of the allylic reactive emulsifier in emulsion polymerization are low, are generally only used for acrylic acid
Class, vinyl acetate esters isoreactivity be higher, in water-soluble biggish monomer polymerization；Phenylethylene reactive emulsifier is due to phenyl ring
Draw electronic effect, reactivity is moderate, and the stability of emulsion being prepared is not good enough, thus usually require add a certain amount of emulsifier
Or change the feeding mode of monomer；Acrylic amide reactive emulsifier reactivity is higher, can be applied to styrene, propylene
In the polymerization reaction of esters of gallic acid monomer, but emulsifier homopolymerization risk can be faced；Maleic acid esters reactive emulsifier reactivity
It is moderate, and it is not easy autohemagglutination, keep participation copolymerization probability higher, emulsifier can effectively be avoided to reduce emulsification effect because of itself homopolymerization
Fruit applies applied to the good combination property in emulsion polymerization and can get high-performance emulsions film in coating and printing ink, be to study most
For extensive a kind of reactive emulsifier.
In maleic acid esters reactive emulsifier, domestic and international correlative study mainly uses C12-C16Straight chain primary alcohol/alcohol ether,
Alkyl phenol polyoxyethylene ether is starting material, through maleated, obtain non-ionic, anionic, anionic and nonionic type and
The maleic acid esters reactive emulsifier of double ion type is simultaneously applied in emulsion polymerization.However, since primary alconol is free of EO hydrophilic chain
Section, spatial stability is poor, the emulsion particle diameter of synthesis is bigger than normal, and resistance to hard water deviation；And the alkyl with excellent emulsifying capacity
Phenol has environmental organism toxicity again, and domestic and international relevant industries are being phased out use.With the C of ordinary construction12-C16Linear primary
Alcohol/alcohol ether, alkyl phenol polyoxyethylene ether are compared, and secondary alcohol is located at carbochain centre rather than both ends, the special space structure of umbrella
Secondary alcohol is imparted with good spatial stability, high emulsifying strength, narrow hydrogel range, low bubble, low hydrodynamic(al) state and balance surface
Tension, to substrate wetting good and there is fine dispersion, wettability to pigment, be the instead of APEO class surfactant
One selection.
Therefore, the maleic acid list secondary alcohol polyoxyethylene ether -2- hydroxyl reacted using secondary alcohol polyoxyethylene ether as starting material
Base propyl sulfonic acid salt anionic and nonionic type reactive emulsifier has than conventional emulsifier and common reactive emulsifier more
The performances such as excellent emulsion dispersion wetting and water-resistance property of coating.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method and applications of anionic and nonionic type reactive emulsifier.
The technical solution used in the present invention is:
A kind of anionic and nonionic type reactive emulsifier, structural formula are as follows:
WhereinN=5~40.
A kind of preparation method of the anionic and nonionic type reactive emulsifier, comprising the following steps:
1) maleic anhydride and secondary alcohol polyoxyethylene ether react synthesis secondary alcohol polyoxyethylene ether maleic acid under the action of catalyst
Monoesters；
2) it uses in aqueous slkali with secondary alcohol polyoxyethylene ether maleic acid monoester, obtains secondary alcohol polyoxyethylene ether maleic acid monoester
Salt；
3) it after secondary alcohol polyoxyethylene ether maleic acid monoester salt is reacted with 3- chlorine-2-hydroxyl propanesulfonate, then adjusts system and consolidates
Anionic and nonionic type reactive emulsifier is made after content.
The maleic anhydride, secondary alcohol polyoxyethylene ether, catalyst, alkali, 3- chlorine-2-hydroxyl propanesulfonate mass ratio be
(50~60): (195~970): (0.3~6): (18~30): (90~110).
The secondary alcohol polyoxyethylene ether is the 6- tridecyl alcohol polyoxyethylene ether or 2,6 that ethylene oxide number is 5~40,
8- trimethyl -4- nonane alcohol polyoxyethylene ether.
The secondary alcohol polyoxyethylene ether is using preceding in 80~110 DEG C of 5~6h of vacuum drying.
The catalyst be p-methyl benzenesulfonic acid or alkali alcoholate, hydroxide, carbonate, in acetate at least
It is a kind of；The alkali is one of alkali alcoholate, hydroxide.
In step 3), the solid content is 25~50%.
The reaction temperature of step 1) is 80~140 DEG C, and the reaction time is 1.5~6h, and reaction carries out under protective atmosphere；Step
System temperature before rapid 2) neutralization is 50~80 DEG C, and neutralization system pH is 6~7 after alkali is added, and reaction temperature is 60~90 DEG C, instead
It is 1~3h between seasonable；The reaction temperature of step 3) is 80~120 DEG C, and the reaction time is 2~6h.
