CN1161340A - Prepn. of aqueous polymer dispersion - Google Patents
Prepn. of aqueous polymer dispersion Download PDFInfo
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- CN1161340A CN1161340A CN 96121508 CN96121508A CN1161340A CN 1161340 A CN1161340 A CN 1161340A CN 96121508 CN96121508 CN 96121508 CN 96121508 A CN96121508 A CN 96121508A CN 1161340 A CN1161340 A CN 1161340A
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- polymerization
- monomer
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- polyreaction
- mixture
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- 239000004815 dispersion polymer Substances 0.000 title claims abstract description 25
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 148
- 239000000178 monomer Substances 0.000 claims abstract description 110
- 238000000034 method Methods 0.000 claims abstract description 72
- 239000000203 mixture Substances 0.000 claims abstract description 68
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 31
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 30
- 150000003254 radicals Chemical class 0.000 claims description 27
- 239000011541 reaction mixture Substances 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 11
- 239000003995 emulsifying agent Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 10
- 239000002612 dispersion medium Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 230000021615 conjugation Effects 0.000 claims description 8
- 239000000084 colloidal system Substances 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- 239000007870 radical polymerization initiator Substances 0.000 claims description 4
- 239000007858 starting material Substances 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000001747 exhibiting effect Effects 0.000 abstract 2
- 229920000642 polymer Polymers 0.000 description 27
- 239000007864 aqueous solution Substances 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- -1 alkali metal salt Chemical class 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 10
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000007046 ethoxylation reaction Methods 0.000 description 8
- SAJLIOLJORWJIO-UHFFFAOYSA-N hydroxymethanesulfinic acid;sodium Chemical compound [Na].OCS(O)=O SAJLIOLJORWJIO-UHFFFAOYSA-N 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000003863 ammonium salts Chemical class 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 6
- 239000004816 latex Substances 0.000 description 6
- 229920000126 latex Polymers 0.000 description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 6
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 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 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- 230000033116 oxidation-reduction process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 229920001821 foam rubber Polymers 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 239000012874 anionic emulsifier Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- XQESJWNDTICJHW-UHFFFAOYSA-N 2-[(2-hydroxy-5-methyl-3-nonylphenyl)methyl]-4-methyl-6-nonylphenol Chemical compound CCCCCCCCCC1=CC(C)=CC(CC=2C(=C(CCCCCCCCC)C=C(C)C=2)O)=C1O XQESJWNDTICJHW-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- KJQMOGOKAYDMOR-UHFFFAOYSA-N CC(=C)C=C.CC(=C)C=C Chemical compound CC(=C)C=C.CC(=C)C=C KJQMOGOKAYDMOR-UHFFFAOYSA-N 0.000 description 1
- 208000006558 Dental Calculus Diseases 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 239000013543 active substance Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- SBGKURINHGJRFN-UHFFFAOYSA-N hydroxymethanesulfinic acid Chemical compound OCS(O)=O SBGKURINHGJRFN-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229960004232 linoleic acid Drugs 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000007785 strong electrolyte Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Abstract
A procedure for the production of an aqueous polymer dispersion by radical aqueous emulsion polymerization of a mixture of at least a ethylenisch insatiated group exhibiting monomers, which conjugated ethylenisch insatiated double bonds exhibiting monomers to at least 30% of its weight from two exists. Wherein, polymerization reaction temperature changes in the process of radical aqueous emulsion polymerization.
Description
The present invention relates to a kind of method for preparing aqueous polymer dispersion, it comprises, make the monomeric mixture with at least one ethylenically unsaturated group carry out free radical water emulsion polymerization, this monomer mixture contains the monomer that 30wt (weight) % at least has two conjugation ethylenical unsaturated double bonds.
Aqueous polymer dispersion (latex) is known.They are to contain the fluid systems of polymeric micellar (being polymer particles) as disperse phase in water base dispersion medium, and polymeric micellar is made up of the polymer chain of a plurality of mutual windings.The particle diameter of polymer particles is generally 10-1500nm.
Different with polymers soln, aqueous polymer dispersion is not a thermodynamic stable system.This system has by little primary fine particles and is gathered into the trend that bigger two atomic grains reduce the interface between polymkeric substance and the dispersion medium, add dispersion agent (but the material at the interface between stabilization dispersed polymeres and the water base dispersion medium) and can suppress this phenomenon, it can make the disperse phase stable dispersion in a long time in aqueous medium.
Therefore, evaporation during water base dispersion medium and/or control when making the dispersion agent inactivation, part or all of gathering by polymer particles, aqueous polymer dispersion can form the cohesive polymeric matrix by liquid or its foamed state (volume content of dispersed polymeres very little situation under), this polymeric matrix is transparent film under the condition of good control, and is the gel state in another case.
For forming above-mentioned polymeric matrix, though at the chemical bonding of the different polymer chains of micro polymer intragranular (particularly chemical bonding) too thick and fast is disadvantageous, but, after forming described matrix, make the polymer chain chemical bonding (crosslinked) that constitutes polymeric matrix normally favourable subsequently to reaching specific mechanical properties (for example elasticity).
At first sight, these two kinds of requirements are obviously contradicted each other, but when this aqueous polymer dispersion of preparation, take some measures simply and just can make their mutual non-contraventions, free radical water emulsion polymerization method as known in the art is adopted in the preparation of aqueous polymer dispersion usually, and (this polymerization process has been disclosed in many documents and has been well known to those skilled in the art, for example can be referring to following document: polymer science and processing be complete works of, the 8th volume, 659 pages (1987); D.C.Blackly, polymer emulsion, the 1st volume, the 35th page (1966); H.Warson, the application of synthetic resin emulsion, 246 pages, the 5th chapter (1972); D.Diederich, applied chemistry (Chemie in unserer Zeit) 24,135-142 page or leaf (1990); Letex polymerization, Interscience Publishers, New York (1965); DE-A 4 003 422 and synthetic polymer dispersion (Dispersionensynthetischer Hochpolymerer), Teil I, F.H lscher, Springer Verlag, Berlin (1969)), promptly, in the presence of dispersion agent and radical polymerization initiator, carry out polymerization by the monomer that has at least one ethylenically unsaturated group and directly exist with disperse phase, and the copolymerization at least a monomer with two conjugation ethylenical unsaturated double bonds that is incorporated into significant quantity (below be referred to as monomer A).The example of suitable monomer A is divinyl, 2-methyl butadiene (isoprene) and 2, the 3-dimethylbutadiene.
