CN106750255A - 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
- CN106750255A CN106750255A CN201611216316.XA CN201611216316A CN106750255A CN 106750255 A CN106750255 A CN 106750255A CN 201611216316 A CN201611216316 A CN 201611216316A CN 106750255 A CN106750255 A CN 106750255A
- Authority
- CN
- China
- Prior art keywords
- anionic
- reactive emulsifier
- nonionic type
- type reactive
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 88
- 125000000129 anionic group Chemical group 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 150000003333 secondary alcohols Chemical class 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000003513 alkali Substances 0.000 claims description 18
- -1 6- tridecyl Chemical group 0.000 claims description 16
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 5
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 230000009257 reactivity Effects 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
- 210000000481 breast Anatomy 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229940087291 tridecyl alcohol Drugs 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 abstract description 39
- 239000002245 particle Substances 0.000 abstract description 13
- 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 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
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 7
- 239000011976 maleic acid Substances 0.000 description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 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
- 239000003999 initiator Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 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
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000002689 maleic acids Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 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
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000001914 filtration Methods 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
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 241001272567 Hominoidea Species 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
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 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
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 238000001035 drying Methods 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
- 230000000977 initiatory effect Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000003973 paint Substances 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
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether 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
- 238000007639 printing Methods 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- 150000003839 salts Chemical class 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
- 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
- GHUXAYLZEGLXDA-UHFFFAOYSA-N 8-azido-5-ethyl-6-phenylphenanthridin-5-ium-3-amine;bromide Chemical compound [Br-].C12=CC(N=[N+]=[N-])=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 GHUXAYLZEGLXDA-UHFFFAOYSA-N 0.000 description 1
- 241001432959 Chernes Species 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 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
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 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
- 241000255964 Pieridae Species 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
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000003841 chloride salts Chemical class 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
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 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
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 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
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process 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
- 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
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000012467 final product Substances 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
- 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
- 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 235000017550 sodium carbonate 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
-
- C—CHEMISTRY; METALLURGY
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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 emulsifying agent.
Background technology
Emulsifying agent is one of key component in emulsion polymerization systems, and the performance to polymer plays decisive role.Pass
The emulsifying agent of system is adsorbed in emulsion particle surface by physical action, temperature change, impose shearing force or add electrolyte when, breast
The stability of liquid can change or even be demulsified；Emulsifying agent can be migrated to film coated surface and form one layer of non-ization in film forming procedure
The hydrophilic emulsifying agent layer of bonding is learned, once encounter water can cause film water absorption and swelling, causes frosting, whiting, gloss to decline
Etc. defect, coating film gloss, rate of film build and water resistance are reduced.
In emulsion polymerization, reactive emulsifier is bonded to by using the double bond functional group in molecule in the way of covalent bond
Polymer particle surface, the part as polymer, it is to avoid emulsifying agent is from desorption on polymer particle or in latex film
Migration, greatly reduces the hydrophilic radical on latex film surface, and emulsifying agent is in base in not only effectively solving water paint ink system
Material 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 (LC) alcohols, ethers, esters quick dry agent and the coalescents that add, so as to printing is greatly reduced
Ink VOC emission.Additionally, most reactive emulsifiers are linked in polymer segment by participating in reaction, high degree
Reduce it is existing with free form, with APEO class emulsifying agents as representative, the conventional emulsifier of difficult degradation is in water body environment
Discharge, reduces water body COD contents, 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 by Greene et al. first, 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 forces and makees reactive emulsifier with hydroxypropyl sodium alkyl sulfonate (SAHS), has synthesized bullet
Property acrylic acid ester emulsion, as a result show the PA emulsions of SAHS modified synthesis compared with stable and viscosity is relatively low.Chern etc. will be reactive newborn
Agent sodium dodecyl allyl base Succinate sodium sulfonate is used in the semi-continuous emulsion polymerizing of butyl acrylate, a small amount of adding
In the case of electrolyte, the polymer emulsion that can be relatively stablized；Wear obviously with 2- acrylamide-2-methylpro panesulfonic acid sodium
(APMS) it is a kind of polymerisable emulsifier, using styrene and butyl acrylate as comonomer, is successfully prepared solid content high
Up to 50% styrene-acrylic emulsion, and the properties such as electrolyte resistance, pH stability, the mechanical stability of emulsion are all preferable；Deng
Sword is as utilized maleic anhydride to be polymerized for pure-acrylic emulsion as a kind of reactive emulsifier 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.