The anionic and nonionic type reactive emulsifier is preparing the application in polymer.
The application, be in the presence of at least one described anionic and nonionic type reactive emulsifier, make monomer into
Row emulsion polymerization.
The beneficial effects of the present invention are: reactive emulsifier disclosed by the invention has spatial stability, high emulsion dispersion
The excellent properties such as ability, low bubble, low surface tension, wetting, applying can prepare in emulsion polymerization especially Styrene-Acrylate Emulsion Polymerization
The high-performance emulsions of the characteristics such as high stability, high glaze, small particle out.
Specific embodiment
A kind of anionic and nonionic type reactive emulsifier, structural formula are as follows:
Wherein(6- tridecyl) or
(2,6,8- trimethyl -4- nonyl)；N=5~40.
A kind of preparation method of the anionic and nonionic type reactive emulsifier, comprising the following steps:
1) maleic anhydride and secondary alcohol polyoxyethylene ether react synthesis secondary alcohol polyoxyethylene ether maleic acid under the action of catalyst
Monoesters；
2) it uses in aqueous slkali with secondary alcohol polyoxyethylene ether maleic acid monoester, obtains secondary alcohol polyoxyethylene ether maleic acid monoester
Salt；
3) it after secondary alcohol polyoxyethylene ether maleic acid monoester salt is reacted with 3- chlorine-2-hydroxyl propanesulfonate, then adjusts system and consolidates
Anionic and nonionic type reactive emulsifier is made after content.
Preferably, the maleic anhydride, secondary alcohol polyoxyethylene ether, catalyst, alkali, 3- chlorine-2-hydroxyl propanesulfonate
Mass ratio is (50~60): (195~970): (0.3~6): (18~30): (90~110)；It is further preferred that the horse
Come acid anhydrides, secondary alcohol polyoxyethylene ether, catalyst, alkali, 3- chlorine-2-hydroxyl propanesulfonate mass ratio be (50~55): (220~
760): (1~4.5): (19~26.5): (98~105).
Preferably, the secondary alcohol polyoxyethylene ether is the 6- tridecyl alcohol polyoxyethylene that ethylene oxide number is 5~40
Ether or 2,6,8- trimethyl -4- nonane alcohol polyoxyethylene ether.
The structural formula of 6- tridecyl alcohol polyoxyethylene ether is as follows:
N=5~40 in formula.
The structural formula of 2,6,8- trimethyl -4- nonane alcohol polyoxyethylene ether is as follows:
N=5~40 in formula.
Preferably, the secondary alcohol polyoxyethylene ether is using preceding in 80~110 DEG C of 5~6h of vacuum drying.
Preferably, the catalyst is p-methyl benzenesulfonic acid or alkali alcoholate, hydroxide, carbonate, acetate
At least one of；It is further preferred that the catalyst is p-methyl benzenesulfonic acid, sodium alkoxide, potassium alcoholate, sodium hydroxide, hydroxide
At least one of potassium, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate；Still further preferably, the catalyst is to first
At least one of benzene sulfonic acid, sodium methoxide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium acetate.
Preferably, the alkali is one of alkali alcoholate, hydroxide；It is further preferred that the alkali
For one of sodium alkoxide, potassium alcoholate, sodium hydroxide, potassium hydroxide；Still further preferably, the alkali is sodium methoxide, hydroxide
One of sodium, potassium hydroxide.
Preferably, in step 3), the solid content is 25~50%；It is further preferred that described consolidates in step 3)
Content is 30~45%.
Preferably, the reaction temperature of step 1) is 80~140 DEG C, and the reaction time is 1.5~6h, is reacted under protective atmosphere
It carries out；Step 2) neutralize before system temperature be 50~80 DEG C, be added alkali after neutralize system pH be 6~7, reaction temperature be 60~
90 DEG C, the reaction time is 1~3h；The reaction temperature of step 3) is 80~120 DEG C, and the reaction time is 2~6h；Further preferably
, the protective atmosphere is one of nitrogen or inert gas；Still further preferably, the protective atmosphere is nitrogen
Gas.
The anionic and nonionic type reactive emulsifier is preparing the application in polymer.
Preferably, the application is made in the presence of at least one described anionic and nonionic type reactive emulsifier
Monomer carries out emulsion polymerization.