If in the presence of monomer A, under not too high temperature, use or do not use molecular weight regulator (mercaptan for example, as uncle's lauryl mercaptan or n-dodecyl mercaptan) carry out free radical water emulsion polymerization, two of monomer A conjugation ethylenical unsaturated double bonds generally have only two keys to participate in polyreaction so.
Like this, the dispersed polymeres micelle is made up of the polymer chain with following feature in the aqueous polymer dispersion of formation: on the one hand, be uncrosslinked (be between them not chemical bonding) between the polymer chain; And on the other hand, still has ethylenical unsaturated double bonds on the polymeric chain, after forming required polymeric matrix, by adopting suitable vulcanization system (for example based on the vulcanization system of sulphur, they added before forming polymeric matrix usually) and elevated temperature, these pairs key is activated again, causes specific reaction and forms intermolecular cross-linking, thereby reach degree of crosslinking required when using.
In the prior art method, when being particularly suitable for preparing the aqueous polymer dispersion of latex product (as condom or gloves) or latex foam, preparation adopt above-mentioned measure (referring to EP-A 378 380, EP-A 456 333, US-2 880 189, DE-A 2 307 804, open DAS 1,297,067 of German patent application and DE-A 1 951 340).
The monomeric mixture that make the monomer that contains 30wt% at least and have two conjugation ethylenical unsaturated double bonds, has at least one ethylenically unsaturated group generally all is substantially constant at temperature Fp≤50 and ℃ carries out free radical water emulsion polymerization, can add molecular weight regulator (for example referring to US-2399 017, DE-A 1 951 340 and DE-A 3 406 231) as needs.
Under the situation that other polymerizing condition is determined, low polymerization temperature only causes low cross-linking, and polymerization temperature raises, degree of crosslinking also increases, the controlled polymerization reaction conditions by the control sulfuration of the polymeric matrix that makes, can be controlled the mechanical property of end product.
But the shortcoming of the free radical water emulsion polymerization method of these prior arts is that particularly when the monomer with conjugated double bond was divinyl, the polymeric speed of reaction can not be satisfactory under the oligomerization temperature.
An object of the present invention is to provide a kind of method for preparing aqueous polymer dispersion, it comprises, make monomeric mixture carry out free radical water emulsion polymerization with at least one ethylenically unsaturated group, this monomer mixture contains the monomer that 30wt% at least has two conjugation ethylenical unsaturated double bonds, under given polyreaction batch of material is formed, with be substantially constant at temperature Tp under the free radical water emulsion polymerization that carries out compare, the inventive method polymerization gets faster, and can form essentially identical with it (elementary) degree of crosslinking.
For the polymkeric substance that given monomer is formed, the suitable sign of degree of crosslinking be the proton of chamical binding on polymkeric substance the horizontal relaxation time of nucleus magnetic resonance (
1HT
2).As described belowly in this article carry out above-mentioned measurement, each aqueous polymer dispersion made film at 25 ℃, obtained sample in 2 hours 80 ℃ of dryings then, with sample at 140 ℃, 20MHz
1Measure under the H resonant frequency.
1HT
2And the relation between the degree of crosslinking for example is described in Macromolecules 27 (1994), among the 2111-2119.At last, this relation is based on the following fact: on the one hand, the horizontal relaxation time of nuclear nucleus magnetic resonance with magnetic moment is externally the measuring of mobility in the magnetic field of described nuclear, and on the other hand, the difference of polymeric chain degree of crosslinking makes that again their mobility is different.The mobility of polymer chain is low more, be that degree of crosslinking is high more, chamical binding is on this polymer chain and to have a horizontal relaxation time of nuclear nucleus magnetic resonance of magnetic moment short more.
We have found that, according to the present invention, above-mentioned purpose is reached by the following method for preparing aqueous polymer dispersion, it comprises, make monomeric mixture carry out free radical water emulsion polymerization with at least one ethylenically unsaturated group, this monomer mixture contains the monomer that 30wt% at least has two conjugation ethylenical unsaturated double bonds, wherein
A) will treat that polymeric monomer intermixture is divided into n endorsement body altogether, Integer n 〉=2, preferred 2≤n≤5, based on the total amount for the treatment of polymeric monomer intermixture, every endorsement body preferably contains at least the polymerization single polymerization monomer for the treatment of of ((100/n)-10) mol (mole) %;
B) in polymerization reactor, at first add the 1st endorsement body and dispersion agent, radical polymerization initiator and water base dispersion medium, carry out the 1st step polyreaction, polymerization temperature during the reaction beginning is TP1,0 ℃≤TP1≤50 ℃ wherein, make at least 20 ℃ of the temperature risings (preferably raising constantly) of polymerization reaction mixture, reach top temperature TP1H, but be no more than 80 ℃ (preferably being no more than 75 ℃); And
Polymerization temperature is constant in TP1H to TP1H-10 ℃ temperature range, treat the amount of polymerization single polymerization monomer-reach 60mol% but be no more than 90mol% at least until polymerisation conversion U1-in the polyreaction based on the 1st step, then polymerization reaction mixture is cooled to polymerization temperature TP2, wherein TP2=TP1 ± 10 ℃ and 0 ℃≤TP2≤50 ℃;
C) add the 2nd endorsement body, make the monomer mixture in the polymerization reactor in the presence of established polymkeric substance and dispersion agent and polymerization starter, carry out the 2nd step polyreaction then, polymerization temperature during the reaction beginning is TP2, make at least 20 ℃ of the temperature risings (preferably raising constantly) of polymerization reaction mixture, reach top temperature TP2H, but be no more than 80 ℃ (preferably being no more than 75 ℃); And
Polymerization temperature is constant in TP2H to TP2H-10 ℃ temperature range, treat the total amount of polymerization single polymerization monomer-reach 60mol% but be no more than 90mol% at least until polymerisation conversion U2-in the polyreaction based on the 2nd step, then polymerization reaction mixture is cooled to polymerization temperature TP3, wherein TP3=TP1 ± 10 ℃ and 0 ℃≤TP3≤50 ℃;
D) then, make remaining n-2 endorsement body in n-2 successive polymerization reactions steps, proceed polymerization by the 2nd batch of monomeric polymerization methods; With
E) after the polymerization of n step finishes, continue polyreaction at 0-50 ℃, if desired, make total polymerisation conversion Utot-based on the total amount for the treatment of polymerization single polymerization monomer-reach 〉=95mol%.