Be prepared for a kind of fluorine-containing reactive emulsifier first, by it with styrene, butyl acrylate copolymerization after obtain a kind of fluorine-containing breast
Preferably, and the corrosion resistance of film, the transparency, glossiness are also fine for liquid, the emulsion intercalation method and film forming；Close in recent years
It is more in the research of maleic diester type reactive emulsifier.Xu Jian etc. has synthesized maleic anhydride list lauryl alcohol ester first, so
Carried out in the basic conditions with 2,3- epoxypropyltrimethylchloride chlorides afterwards reaction generate a kind of maleic diester type sun from
Sub- emulsifying agent, its surface tension that can significantly reduce water, and with relatively low critical micelle concentration (0.2-0.6mmol.L-1)。He
Etc. a kind of diester-type reactive emulsifier maleic anhydride lauryl alcohol ester sulfopropyl sodium salt (M-12) has been synthesized, for styrene, third
The ultrasonic radiation polymerisation of olefin(e) acid butyl ester.With the increase of M-12 consumptions, emulsion particle diameter is tapered into and is distributed and broadens, while
It is chemically bound in the surface of emulsion particle securely due to emulsifying agent, 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
During class, vinyl acetate esters isoreactivity are higher, water-soluble larger monomer is polymerized；Phenylethylene reactive emulsifier is due to phenyl ring
Draw electronic effect, reactivity is moderate, and the stability of emulsion for preparing is not good enough, therefore generally needs to add a certain amount of emulsifying agent
Or change the feeding mode of monomer；Acrylic amide reactive emulsifier reactivity is higher, can be applied to styrene, propylene
In the polymerisation of esters of gallic acid monomer, but emulsifying agent homopolymerization risk can be faced；Maleic acid esters reactive emulsifier reactivity
It is moderate, and autohemagglutination is difficult, make participation copolymerization probability higher, can effectively avoid emulsifying agent that emulsification effect is reduced because of itself homopolymerization
Really, the good combination property in emulsion polymerization is applied to, applying can obtain high-performance emulsions film in coating and printing ink, is to study most
It is extensive class reactive emulsifier.
In maleic acid esters reactive emulsifier, domestic and international correlative study mainly uses C12-C16Straight chain primary alcohol/alcohol ether,
APES is initiation material, through maleated, obtain nonionic, anionic, anionic and nonionic type and
The maleic acid esters reactive emulsifier of double ion type is simultaneously applied in emulsion polymerization.However, because primary alconol is free of EO hydrophilic chains
Section, spatial stability is poor, synthesis emulsion particle diameter is bigger than normal, and resistance to hard water deviation；And there is the alkyl of excellent emulsifying capacity
Phenol has environmental organism toxicity again, and domestic and international relevant industries are phased out using.With the C of ordinary construction12-C16Linear primary
Alcohol/alcohol ether, APES are compared, secondary alcohol in the middle of carbochain rather than two ends, the special space structure of umbrella
Imparting secondary alcohol has good spatial stability, high emulsifying strength, narrow hydrogel scope, low bubble, low hydrodynamic(al) state and balance surface
Tension force, to substrate wetting good and to pigment there is fine dispersion, wettability, be that instead of the of APEO class surfactants
One selection.
Therefore, the maleic acid list secondary alcohol APEO -2- hydroxyls for being obtained as initiation material reaction with secondary alcohol APEO
Base propyl sulfonic acid salt anionic and nonionic type reactive emulsifier has than conventional emulsifier and common reactive emulsifying agent more
The performance such as excellent emulsion dispersion wetting and water-resistance property of coating.
The content of the invention
It is an object of the invention 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, its structural formula is as follows：
WhereinN=5~40.
A kind of preparation method of described anionic and nonionic type reactive emulsifier, comprises the following steps：
1) maleic anhydride and secondary alcohol APEO are synthesized secondary alcohol APEO maleic acid under catalyst action
Monoesters；
2) with aqueous slkali and secondary alcohol APEO maleic mono-ester, secondary alcohol APEO maleic mono-ester is obtained
Salt；
3) after the reaction of secondary alcohol APEO maleic mono-ester salt and 3- chlorine-2-hydroxyls propanesulfonate, then adjust system and consolidate
Anionic and nonionic type reactive emulsifier is obtained after content.