Preferably, the monomer is acrylate, methacrylate, unsaturated amides, unsaturated nitrile, styrene spread out
At least one of biology, diene derivatives, polyethyleneglycol diacrylate and polyethylene glycol dimethacrylate；Into one
Step is preferred, the monomer be in acrylate, methacrylate, styrene derivative and diene derivatives at least
It is a kind of；Still further preferably, the monomer is ethyl acrylate, butyl acrylate, 2-EHA, methyl-prop
E pioic acid methyl ester, ethyl methacrylate, 2-Hydroxyethyl methacrylate, glycidyl methacrylate, α-methylstyrene,
At least one of butadiene and isoprene.
Preferably, the anionic and nonionic type reactive emulsifier accounts for polymerization reaction system (amount based on whole monomers)
Mass fraction is 0.1~20%；It is further preferred that the anionic and nonionic type reactive emulsifier accounts for polymerization reaction system
Mass fraction is 0.2~5%；Still further preferably, the anionic and nonionic type reactive emulsifier accounts for polymerization reaction system
Mass fraction be 0.5~4%.
Furthermore, it is understood that the application, is selected one or more of the anionic and nonionic type reactive emulsifier, or
Use at least one anionic and nonionic type reactive emulsifier and other emulsifiers or protecting colloid.
Preferably, other emulsifiers are dodecyl benzene sulfonate, alkyl sulfate, alkyl polyoxyethylene ether sulphur
Hydrochlorate, alkyl phenyl polyethylene oxides ether sulfate, dialkyl sulfosuccinates, alkyl polyoxyethylene ether and alkyl phenyl polyoxy
At least one of vinethene.
Preferably, the protecting colloid is polyacrylic acid hard resin protective glue, polyvinyl alcohol and hydroxyethyl cellulose
At least one of.
Preferably, other emulsifiers or protecting colloid account for the quality of total emulsifiers no more than 50%；It is further excellent
Choosing, other emulsifiers or protecting colloid account for the quality of total emulsifiers no more than 25%.
Preferably, described to be aggregated in that initiator effect is lower to be carried out, the initiator be inorganic peroxide initiator,
At least one of organic peroxide evocating agent, azo initiator, redox initiator；It is further preferred that described
Initiator is hydrogen peroxide, potassium peroxydisulfate, ammonium persulfate, isopropyl benzene hydroperoxide, diisopropylbenzene hydroperoxide, two isobutyl of azo
Nitrile, azo isobutyl cyano formamide or the compositions such as peroxide and sodium hydrogensulfite, sodium thiosulfate, ferrous sulfate, carbohydrate
At least one of redox initiator.
The contents of the present invention are described in further detail below by way of specific embodiment.
In these embodiments, unless otherwise noted, all percentage is weight percent.6- tridecyl alcohol is poly-
Ethylene oxide ether or 2,6,8- trimethyl -4- nonane alcohol polyoxyethylene ether are to buy gained from commercial channel import.
Synthetic example 1:
By mass fraction, takes 300 parts of 6- ammonium trideceth 9EO into four-hole boiling flask, 52 parts of maleic acids are added
Acid anhydride and 1.0 parts of sodium methoxides are in N2The lower 88 DEG C of reactions 6h of gas shielded；80 DEG C are cooled to, is added in 26.5 parts of sodium methoxides and system pH is arrived
6.5~7.0,85 DEG C vacuumize 2h；It is added 98 parts of 3- chlorine-2-hydroxyl propyl sulfonic acid sodium, after 100 DEG C of reaction 4h, stirs at low speed down
Quantitative water adjustment system solid content is added to 35%, obtains maleic acid list secondary alcohol polyoxyethylene ether -2- propane sulfonate
Anionic and nonionic type reactive emulsifier.
Synthetic example 2:
By mass fraction, takes 255 parts of 6- ammonium trideceth 7EO into four-hole boiling flask, 50 parts of maleic acids are added
Acid anhydride and 1.0 parts of potassium hydroxide are in N2The lower 100 DEG C of reactions 4.0h of gas shielded；70 DEG C are cooled to, is added in 25.5 parts of sodium methoxides and body
It is pH to 6.5~6.8,90 DEG C vacuumize 1h；It is added 100 parts of 3- chlorine-2-hydroxyl propyl sulfonic acid sodium, it is low after 110 DEG C of reaction 3.5h
Speed is added with stirring quantitative water adjustment system solid content to 30%, obtains maleic acid list secondary alcohol polyoxyethylene ether -2- hydroxyl third
Base sulfonate anionic and nonionic type reactive emulsifier.