The inventive method for example is suitable for polymerization and contains at least a divinyl, 2-methyl butadiene and 2, and the 3-dimethylbutadiene is as the monomer mixture with monomer (monomer A) of two conjugation ethylenical unsaturated double bonds.
The used monomer mixture of the inventive method can only be made up of monomer A, but also can contain comonomer different with monomer A, that have at least one ethylenically unsaturated group.Generally speaking, the used monomer mixture of the inventive method contains 30-90wt%, common 40-70wt%, preferred 50-60wt% monomer A.
In the used monomer mixture of the present invention, be generally at the most 10wt%, be generally 3-8wt% at the content of the comonomer of normal pressure (1 crust) and 25 ℃ of molar solubility height in water (solubleness of 〉=vinyl cyanide).Monomers B commonly used for example is: α, β-monoene belong to unsaturated C
3-C
6Single and two carboxylic acid is as vinylformic acid, methacrylic acid, toxilic acid, fumaric acid and methylene-succinic acid; The salt of above-mentioned carboxylic acid (particularly an alkali metal salt and ammonium salt); The acid amides of above-mentioned carboxylic acid is as acrylamide and Methacrylamide; Vinyl sulfonic acid and water-soluble salt thereof (particularly an alkali metal salt and ammonium salt); And N-vinyl pyrrolidone.Monomer A is preferably divinyl, and monomers B is preferably methacrylic acid.
In the used monomer mixture of the present invention, the amount with other copolymerizable monomer (monomer C) of at least one ethylenically unsaturated group can be at most 70wt%, is generally 10-70wt%, is preferably 30-60wt%, more preferably 40-50wt%.Suitable monomer C for example is: vinyl aromatic monomer, and as vinylbenzene, Vinyl toluene or chloro styrene, vinyl cyanide, methacrylonitrile, vinylformic acid and methacrylic acid and C
1-C
8The ester of alkanol.Wherein, monomer C is preferably vinylbenzene, vinyl cyanide and methyl methacrylate especially.
This is meaning, and the inventive method is suitable for having the free radical water emulsion polymerization of the monomer mixture of following composition:
The 30-100wt% monomer A,
The 0-10wt% monomers B and
0-70wt% monomer C.
Therefore, be applicable to that the monomer mixture in the inventive method comprises the monomer mixture with following composition:
30-100wt% is at least a be selected from divinyl, 2-methyl butadiene and
2, the monomer of 3-dimethylbutadiene,
At least a vinylformic acid, methacrylic acid, the Malaysia of being selected from of 0-10wt%
Acid, fumaric acid, methylene-succinic acid, acrylamide and methyl-prop
The monomer of alkene acid amides and
At least a vinylbenzene, vinyl cyanide and the methacrylic of being selected from of 0-70wt%
The monomer of acid methyl esters.
Particularly comprise monomer mixture with following composition:
The 30-100wt% divinyl,
The 0-10wt% methacrylic acid and
The 0-70wt% vinyl cyanide.
The inventive method also is applicable to the monomer mixture with following composition:
The 30-90wt% monomer A,
The 1-10wt% monomers B and
9-60wt% monomer C.
But the inventive method also is applicable to the monomer mixture with following composition:
The 40-70wt% monomer A,
The 1-10wt% monomers B and
29-50wt% monomer C.
The same with the prior art method, in the methods of the invention, free radical water emulsion polymerization reaction is generally also carried out in the presence of molecular weight regulator (chain-transfer agent), with further control degree of crosslinking, and mercaptan (alkanethiol), particularly C for example
3-C
15Mercaptan.According to the present invention, molecular weight regulator preferred tertiary lauryl mercaptan or n-dodecyl mercaptan.In this case, in each polymerization procedure of the inventive method, based on the amount for the treatment of polymerization single polymerization monomer in each polymerization procedure, free radical water emulsion polymerization at 0.1-3wt%, be generally in the presence of the 0.5-1.5wt% molecular weight regulator and carry out.
Dispersion stabilization for the polymer particles that guarantees to make can use to be usually used in carrying out protective colloid and the emulsifying agent that free radical water emulsion polymerization reacts after the neutralization of free radical water emulsion polymerization process.