Described maleic anhydride, secondary alcohol APEO, catalyst, alkali, the mass ratio of 3- chlorine-2-hydroxyl propanesulfonates are
(50~60):(195~970):(0.3~6):(18~30):(90~110).
Described secondary alcohol APEO is the 6- tridecyl alcohol APEOs or 2,6 that ethylene oxide number is 5~40,
8- trimethyl -4- nonane alcohol APEOs.
Described secondary alcohol APEO is vacuum dried 5~6h using preceding at 80~110 DEG C.
Described catalyst be in p-methyl benzenesulfonic acid or alkali alcoholate, hydroxide, carbonate, acetate at least
It is a kind of；Described alkali is the one kind in alkali alcoholate, hydroxide.
Step 3) in, described solid content is 25~50%.
Step 1) reaction temperature be 80~140 DEG C, the reaction time be 1.5~6h, reaction carried out under protective atmosphere；Step
System temperature before rapid 2) neutralization is 50~80 DEG C, and neutralization system pH is 6~7 after adding alkali, and reaction temperature is 60~90 DEG C, instead
It is 1~3h between seasonable；Step 3) reaction temperature be 80~120 DEG C, the reaction time be 2~6h.
Application of the described anionic and nonionic type reactive emulsifier in polymer is prepared.
Described application, is in the presence of at least one described anionic and nonionic type reactive emulsifier, to enter monomer
Row emulsion polymerization.
The beneficial effects of the invention are as follows：Reactive emulsifier disclosed by the invention has spatial stability, emulsion dispersion high
The excellent properties such as ability, low bubble, low surface tension, wetting, applying can prepare in emulsion polymerization particularly Styrene-Acrylate Emulsion Polymerization
Go out the high-performance emulsions of the characteristics such as high stability, high glaze, small particle.
Specific embodiment
A kind of anionic and nonionic type reactive emulsifier, its structural formula is as follows：
Wherein(6- tridecyls) or
(2,6,8- trimethyl -4- nonyls)；N=5~40.
A kind of preparation method of described anionic and nonionic type reactive emulsifier, comprises the following steps：
1) maleic anhydride and secondary alcohol APEO are synthesized secondary alcohol APEO maleic acid under catalyst action
Monoesters；
2) with aqueous slkali and secondary alcohol APEO maleic mono-ester, secondary alcohol APEO maleic mono-ester is obtained
Salt；
3) after the reaction of secondary alcohol APEO maleic mono-ester salt and 3- chlorine-2-hydroxyls propanesulfonate, then adjust system and consolidate
Anionic and nonionic type reactive emulsifier is obtained after content.
Preferably, described maleic anhydride, secondary alcohol APEO, catalyst, alkali, 3- chlorine-2-hydroxyl propanesulfonates
Mass ratio is (50~60):(195~970):(0.3~6):(18~30):(90~110)；It is further preferred that described horse
It is (50~55) to come acid anhydrides, secondary alcohol APEO, catalyst, alkali, the mass ratio of 3- chlorine-2-hydroxyl propanesulfonates:(220~
760):(1~4.5):(19~26.5):(98~105).
Preferably, described secondary alcohol APEO is 6- tridecyl alcohol polyoxyethylene that ethylene oxide number is 5~40
Ether or 2,6,8- trimethyl -4- nonane alcohol APEOs.
The structural formula of 6- tridecyl alcohol APEOs is as follows：
N=5~40 in formula.
The structural formula of 2,6,8- trimethyl -4- nonane alcohol APEOs is as follows：
N=5~40 in formula.
Preferably, described secondary alcohol APEO is vacuum dried 5~6h using preceding at 80~110 DEG C.
Preferably, described catalyst is p-methyl benzenesulfonic acid or alkali alcoholate, hydroxide, carbonate, acetate
In at least one；It is further preferred that described catalyst is p-methyl benzenesulfonic acid, sodium alkoxide, potassium alcoholate, NaOH, hydroxide
At least one in potassium, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate；Still further preferably, described catalyst is to first
At least one in benzene sulfonic acid, sodium methoxide, NaOH, potassium hydroxide, sodium carbonate, sodium acetate.