Synthetic example 3:
By mass fraction, takes 760 parts of 6- ammonium trideceth 30EO into four-hole boiling flask, 55 parts of maleic acids are added
Acid anhydride and 4.5 parts of sodium acetates are in N2The lower 120 DEG C of reactions 6h of gas shielded；65 DEG C are cooled to, is added in 19 parts of sodium hydroxides and system pH
2.5h is vacuumized to 6.3~6.8,90 DEG C；It is added 105 parts of 3- chlorine-2-hydroxyl propyl sulfonic acid sodium, after 105 DEG C of reaction 5h, low speed is stirred
The quantitative water adjustment system solid content of lower addition is mixed to 35%, obtains maleic acid list secondary alcohol polyoxyethylene ether -2- hydroxypropyl sulphur
Hydrochlorate anionic and nonionic type reactive emulsifier.
Synthetic example 4:
By mass fraction, 220 part 2 is taken, 6,8- trimethyl -4- nonane alcohol polyoxyethylene ether 6EO are added into four-hole boiling flask
50 parts of maleic anhydrides and 1.0 parts of p-methyl benzenesulfonic acid are in N2The lower 83 DEG C of reactions 3.5h of gas shielded；80 DEG C are cooled to, 26 parts of methanol are added
With system pH to 6.5~6.8 in sodium, 85 DEG C vacuumize 2h；98 parts of 3- chlorine-2-hydroxyl propyl sulfonic acid sodium, 100 DEG C of reaction 4h are added
Afterwards, the quantitative water adjustment system solid content of lower addition is stirred at low speed to 45%, obtains maleic acid list secondary alcohol polyoxyethylene ether -2- hydroxyl
Base propyl sulfonic acid salt anionic and nonionic type reactive emulsifier.
Synthesize comparative example 1:
By mass fraction, 240 parts of C are taken1252 parts of maleic anhydrides are added into four-hole boiling flask in fatty alcohol polyoxyethylene ether 7EO
With 1.5 parts of sodium methoxides in N2The lower 95 DEG C of reactions 5h of gas shielded, it is 7 that the product sodium hydroxide solution of 5wt%, which adjusts pH, and low speed stirs
The quantitative water adjustment system solid content of lower addition is mixed to 35wt%, obtains 1 reactive emulsifier of comparative example.
Synthesize comparative example 2:
It by mass fraction, takes 95 parts of lauryl alcohols into four-hole boiling flask, 50 parts of maleic anhydrides and 1.0 parts of sodium methoxides is added in N2
The lower 95 DEG C of reactions 5h of gas shielded, it is 7 that the product sodium hydroxide solution of 5wt%, which adjusts pH, stirs at low speed the quantitative water of lower addition
Adjustment system solid content obtains 2 reactive emulsifier of comparative example to 35wt%.
According to following aggregation schemes, with the reactive emulsifier of reactive emulsifier and comparative example 1 to 2 of the invention
Carry out emulsion polymerization.Then the evaluation of polymerization stability, particle size and mechanical stability is carried out to resulting polymerized emulsion, and
The water resistance of emulsion film forming caudacoria is evaluated.The results are shown in Table 1.It will be also found in the resulting data of common emulsifier
In table 1, with comparing.
Aggregation scheme
2 are added in 1 liter of glass reactor equipped with thermometer, blender, condenser, nitrogen inlet and dropping funel
Gram emulsifier, 300 grams of distilled water, 10 grams of n-butyl acrylates and 0.4 gram of ammonium persulfate.Logical nitrogen, then heats mixture
Stirring, when temperature is raised to 70 DEG C, is being added dropwise to 80 grams of styrene, 20 grams of methacrylic acids and 90 grams of acrylic acid just in 3 hours
The mixture of butyl ester.After being added dropwise to complete, keep reaction temperature be 80 DEG C the reaction was continued 2 hours, then with water-bath cooling to 30~
40 DEG C, emulsion system pH to 8-9 is adjusted to get styrene-acrylic emulsion with 10% ammonium hydroxide.
Polymerized emulsion performance test is as follows:
1, polymerization stability (gel fraction)
After the completion of polymerization, polymerized emulsion is filtered by the wire cloth of 100 mesh.The residue of filtering is washed with water,
It is dried overnight under 200mmHg in 105 DEG C, then weighs.Based on amount of monomer used, thus resulting value " weight will be expressed as
Measure % ".
2, partial size
After the wire cloth filtering of 100 mesh of polymerized emulsion, using 3000 laser particle analyzer of Mastersize of Malvern
Carry out partial size test.