The example of suitable protective colloid has polyvinyl alcohol, derivatived cellulose, contains the polycondensate of vinylpyrrolidone copolymers or naphthene sulfonic acid and formaldehyde, and based on atomic hydrogen, their number average relative molecular weight is generally 4000-8000.The detailed description of other suitable protective colloid can be referring to Houben-Weyl, Methoden der organischenChemie, Volume XIV/1, Makromolekulare Stoffe, Georg-Thieme-Verlag, Stuttgart, 1961,411-420 page or leaf.Can certainly use the mixture of emulsifying agent and/or protective colloid.Different with monomer A and C; because monomers B has polarity; therefore monomers B has tangible solvability in water base dispersion medium, when being intended to prepare polymer particles chemically very during the homogeneous polymer water dispersion with the inventive method, preferably use the combination of emulsifying agent and protective colloid.
The preferred emulsifying agent that uses, different with protective colloid, they are tensio-active agents, thereby can form micella, its relative molecular weight is generally less than 2000, usually less than 1000.They can be anionic, cationic or non-ionic type.When using surfactant mixtures, they certainly must be compatible, and these available several tentative experiments are determined.Generally speaking, anionic emulsifier oneself is compatible mutually, and compatible with nonionic emulsifier, and cationic emulsifier also is like this, but anionic emulsifier and cationic emulsifier are generally incompatible.Emulsifying agent commonly used for example is: single, double and trialkyl phenol (ethoxylation degree 3-100, the alkyl C of ethoxylation
4-C
12); The Fatty Alcohol(C12-C14 and C12-C18) of ethoxylation (ethoxylation degree 3-100, alkyl C
8-C
18); Alkylsurfuric acid (alkyl C
8-C
16), sulfate hemiester (ethoxylation degree 1-70, the alkyl C of ethoxylation alkanol
12-C
18), alkylphenol (ethoxylation degree 3-100, the alkyl C of ethoxylation
4-C
12), alkylsulphonic acid (alkyl C
12-C
18), aryl sulfonic acid and an alkarylsulphonic acid (alkyl C
9-C
18) an alkali metal salt and ammonium salt.Other suitable emulsifying agent is alkylsurfuric acid (alkyl C
10-C
18) and aromatic sulfuric acid and alkaryl sulfuric acid (alkyl C
9-C
18) an alkali metal salt and ammonium salt.Other suitable emulsifying agent (as sulfosuccinic ester) is described in Houben-Weyl, Methodender organischen Chemie, Volume XIV/1, MakromolekulareStoffe, Georg-Thieme-Verlag, Stuttgart, 1961, in the 192-208 page or leaf.
Because two kinds of topmost method-Dunlop methods of preparation latex foam glue and Talalay method-ultimate principle be, make it that gelling take place by the pH value that is reduced in o'clock stable foamable polymer water dispersion in pH＞7, therefore, the aqueous polymer dispersion of the inventive method preparation is especially preferably used C
8-C
18An alkali metal salt (particularly sodium salt and sylvite) of lipid acid (saturated and undersaturated) and the disproportionation resinous acid that obtained by rosin (rosined soap) and ammonium salt are as emulsifying agent.Sylvite, sodium salt and the ammonium salt of preferred especially palmitinic acid, oleic acid, stearic acid, linolic acid and Semen Lini acid wherein.Generally, preferably adopt the anionic stabilization.
Generally speaking, based on the amount for the treatment of polymerization single polymerization monomer in each polymerization procedure, in each step of the inventive method, use 0.5-10wt%, be generally the dispersion agent of 1-5wt%.
Comprise on the suitable radical polymerization initiator principle of free radical water emulsion polymerization reaction of the present invention that all can be at≤50 ℃ of initiators that cause free radical water emulsion polymerization.They can be superoxide and azo-compound.The preferred initiator system of being made up of at least a reductive agent and at least a superoxide and/or hydroperoxide that uses because reductive agent can promote the formation of free radical, makes that can cause free radical water emulsion polymerization at low temperatures reacts.
The example of suitable reductive agent is sodium salt, S-WAT, sodium bisulfite and the V-Brite B that xitix, acetone close hydrosulphite, hydroxyl methane-sulfinic acid.Above-mentioned initiator system (oxidation-reduction trigger system) is preferred especially also to be contained in addition and dissolves in the polymerization reaction medium on a small quantity and its metal ingredient can have the metallic compound of multiple valence state.The example of this metal compound is iron (II) salt, as ferrous sulfate (II).Except water-soluble iron (II) salt, also can use water-soluble Fe/V composite salt.The advantage that contains the oxidation-reduction trigger system of this metallic compound is that they can cause the free radical water emulsion polymerization reaction under lower temperature.The example of this class oxidation-reduction trigger system is xitix/ferrous sulfate (II)/hydrogen peroxide or V-Brite B+formaldehyde sodium sulfoxylate/ferrous sulfate (II)/hydroperoxidation terpene or hydroperoxidation diisopropyl benzene or cumene hydroperoxide.Generally speaking, also in this oxidation-reduction trigger system that contains metallic compound, add a small amount of chelating reagent, can't from reaction system, be removed (for example because precipitin reaction) to guarantee that metal ingredient exists in solution.The example of chelating reagent can be mentioned the sodium salt of ethylenediamine tetraacetic acid (EDTA).Generally speaking, metal component directly adds with the form of inner complex.
In each polymerization procedure of the inventive method, based on the amount for the treatment of polymerization single polymerization monomer, the consumption of initiator is generally 0.01-5wt%, is generally 0.01-1wt%.According to the present invention, polyreaction is generally carried out under inert gas atmosphere.
According to the present invention, treat that polymerization single polymerization monomer is divided into n endorsement body altogether, n wherein for example can be 2,3,4 or 5, n can certainly be greater than 5, but this does not have benefit to suitability for industrialized production.N is preferably 2 or 3.
In each polymerization procedure, based on the amount for the treatment of polymerization single polymerization monomer in each polymerization procedure (this total amount is made up of initiate monomeric amount in the amount of unconverted monomer residual in the last polymerization procedure and this polymerization procedure), the polymerisation conversion U that reaches is preferably 70-85mol%.