Preferably, described alkali is the one kind in alkali alcoholate, hydroxide；It is further preferred that described alkali
It is the one kind in sodium alkoxide, potassium alcoholate, NaOH, potassium hydroxide；Still further preferably, described alkali is sodium methoxide, hydroxide
One kind in sodium, potassium hydroxide.
Preferably, step 3) in, described solid content is 25~50%；It is further preferred that step 3) in, described consolidates
Content is 30~45%.
Preferably, step 1) reaction temperature be 80~140 DEG C, the reaction time be 1.5~6h, react under protective atmosphere
Carry out；Step 2) neutralize before system temperature be 50~80 DEG C, adding and neutralize system pH after alkali is 6~7, reaction temperature is 60~
90 DEG C, the reaction time is 1~3h；Step 3) reaction temperature be 80~120 DEG C, the reaction time be 2~6h；Further preferably
, described protective atmosphere is the one kind in nitrogen or inert gas；Still further preferably, described protective atmosphere is nitrogen
Gas.
Application of the described anionic and nonionic type reactive emulsifier in polymer is prepared.
Preferably, described application, is in the presence of at least one described anionic and nonionic type reactive emulsifier, to make
Monomer carries out emulsion polymerization.
Preferably, described monomer is that acrylate, methacrylate, unsaturated amides, unsaturated nitrile, styrene spread out
At least one in biology, diene derivatives, polyethyleneglycol diacrylate and polyethylene glycol dimethacrylate；Enter one
Step is preferred, described monomer in acrylate, methacrylate, styrene derivative and diene derivatives at least
It is a kind of；Still further preferably, described monomer is ethyl acrylate, butyl acrylate, 2-EHA, methyl-prop
E pioic acid methyl ester, EMA, HEMA, GMA, AMS,
At least one in butadiene and isoprene.
Preferably, described 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 described anionic and nonionic type reactive emulsifier accounts for polymerization reaction system
Mass fraction is 0.2~5%；Still further preferably, described anionic and nonionic type reactive emulsifier accounts for polymerization reaction system
Mass fraction be 0.5~4%.
Furthermore, it is understood that described application, from described anionic and nonionic type reactive emulsifier one or more, or
Use at least one described anionic and nonionic type reactive emulsifier and other emulsifying agents or protecting colloid.
Preferably, other described emulsifying agents 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 in vinethene.
Preferably, described protecting colloid is polyacrylic acid hard resin Protection glue, polyvinyl alcohol and hydroxyethyl cellulose
In at least one.
Preferably, other described emulsifying agents or protecting colloid account for the quality of total emulsifiers and are not more than 50%；It is further excellent
Choosing, the quality that other described emulsifying agents or protecting colloid account for total emulsifiers is not more than 25%.
Preferably, described being aggregated under initiator effect is carried out, described initiator is inorganic peroxide initiator,
At least one in 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, DIBHP, the isobutyl of azo two
Nitrile, azo isobutyl cyano group formamide or the composition such as peroxide and sodium hydrogensulfite, sodium thiosulfate, ferrous sulfate, carbohydrate
At least one in redox initiator.
Present disclosure is described in further detail below by way of specific embodiment.
In these embodiments, unless otherwise noted, all of percentage is percetage by weight.6- tridecyls alcohol gathers
Oxygen vinethene or 2,6,8- trimethyl -4- nonane alcohol APEOs are to buy gained from commercial channel import.
Synthetic example 1：
By mass fraction, 300 parts of 6- ammonium trideceths 9EO are taken in four-hole boiling flask, add 52 parts of maleic acids
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 arrived with system pH in 26.5 parts of sodium methoxides of addition
6.5~7.0,85 DEG C vacuumize 2h；98 parts of 3- chlorine-2-hydroxyl propyl sulfonic acid sodium are added, after 100 DEG C of reaction 4h, under stirring at low speed
Add quantitative water to adjust system solid content to 35%, obtain maleic acid list secondary alcohol APEO -2- propane sulfonates
Anionic and nonionic type reactive emulsifier.
Synthetic example 2：
By mass fraction, 255 parts of 6- ammonium trideceths 7EO are taken in four-hole boiling flask, add 50 parts of maleic acids
Acid anhydride and 1.0 parts of potassium hydroxide are in N2The lower 100 DEG C of reactions 4.0h of gas shielded；Cool to 70 DEG C, add in 25.5 parts of sodium methoxides and body
It is pH to 6.5~6.8,90 DEG C vacuumize 1h；100 parts of 3- chlorine-2-hydroxyl propyl sulfonic acid sodium are added, it is low after 110 DEG C of reaction 3.5h
Speed stirring is lower to add quantitative water to adjust system solid content to 30%, obtains maleic acid list secondary alcohol APEO -2- hydroxyls third
Base sulfonate anionic and nonionic type reactive emulsifier.
