CN1266065A - 用于乳液聚合的表面活性组合物 - Google Patents
用于乳液聚合的表面活性组合物 Download PDFInfo
- Publication number
- CN1266065A CN1266065A CN00103836A CN00103836A CN1266065A CN 1266065 A CN1266065 A CN 1266065A CN 00103836 A CN00103836 A CN 00103836A CN 00103836 A CN00103836 A CN 00103836A CN 1266065 A CN1266065 A CN 1266065A
- Authority
- CN
- China
- Prior art keywords
- cmc
- mol
- component
- active compositions
- emulsion
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 238000007720 emulsion polymerization reaction Methods 0.000 title abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 30
- 239000000839 emulsion Substances 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- 239000000693 micelle Substances 0.000 claims abstract description 5
- 150000001768 cations Chemical class 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 5
- 239000003995 emulsifying agent Substances 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 4
- 125000001931 aliphatic group Chemical group 0.000 abstract 1
- -1 polyoxyethylene Polymers 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 10
- 239000011734 sodium Substances 0.000 description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000013543 active substance Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000004159 Potassium persulphate Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 235000019394 potassium persulphate Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920013701 VORANOL™ Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- VFIJBTVGUHVPPW-UHFFFAOYSA-N [Br].C=C Chemical compound [Br].C=C VFIJBTVGUHVPPW-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000000402 conductometric titration Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/02—Alkyl sulfonates or sulfuric acid ester salts derived from monohydric alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S524/91—Antistatic compositions
- Y10S524/911—Composition to apply to a substrate to be destaticized
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polymerisation Methods In General (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyethers (AREA)
Abstract
本发明提供用于乳液聚合的表面活性组合物,它具有良好的聚合时稳定性和机械稳定性,而且颗粒小,粘度低。该表面活性组合物包含:以通式(Ⅰ)表示的化合物a,其临界胶团浓度(CMC)为0.007mol/l至0.1mol/l;和以通式(Ⅱ)表示的化合物b,CMC为1×10-5mol/l至0.007mol/l;组分摩尔比(a)/(b)为5/95至75/25:R1O－(A1O)m－SO3M1(Ⅰ),R2O－(A2O)n－SO3M2(Ⅱ),其中,R1和R2都是一价脂肪烃基团;A1和A2都是2至4碳的亚烷基;m和n选自1至50;M1和M2都是一价阳离子。
Description
本发明涉及用于乳液聚合的表面活性组合物。
在乙烯单体等不饱和单体的乳液聚合中，目前使用的是非离子表面活性剂和阴离子表面活性剂，前者例如聚氧乙烯烷基醚和聚氧乙烯烷基苯基醚，后者例如烷基苯磺酸盐、烷基硫酸盐、聚氧乙烯烷基醚硫酸盐、聚氧乙烯烷基苯基醚硫酸盐和高级脂肪酸盐。