In addition, polymerization process of the present invention is particularly including following embodiment, and wherein TP1 is 0 ℃-20 ℃, and the top temperature TPnH in each polymerization procedure is 50-75 ℃ or 40-50 ℃.
Generally speaking, in the methods of the invention, the composition of polymeric monomer mixture is basic identical in each polymerization procedure, that is, at first different monomers is mixed with plain mode, then this mixture is divided into n part.Certainly, the polymeric monomer mixture also can have different compositions in each polymerization procedure.
For example, if the monomer that the monomer of copolymerization left behind is difficult to remove (for example vinyl cyanide), be preferably in the relative quantity of the monomer (for example divinyl) that its residual monomer of raising is easy to remove in last polymerization procedure after free radical water emulsion polymerization finishes.In addition, if desired, the consumption of molecular weight regulator can be different in each polymerization procedure.
According to needs of the present invention, can be simply in each polymerization procedure by quasi-adiabatic reaction (polymerization reaction heat is retained in the polymerization reaction mixture) polymerization temperature that raises, until the top temperature that reaches each reactions steps.If reached required polymerisation conversion (60mol%, but be not higher than 90mol%) at least in the past reaching required top temperature, can after reaching top temperature, immediately polymerization reaction mixture be cooled to TP1 ± 10 ℃.Otherwise,, this top temperature is kept for some time, until reaching required transformation efficiency according to the present invention.
Free radical water emulsion polymerization of the present invention is reflected in each polymerization procedure, polyreaction batch of material (the molecular weight regulator that comprises use that normally at first will be used for this step, but do not comprise radical initiator) be added in the polymerization reactor, temperature when making mixture reach polymerization to begin, add radical initiator (normally disposable whole addings) then, carry out polyreaction.In the quasi-adiabatic polymerization stage, working pressure generally raises along with the rising of polymerization temperature.Working pressure is generally 1-15atm, is generally 1-6atm, is preferably 1-3atm.In the quasi-adiabatic step of reaction, when working pressure has reached its maximum value, generally be to regulate with outside temperature to stop to heat up.
Preferably, the great majority of required water base dispersion medium total amount (〉=50%) (still, being generally at least 10%) added in the polyreaction in the 1st step, because can improve the contact area (heat exchange area) with polymerization reactor like this.In each polymerization procedure, in the time of will treating that polymerization single polymerization monomer is added in the polymerization reactor, preferably add with pre-emulsified form in aqueous medium.
In the 1st step polyreaction, can add seed latex (being not more than 1wt% usually) based on the amount of in this step, treating polymerization single polymerization monomer as needs.This can guarantee controllable polymerization order usually.For example, can use the polystyrene seed latex of polymer particles particle diameter at this for about 30nm.
The final big I of the polymer particles of the aqueous polymer dispersion that can be made by the inventive method is by the amount control of dispersion agent.General formation weight average particle diameter dw is the particulate of 50-200nm, particularly 50-150nm.Solids content in volume is generally 30-60%, is generally 40-50%.During polyreaction,, can certainly in each polymerization procedure, add radical initiator and/or dispersion agent again for reaching required polymerisation conversion and further stabilization of polymer water dispersion.
In addition, be the pH of stable waterborne dispersion medium, can during emulsion polymerization, add buffer reagent, as alkali-metal phosphoric acid salt.Add a small amount of strong electrolyte (as vitriolate of tartar, Repone K and/or sodium sulfate) in the formation stage of polymer particles, help the particle diameter that reaches required.
The polymerization of proceeding after n step polyreaction (is mainly used in the amount that reduces residual monomer, can reaches until transformation efficiency 〉=95mol%) preferably ℃ carry out in TP1 ± 10.As needs, can add polymerization starter again.This moment, the preferred acetone and the anionic adducts of bisulfite and t-butyl peroxy hydrogen of using was (and as needing, transition metal ion) combination (referring to DE-A 4 419 518 and DE-A 4 435 423) is because this initiator system only causes seldom follow-up crosslinked.
For stopping the free-radical emulsion polymerization reaction, generally be to add polymerization inhibitor such as diethyl hydroxylamine, and remove unconverted monomer with known deodorizing method (preferably extracting and/or steam distillation).
As mentioned above, the aqueous polymer dispersion of the inventive method preparation is suitable for use as synthetic cold gum, especially for preparation latex product (condom, gloves) with based on the latex foam (as mattress and carpet backing) of latex.Relevant preparation method is as known in the art.
Generally also add antiaging agent in the aqueous polymer dispersion of the inventive method preparation before application, as oxidation inhibitor or sterilant, its example has Naugawhite
, Wingstay
And Proxel
XL2.
(polyreaction is all at N for the Embodiment B D of Comparative Examples VD and the inventive method
2Carry out under the atmosphere, and add V-Brite B) as oxygen scavenger
VD1: the mixture that at first in polymerization reactor (the withstand voltage reactor of V2A stainless steel that band stirs), adds following material:
438g water,
76g concentration is the aqueous solution of the Sodium dodecylbenzene sulfonate of 15wt%,
8g Tamol
NN 4501 (concentration be 45wt% sodium naphthalene sulfonate/formaldehyde condensation products (the number average relative molecular weight: the aqueous solution 6500)),
0.8g sodium sulfate,
Uncle's 3g lauryl mercaptan,
22.8g methacrylic acid (6wt%),
148.2g vinyl cyanide (39wt%) and
209g divinyl (55wt%) also is cooled to 10 ℃.
Then, keeping temperature is 10 ℃, the mixture of at first disposable adding 3g water and 0.1g V-Brite B, disposable subsequently 0.05g hydroxyl methane-sulfinic acid sodium, the 0.015g Sequestrene of adding
The mixture of Na-Fe (the mixing Na/Fe salt of ethylenediamine tetraacetic acid (EDTA)) and 3g water.