Synthetic example 3：
By mass fraction, 760 parts of 6- ammonium trideceths 30EO are taken in four-hole boiling flask, add 55 parts of maleic acids
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, with system pH in 19 parts of NaOH of addition
To 6.3~6.8,90 DEG C vacuumize 2.5h；105 parts of 3- chlorine-2-hydroxyl propyl sulfonic acid sodium are added, after 105 DEG C of reaction 5h, low speed is stirred
Mix the quantitative water of lower addition and adjust system solid content to 35%, obtain maleic acid list secondary alcohol APEO -2- hydroxypropyl sulphurs
Hydrochlorate anionic and nonionic type reactive emulsifier.
Synthetic example 4：
By mass fraction, 220 part 2, in 6,8- trimethyl -4- nonanes alcohol APEO 6EO to four-hole boiling flask is taken, added
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 methyl alcohol are added
With system pH to 6.5~6.8 in sodium, 85 DEG C vacuumize 2h；Add 98 parts of 3- chlorine-2-hydroxyl propyl sulfonic acid sodium, 100 DEG C of reaction 4h
Afterwards, add quantitative water to adjust system solid content to 45% under stirring at low speed, obtain maleic acid list secondary alcohol APEO -2- hydroxyls
Base propyl sulfonic acid salt anionic and nonionic type reactive emulsifier.
Synthesis comparative example 1：
By mass fraction, 240 parts of C are taken12AEO 7EO adds 52 parts of maleic anhydrides in four-hole boiling flask
With 1.5 parts of sodium methoxides in N2The lower 95 DEG C of reactions 5h of gas shielded, it is 7 that product adjusts pH with the sodium hydroxide solution of 5wt%, and low speed is stirred
Mix the quantitative water of lower addition and adjust system solid content to 35wt%, obtain the reactive emulsifier of comparative example 1.
Synthesis comparative example 2：
By mass fraction, 95 parts of lauryl alcohols are taken in four-hole boiling flask, adding 50 parts of maleic anhydrides and 1.0 parts of sodium methoxides in N2
The lower 95 DEG C of reactions 5h of gas shielded, it is 7 that product adjusts pH with the sodium hydroxide solution of 5wt%, and quantitative water is added under stirring at low speed
Adjustment system solid content obtains the reactive emulsifier of comparative example 2 to 35wt%.
According to following aggregation schemes, with reactive emulsifier of the invention and the reactive emulsifier of comparative example 1 to 2
Carry out emulsion polymerization.Then the polymerized emulsion to gained carries out the evaluation of polymerization stability, particle size and mechanical stability, and
Water resistance to emulsion film forming caudacoria is evaluated.The results are shown in Table 1.To be also found in the data obtained by common emulsifying agent
In table 1, with comparing.
Aggregation scheme
2 are added in 1 liter of glass reactor equipped with thermometer, agitator, condenser, nitrogen inlet and dropping funel
Gram emulsifying agent, 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, had been 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 to be 80 DEG C and continue to react 2 hours, then 30 are cooled to water-bath~
, emulsion system pH is adjusted to 8-9 with 10% ammoniacal liquor, obtain final product styrene-acrylic emulsion by 40 DEG C.
Polymerized emulsion performance test is as follows：
1st, 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 in 105 DEG C under 200mmHg, is then weighed.Based on amount of monomer used, the value of thus gained is expressed as " weight
Amount % ".
2nd, particle diameter
After polymerized emulsion is filtered with the wire cloth of 100 mesh, using the laser particle analyzers of Mastersize 3000 of Malvern
Carry out particle diameter test.
3rd, mechanical stability
After polymerized emulsion is filtered with the wire cloth of 100 mesh, under conditions of 10kg and 1000rpm, with MARON methods machinery
Stability test machine rotates 50 grams of polymerized emulsions 5 minutes.The aggregation that will be consequently formed is entered by the wire cloth of one 100 mesh
Row filtering.The residue of filtering is washed with water, is dried overnight in 105 DEG C under 200mmHg, then weighed.And the amount with polymer,
The value of thus gained is expressed as " weight % ".