3, mechanical stability
It is mechanical with MARON method under conditions of 10kg and 1000rpm after the wire cloth filtering of 100 mesh of polymerized emulsion
Stability test machine rotates 50 grams of polymerized emulsions 5 minutes.By the aggregation being consequently formed by the wire cloths of one 100 mesh into
Row filtering.The residue of filtering is washed with water, is dried overnight under 200mmHg in 105 DEG C, then weighs.And the amount with polymer,
Thus resulting value it will be expressed as " weight % ".
4, glossiness is tested
After the wire cloth filtering of 100 mesh of polymerized emulsion, polymerized emulsion is coated in glass with 150um wet film maker
On plate, it is poly- that the ZGM1022Glossmeter glossometer after paint film is dry using ZEHNTNER company carries out 60 ° of glossiness tests
The gloss of compound film.To exclude the interference such as ground water absorption rate, flatness, shrinkage stress, first coated one side is wiped with alcohol
It wipes completely, to dispel influence of the grease stain to test.
5, water resistance (film-brightens test)
After the wire cloth filtering of 100 mesh of polymerized emulsion, polymerized emulsion is coated on a slide glass (76 × 26mm), it is thick
Degree is 125 μm, and the film forming for carrying out it at 100 DEG C 5 minutes.After being cooled to room temperature, a testing piece is obtained.One with 8 points
Type is placed in the petrie dish on newspaper, and the slide glass for having film attached thereto is immersed in the water at room temperature.Measurement is until lead
The word time required until becoming unable to identification.
Test result is shown in Table 1.
Polymerized emulsion the performance test results obtained by 1 different emulsifiers of table
Show from the test result of table 1: can obtain that there is high cream using anionic and nonionic type reactive emulsifier of the invention
The lotion of liquid stability, low partial size.Moreover, the polymer film of gained polymerized emulsion has splendid water resistance and high glaze etc. excellent
Benign energy.
Claims (7)
1. a kind of preparation method of anionic and nonionic type reactive emulsifier, it is characterised in that: the following steps are included:
1) maleic anhydride and secondary alcohol polyoxyethylene ether react synthesis secondary alcohol polyoxyethylene ether maleic acid monoester under the action of catalyst；
2) alkali neutralization secondary alcohol polyoxyethylene ether maleic acid monoester is used, secondary alcohol polyoxyethylene ether maleic acid monoester salt is obtained；
3) after secondary alcohol polyoxyethylene ether maleic acid monoester salt is reacted with 3- chlorine-2-hydroxyl propanesulfonate, then system solid content is adjusted
Anionic and nonionic type reactive emulsifier is made afterwards；
Its structural formula of the anionic and nonionic type reactive emulsifier is as follows:
WhereinN=5~40.
2. a kind of preparation method of anionic and nonionic type reactive emulsifier according to claim 1, it is characterised in that: described
Maleic anhydride, secondary alcohol polyoxyethylene ether, catalyst, alkali, 3- chlorine-2-hydroxyl propanesulfonate mass ratio be (50~60):
(195~970): (0.3~6): (18~30): (90~110).
3. a kind of preparation method of anionic and nonionic type reactive emulsifier according to claim 2, it is characterised in that: described
Secondary alcohol polyoxyethylene ether using preceding in 80~110 DEG C of 5~6h of vacuum drying.
4. a kind of preparation method of anionic and nonionic type reactive emulsifier according to claim 2, it is characterised in that: described
Catalyst be p-methyl benzenesulfonic acid, alkali alcoholate, the hydroxide of alkali metal, the carbonate of alkali metal, alkali metal vinegar
At least one of hydrochlorate；The alkali is one of alkali alcoholate, the hydroxide of alkali metal.
5. a kind of preparation method of anionic and nonionic type reactive emulsifier according to claim 1, it is characterised in that: step
3) in, the solid content is 25~50%.
6. a kind of preparation method of anionic and nonionic type reactive emulsifier according to claim 1, it is characterised in that: step
1) reaction temperature is 80~140 DEG C, and the reaction time is 1.5~6h, and reaction carries out under protective atmosphere；Before step 2) neutralizes
System temperature be 50~80 DEG C, be added alkali after neutralize system pH be 6~7, reaction temperature be 60~90 DEG C, the reaction time be 1~
3h；The reaction temperature of step 3) is 80~120 DEG C, and the reaction time is 2~6h.
7. any one of claim 1~6 prepares resulting anionic and nonionic type reactive emulsifier and is preparing the application in polymer,
It is characterized by: making monomer carry out emulsion polymerization in the presence of at least one described anionic and nonionic type reactive emulsifier.
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