Afterwards, the solution of the cumene hydroperoxide aqueous solution in 6g water that disposable adding 0.20g concentration is 80wt% keeps temperature to be 10 ℃ and carries out polymerization.11 hours post polymerization transformation efficiencys are 50mol%.After 24 hours, be under the 95mol% at polymerisation conversion, the mixture that adds following material stops polyreaction:
6g water,
0.2g diethyl hydroxylamine,
0.3g hydroxyl methane-sulfinic acid sodium and
8.7g concentration is the ammoniacal liquor of 25wt%.
The monomer water steam stripped of remnants is removed.
The film of the aqueous polymer dispersion that obtains
1HT
2Value is 3.8ms.
VD2: with the preparation of VD1, but polyreaction is carried out at 70 ℃.Only 6 hours post polymerization transformation efficiencys reach 95mol%.The water steam stripped is removed residual monomer.The film of the aqueous polymer dispersion that forms
1HT
2Value is 0.3ms.
VD3: the mixture that at first in polymerization reactor (the withstand voltage reactor of V2A stainless steel that band stirs), adds following material:
441g water,
76g concentration is the secondary alkyl sodium sulfonate (C of 15wt%
13/ C
17Mixture) the aqueous solution,
8g?Tamol?NN?4501，
0.8g sodium sulfate,
4.8g uncle's lauryl mercaptan,
22.8g methacrylic acid (6wt%),
167.2g vinyl cyanide (44wt%) and
190g divinyl (50wt%) also is cooled to 10 ℃.
Then, keeping temperature is 10 ℃, the mixture of at first disposable adding 3g water and 0.1g V-Brite B, the mixture of disposable subsequently adding 0.05g hydroxyl methane-sulfinic acid sodium, 0.015g Sequestrene Na-Fe and 3g water.
The solution of the cumene hydroperoxide aqueous solution in 6g water that the disposable then 0.20g of adding concentration is 80wt% keeps temperature to be 10 ℃ afterwards and carries out polyreaction.
After 24 hours, under polymerisation conversion 95mol%, adding 6g water, 0.2g diethyl hydroxylamine, 0.3g hydroxyl methane-sulfinic acid sodium and 8.7g concentration is the mixture termination polyreaction of the ammoniacal liquor of 25wt%.The water steam stripped is removed residual monomer.
The film of the aqueous polymer dispersion that forms
1HT
2Be 4.2ms.
BD1: the mixture that at first in polymerization reactor (the withstand voltage reactor of V2A stainless steel that band stirs), adds following material:
436g water,
0.8g sodium sulfate,
8.4g?Tamol?NN?4501，
53.3g concentration is the aqueous solution of the Sodium dodecylbenzene sulfonate of 15wt%,
1.6g uncle's lauryl mercaptan,
0.02g?Sequestrene?Fe-Na，
12g methacrylic acid (3wt%),
78g vinyl cyanide (19.5wt%) and
110g divinyl (27.5wt%) also is cooled to 10 ℃.
Then, keeping temperature is 10 ℃, the at first disposable mixture that adds 4.3g water and 0.1g V-Brite B, the disposable subsequently mixture that adds 0.04g hydroxyl methane-sulfinic acid sodium and 5g water.
Then, disposable adding 10g water, 0.08g concentration are the aqueous solution of Sodium dodecylbenzene sulfonate of 15wt% and the mixture of the cumene hydroperoxide aqueous solution that 0.1g concentration is 80wt%, carry out the quasi-adiabatic polyreaction afterwards, temperature until reaction mixture continues to rise to 50 ℃, has experienced 1.5 hours around here.Keep temperature to be 50 ℃ then and continue polymerization 2 hours.The transformation efficiency that reaches is 70mol%.
Then with indirect cooling with polymerization reaction mixture at 10 minutes internal cooling to 10 ℃.
The mixture of the following material of disposable adding in polymerization reactor then:
110g divinyl (27.5wt%),
78g vinyl cyanide (19.5wt%),
12g methacrylic acid (3wt%),
25.6g concentration be 15wt% sodium dodecyl benzene sulfonate aqueous solution and
1.6g the solution of the disposable subsequently adding of uncle's lauryl mercaptan (10 ℃) 0.04g hydroxyl methane-sulfinic acid sodium in 9g water.
At last, disposable adding 68g water, 0.1g concentration are the sodium dodecyl benzene sulfonate aqueous solution of 15wt% and the mixture of the cumene hydroperoxide aqueous solution that 0.1g concentration is 80wt%, carry out the quasi-adiabatic polyreaction afterwards, continue to rise to 72 ℃ until the temperature of reaction mixture.(go on foot polyreaction 1.5 hours since the 2nd) at this moment, based on the total amount for the treatment of polymerization single polymerization monomer in the 2nd step polyreaction, polymerisation conversion U2 is 69mol%, and based on the total amount for the treatment of polymerization single polymerization monomer, total polymerisation conversion of this moment is 80mol%.Then with indirect cooling with polymerization reaction mixture at 10 minutes internal cooling to 10 ℃, and keep this temperature to continue polymerization 5 hours (post-polymerization).For stopping polyreaction, adding 5g water, 0.24g diethyl hydroxylamine and 8g concentration is the mixture of the ammoniacal liquor of 25wt%.Based on the total amount for the treatment of polymerization single polymerization monomer, the polymerisation conversion of this moment is 〉=95mol%.The water steam stripped is removed residual monomer.The film of the aqueous polymer dispersion that forms
1HT
2Value is 3.7ms.In other words, compare, in polymerization time, obtain having the product of equal in quality less than half with VD1.