4th, glossiness test
After polymerized emulsion is filtered with the wire cloth of 100 mesh, polymerized emulsion is coated in glass with 150um wet film makers
On plate, 60 ° of glossiness tests are carried out after the ZGM1022Glossmeter glossometers after drying varniss using ZEHNTNER companies poly-
The gloss of compound film.To exclude the interference such as ground water absorption rate, flatness, shrinkage stress, coated one side is wiped with alcohol first
Wipe clean, to dispel influence of the oil stain to testing.
5th, water resistance (film-brighten test)
After polymerized emulsion is filtered with the wire cloth of 100 mesh, polymerized emulsion is coated on a slide glass (76 × 26mm), it is thick
It is 125 μm to spend, and makes the film forming that it carries out 5 minutes at 100 DEG C.After being cooled to room temperature, a test 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.Determine until lead
Word becomes the time required untill can not recognizing.
Test result is shown in Table 1.
The different emulsifiers of table 1 gained polymerized emulsion the performance test results
Show from the test result of table 1：Can obtain that there is breast high using anionic and nonionic type reactive emulsifier of the invention
The emulsion of liquid stability, low particle diameter.And, the polymer film of gained polymerized emulsion has splendid water resistance and high glaze etc. excellent
Benign energy.
Claims (10)
1. a kind of anionic and nonionic type reactive emulsifier, it is characterised in that：Its structural formula is as follows：
WhereinN=5~40.
2. the preparation method of a kind of anionic and nonionic type reactive emulsifier described in claim 1, it is characterised in that：Including following
Step：
1) maleic anhydride and secondary alcohol APEO are synthesized secondary alcohol APEO maleic mono-ester under catalyst action；
2) with aqueous slkali and secondary alcohol APEO maleic mono-ester, secondary alcohol APEO maleic mono-ester salt is obtained；
3) after secondary alcohol APEO maleic mono-ester salt reacts with 3- chlorine-2-hydroxyls propanesulfonate, then system solid content is adjusted
Anionic and nonionic type reactive emulsifier is obtained afterwards.
3. the preparation method of a kind of anionic and nonionic type reactive emulsifier according to claim 2, it is characterised in that：It is described
Maleic anhydride, secondary alcohol APEO, catalyst, alkali, 3- chlorine-2-hydroxyl propanesulfonates mass ratio be (50~60):
(195~970): (0.3~6): (18~30): (90~110).
4. the preparation method of a kind of anionic and nonionic type reactive emulsifier according to claim 3, it is characterised in that：It is described
Secondary alcohol APEO be the 6- tridecyl alcohol APEOs or 2 that ethylene oxide number is 5~40,6,8- trimethyl -4-
Nonane alcohol APEO.
5. the preparation method of a kind of anionic and nonionic type reactive emulsifier according to claim 4, it is characterised in that：It is described
Secondary alcohol APEO using it is preceding 80~110 DEG C be vacuum dried 5~6h.
6. the preparation method of a kind of anionic and nonionic type reactive emulsifier according to claim 3, it is characterised in that：It is described
Catalyst be at least one in p-methyl benzenesulfonic acid or alkali alcoholate, hydroxide, carbonate, acetate；Described
Alkali is the one kind in alkali alcoholate, hydroxide.
7. the preparation method of a kind of anionic and nonionic type reactive emulsifier according to claim 2, it is characterised in that：Step
3) in, described solid content is 25~50%.
8. the preparation method of a kind of anionic and nonionic type reactive emulsifier according to claim 2, it is characterised in that：Step
1) reaction temperature is 80~140 DEG C, and the reaction time is 1.5~6h, and reaction is carried out under protective atmosphere；Step 2) neutralize before
System temperature is 50~80 DEG C, and adding and neutralize system pH after alkali is 6~7, and reaction temperature is 60~90 DEG C, the reaction time is 1~
3h；Step 3) reaction temperature be 80~120 DEG C, the reaction time be 2~6h.
9. application of the anionic and nonionic type reactive emulsifier described in any one of claim 1~8 in polymer is prepared.
10. application according to claim 9, it is characterised in that：In at least one described anionic and nonionic type reactivity breast
In the presence of agent, monomer is set to carry out emulsion polymerization.
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