BD2: the mixture that at first in polymerization reactor (the withstand voltage reactor of V2A stainless steel that band stirs), adds following material:
436g water,
0.8g sodium sulfate,
8.4g?Tamol?NN?4501，
53.3g concentration is the secondary alkyl sodium sulfonate (C of 15wt%
13/ C
17Mixture) the aqueous solution,
1.6g uncle's lauryl mercaptan,
0.02g?Sequestrene?Fe-Na，
12g methacrylic acid (3wt%),
88g vinyl cyanide (22wt%) and
100g divinyl (25wt%) also is cooled to 10 ℃.
Then, keeping temperature is 10 ℃, the mixture of at first disposable adding 4.3g water and 0.04g hydroxyl methane-sulfinic acid sodium, the mixture of disposable subsequently adding 5.3g water and 0.1g V-Brite B.
Then, disposable adding 10g water, 0.08g concentration are the sodium dodecyl benzene sulfonate aqueous solution of 15wt% and the mixture of the cumene hydroperoxide aqueous solution that 0.1g concentration is 80wt%, carry out the quasi-adiabatic polyreaction afterwards, continue to rise to 71 ℃ until the temperature of reaction mixture.(polyreaction begin 1.5 hours after) at this moment, the polymerisation conversion U1 in the 1st step polyreaction is 85mol%.
Then with indirect cooling with polymerization reaction mixture at 10 minutes internal cooling to 10 ℃.
The mixture of the following material of disposable adding in polymerization reactor then:
100g divinyl (25wt%),
88g vinyl cyanide (22wt%),
12g methacrylic acid (3wt%),
25.6g concentration is the secondary alkyl sodium sulfonate (C of 15wt%
13/ C
17Mixture) the aqueous solution and
1.6g the solution of the disposable subsequently adding of uncle's lauryl mercaptan (10 ℃) 0.04g hydroxyl methane-sulfinic acid sodium in 9g water.
At last, disposable adding 68g water, 0.1g concentration are the secondary alkyl sodium sulfonate (C of 15wt%
13/ C
17Mixture) aqueous solution and 0.1g concentration are the mixture of the cumene hydroperoxide aqueous solution of 80wt%, carry out the quasi-adiabatic polyreaction afterwards, continue to rise to 70 ℃ until the temperature of reaction mixture.(go on foot polyreaction 1.5 hours since the 2nd) at this moment, based on the total amount for the treatment of polymerization single polymerization monomer in the 2nd step polyreaction, polymerisation conversion U2 is 74mol%, and based on the total amount for the treatment of polymerization single polymerization monomer, total polymerisation conversion of this moment is 85mol%.Then with indirect cooling with polymerization reaction mixture at 10 minutes internal cooling to 10 ℃, and keep this temperature to continue to stir 4 hours (post-polymerization).For stopping polyreaction, adding 5g water, 0.24g diethyl hydroxylamine and 8g concentration is the mixture of the ammoniacal liquor of 25wt%.Based on the total amount for the treatment of polymerization single polymerization monomer, the polymerisation conversion of this moment is 〉=95mol%.The water steam stripped is removed residual monomer.The film of the aqueous polymer dispersion that forms
1HT
2Value is 4.4ms.In other words, compare, in polymerization time, obtain having the product of equal in quality less than half with VD3.
BD3: with the preparation of BD1, still, in the 1st step polyreaction, temperature rises to 51 ℃ (during: 1 hour), keeps 2 hours (U1:80mol% at this moment) then under this temperature again, is cooled to 10 ℃ subsequently.
Similarly, in the 2nd step polyreaction, temperature only rises to 54 ℃ (during: 1 hour), keeps 2 hours (U2:83mol% of this moment afterwards under this temperature; The Utot:90mol% of this moment).After being cooled to 10 ℃, under this temperature, continue to stir last Utot 〉=95mol% 1 hour.After stripping is removed residual monomer, the film that records
1HT
2Be 4.2ms.
BD4: with the preparation of BD1, still, in the 1st step polyreaction, temperature only rises to 35 ℃ (during: 0.5 hour), keeps 3 hours (U1:85mol% at this moment) then under this temperature again, is cooled to 10 ℃ subsequently.
Similarly, in the 2nd step polyreaction, temperature only rises to 30 ℃ (during: 0.5 hour), keeps 3 hours (U2:60mol% of this moment afterwards under this temperature; The Utot:57.5mol% of this moment).After being cooled to 10 ℃, under this temperature, continued 3 hours last Utot 〉=95mol%.After stripping is removed residual monomer, the film that records
1HT
2Be 4.1ms.
BD5: with the preparation of BD1, still, TP1 is 20 ℃, and in addition, in the 1st step polyreaction, temperature only rises to 42 ℃ (during: 1 hour), keeps 2 hours (U1:80mol% at this moment) then under this temperature again, is cooled to 20 ℃ subsequently.
Similarly, in the 2nd step polyreaction, temperature only rises to 42 ℃ (during: 1 hour), keeps 2 hours (U2:83mol% of this moment afterwards under this temperature; The Utot:90mol% of this moment).After being cooled to 20 ℃, under this temperature, continue to stir last Utot 〉=95mol% 2 hours.After stripping is removed residual monomer, the film that records
1HT
2Be 3.8ms.
Claims (15)
1. method for preparing aqueous polymer dispersion, it comprises, make the monomeric mixture with at least one ethylenically unsaturated group carry out free radical water emulsion polymerization, this monomer mixture contains the monomer A with two conjugation ethylenical unsaturated double bonds of 30wt% at least, wherein
A) will treat that polymeric monomer intermixture is divided into n endorsement body, n 〉=2 altogether;
B) in polymerization reactor, at first add the 1st endorsement body and dispersion agent, radical polymerization initiator and water base dispersion medium, carry out the 1st step polyreaction, temperature during the reaction beginning is TP1,0 ℃≤TP1≤50 ℃ wherein, the temperature of polymerization reaction mixture is raise 20 ℃ at least, reach top temperature TP1H, but be no more than 80 ℃; And
Polymerization temperature is constant in TP1H to TP1H-10 ℃ temperature range, until polymerisation conversion U1 ,-treat the amount of polymerization single polymerization monomer-reach 60mol% but be no more than 90mol% at least in the polyreaction based on the 1st step, then polymerization reaction mixture is cooled to polymerization temperature TP2, wherein TP2=TP1 ± 10 ℃ and 0 ℃≤TP2≤50 ℃;
C) add the 2nd endorsement body, make the monomer mixture in the polymerization reactor in the presence of established polymkeric substance and dispersion agent and polymerization starter, carry out the 2nd step polyreaction then, polymerization temperature during the reaction beginning is TP2, the temperature of polymerization reaction mixture is raise 20 ℃ at least, reach top temperature TP2H, but be no more than 80 ℃; And
Polymerization temperature is constant in TP2H to TP2H-10 ℃ temperature range, treat the total amount of polymerization single polymerization monomer-reach 60mol% but be no more than 90mol% at least until polymerisation conversion U2-in the polyreaction based on the 2nd step, then polymerization reaction mixture is cooled to polymerization temperature TP3, wherein TP3=TP1 ± 10 ℃ and 0 ℃≤TP3≤50 ℃;
D) then, make remaining n-2 endorsement body in n-2 successive polymerization reactions steps, proceed polymerization by the 2nd batch of monomeric polymerization methods; With
E) after n step polyreaction finishes, continue polyreaction at 0-50 ℃, if desired, make total polymerisation conversion Utot-based on the total amount for the treatment of polymerization single polymerization monomer-reach 〉=95mol%.
2. according to the process of claim 1 wherein 2≤n≤5.
3. according to the method for claim 1 or 2, wherein, in each polymerization procedure, it is to continue to raise that temperature temperature from the outset rises to top temperature.
4. according to each method among the claim 1-3, wherein, treat that the polymeric monomer mixture is made up of following monomer:
At least a monomer A of 30-100wt%,
One or more have at least one olefinic unsaturated group 0-10wt%
The group and 1 the crust and 25 ℃ under in water the mole molten
Xie Du 〉=1 crust and the mole of 25 ℃ of following vinyl cyanide in water
The monomer of solubleness (monomers B) and
0-70wt% one or more be different from monomer A and B and have to
The copolymerizable monomer of a few ethylenically unsaturated group
(monomer C).
5. according to each method among the claim 1-4, wherein, treat that the polymeric monomer mixture contains divinyl as monomer A.
6. according to each method among the claim 1-5, wherein, treat that the polymeric monomer mixture is made up of following monomer:
The 30-90wt% divinyl,
The 1-10wt% methacrylic acid and
The 9-60wt% vinyl cyanide.
7. according to each method among the claim 1-6, wherein, the polyreaction in each polymerization procedure is carried out in the presence of molecular weight regulator.
8. according to each method among the claim 1-7, wherein, the polyreaction in each polymerization procedure is containing the mixture of at least a protective colloid and at least a emulsifying agent as carrying out in the presence of the dispersion agent.
9. according to each method among the claim 1-8, wherein, the polyreaction in each polymerization procedure is caused by free-radical oxidn-reduction initiating system.
10. according to each method among the claim 1-9, wherein, in each polymerization procedure, based on the amount for the treatment of polymerization single polymerization monomer in this polymerization procedure, the polymerisation conversion that reaches is 70-85mol%.
11. according to each method among the claim 1-10, wherein, TP1 is 0 ℃-20 ℃, and the top temperature of polyreaction is 40-50 ℃ in each polymerization procedure.
12., wherein, in each polymerization procedure, carry out the polymeric monomer mixture and have essentially identical composition according to each method among the claim 1-11.
13. according to each method among the claim 1-12, wherein, as described below the carrying out of free radical water emulsion polymerization reaction in each polymerization procedure: at first all that add except that radical initiator in polymerization reactor are treated the polymeric batch of material in this step, temperature when adjusting to the beginning polymerization adds radical initiator then and carries out polyreaction in polymerization reactor.
14. according to each method among the claim 1-13, wherein, after n step polyreaction, continue in TP1 ± 10 ℃ to carry out polymerization, reach 〉=95mol% until total polymerisation conversion.
15. according to each method among the claim 1-14, wherein, n criticizes monomeric each batch and contains and remain ((100/n)-10) mol% of polymeric monomer intermixture total amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96121508 CN1161340A (en) | 1995-12-04 | 1996-12-03 | Prepn. of aqueous polymer dispersion |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19545096.5 | 1995-12-04 | ||
| CN 96121508 CN1161340A (en) | 1995-12-04 | 1996-12-03 | Prepn. of aqueous polymer dispersion |
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| Publication Number | Publication Date |
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ID=5126927
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| CN 96121508 Pending CN1161340A (en) | 1995-12-04 | 1996-12-03 | Prepn. of aqueous polymer dispersion |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100369938C (en) * | 1999-11-09 | 2008-02-20 | 罗姆和哈斯公司 | Emulsion polymer |
| CN113773260A (en) * | 2021-08-26 | 2021-12-10 | 华南师范大学 | Covalent-like organic material and preparation method and application thereof |
-
1996
- 1996-12-03 CN CN 96121508 patent/CN1161340A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100369938C (en) * | 1999-11-09 | 2008-02-20 | 罗姆和哈斯公司 | Emulsion polymer |
| CN113773260A (en) * | 2021-08-26 | 2021-12-10 | 华南师范大学 | Covalent-like organic material and preparation method and application thereof |
| CN113773260B (en) * | 2021-08-26 | 2023-09-22 | 华南师范大学 | Covalent-like organic material and preparation method and application thereof |
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