其中，目前使用的是低临界胶团浓度(CMC)的表面活性剂，因为它们仅需少量即可起效。相反，高CMC的表面活性剂则不适合用作乳液聚合的表面活性剂。高CMC表面活性剂因乳液聚合所需的高于其CMC的必需浓度而不适用。(A.S.Dunn和W.A.Al-Shahib，Polymer Colloids II，R.F.Fitch编，P1enumPress，New York出版，1980，p619-628)。
在B.B.Kine & G.H.Ridlick，Surfactants in Chemical/ProcessEngineering，D.T.Wasan，M.E.Ginn & D.O.Shah编，Marcel Dekker，New York出版，1988，p305-310中，将聚氧乙烯烷基醚硫酸盐用于乳液聚合。
JP-A57-78936将聚氧乙烯烷基醚硫酸盐和聚氧乙烯聚氧丙烯烷基醚硫酸盐用于乳液聚合。
用于乳液聚合的表面活性所需的特性包括，聚合反应时的稳定性和乳液的机械稳定性良好，乳液中的颗粒小而表现为粘度低，不造成环境污染，但是，目前尚未有具备所有上述特性的表面活性剂。
本发明目的之一是提供一种用于乳液聚合的表面活性剂组合物，它具备所有上述特性。
即，本发明提供一种用于乳液聚合的表面活性组合物，它包含以通式(I)表示的化合物(a)，其CMC为0.007mol/L至0.1mol/L，还有以通式(II)表示的化合物(b)，其CMC为1×10-5mol/L至0.007mol/L，(a)/(b)的摩尔比为5/95至75/25：
R1O-(A1O)m-SO3M1 (I)
R2O-(A2O)n-SO3M2 (II)(以上通式中，R1和R2都是一价脂肪烃基团；A1和A2都是2至4碳的亚烷基；m和n表示所加烯化氧的平均摩尔数，选自1至50；M1和M2都是一价阳离子；如果A1的数量为m，A2的数量为n，则多个A1和多个A2可以彼此相同或不同。)
较好的是，组分(a)的CMC为0.01mol/L至0.06mol/L；R1有7至11个碳原子；m选自3至30；组分(b)的CMC为0.001mol/L至0.005mol/L；R2有12至16个碳原子；n选自3至30；而且，(a)/(b)为10/90至50/50。
此外，本发明还提供乳液聚合的方法，即在上述组合物存在下聚合不饱和单体，还提供上述组合物的用途，即用作不饱和单体乳液聚合的乳化剂。
本发明的组分(a)是以通式(I)表示的化合物，其CMC为0.007mol/L至0.1mol/L，以0.01mol/L至0.06mol/L为佳，可以一种独用，也可以两种或两种以上联用。另一组分(b)是以通式(II)表示的化合物，其CMC为1×10-5mol/L至0.007mol/L，以0.001mol/L至0.005mol/L为佳，可以一种独用，也可以两种或两种以上联用。
本发明中，CMC由电导滴定法测定。
通式(I)和(II)中，R1以7至11碳的直链或支链烷基为佳，R2以12至24碳的直链或支链烷基为佳，12至16碳的更好。A1和A2以亚乙基或亚丙基为佳。在加入多种烯化氧时，可采用随机加入或嵌段加入。或者，两种方法可以联用。较好的是，半数即m/2的A1是亚乙基，半数即n/2的A2是亚乙基。特别好的是，A1和A2都是亚乙基。m和n最好都选自3至30。M1和M2都以钠和钾等碱金属，铵离子或烷醇胺之类质子化的胺为佳。
通式(I)和(II)化合物可如下制造：将烯化氧例如环氧乙烷和环氧丙烷加入一元脂肪醇，然后用磺化剂例如SO3气体硫酸盐化，再用NaOH等中和。
本发明组合物中组分(a)与组分(b)的(a)/(b)摩尔比为5/95至75/25，以10/90至50/50为佳。当(a)/(b)低于5/95时，乳液的粘度过高，而且机械稳定性不够。另一方面，当(a)/(b)高于75/25时，颗粒太大，聚合时的稳定性和机械稳定性都不够。
可用本发明表面活性组合物进行乳液聚合的单体具体例如：芳族乙烯基单体，例如苯乙烯，α-甲基苯乙烯和氯苯乙烯；丙烯酸酯，例如丙烯酸甲酯，丙烯酸乙酯和丙烯酸丁酯；甲基丙烯酸酯，例如甲基丙烯酸甲酯和甲基丙烯酸乙酯；卤乙烯和二卤乙烯，例如氯乙烯，溴乙烯和二氯乙烯；乙烯酯，例如乙酸乙烯酯和丙酸乙烯酯；腈，例如丙烯腈和甲基丙烯腈；共轭二烯，例如丁二烯和异戊二烯。以上单体都既可以单用一种也可以多种联用。
本发明表面活性组合物以每100重量份单体使用0.1至20重量份为宜，0.5至5重量份更好。
本发明表面活性组合物可与一种非离子表面活性剂联用，例如聚氧乙烯(所加烯化氧的摩尔数为0至100)烷基或烯基醚(烷基或烯基的碳原子数为12至24)。还可以与水溶性保护胶联用。
对于使用本发明表面活性组合物乳液聚合的条件没有特殊的限制。全系统中，单体量以20至70(重量)％为宜，40至50(重量)％尤其好。此外，就本发明的乳液聚合而言，可使用任何一种乳液聚合法，例如单体加入法，批量法和乳液加入法。
当用本发明表面活性组合物作为乳液聚合的乳化剂时，聚合反应中的凝固量很小。即，聚合时的稳定性良好，所得乳液的机械稳定性也很好，而且，乳液的颗粒小，粘度低。
实施例1至8和比较实施例1至5
如下制备本发明的表面活性组合物和用于比较的表面活性组合物：用(a-1)至(a-3)作为组分(a)，用(b-1)至(b-4)作为组分(b)，混合比见表1。
(a-1)：C8H17O(CH2CH2O)18SO3Na CMC：0.029mol/L
(a-2)：i-C9H19O(CH2CH2O)18SO3Na CMC：0.021mol/L
(a-3)：i-C11H23O(CH2CH2O)18SO3Na CMC：0.012mol/L
(b-1)：C12H25O(CH2CH2O)18SO3Na CMC：0.0046mol/L
(b-2)：C14H29O(CH2CH2O)18SO3Na CMC：0.0012mol/L
(b-3)：C12H25O(CH2CH2O)18SO3Na CMC：0.004mol/L
(b-4)：
以上CMC是由以下方法测得的。
<CMC的测定方法>
在烧杯中加100mL蒸馏水，搅拌，测定电导(所用的电导测定仪是TOAElectronics Ltd.生产的CM-20S型，CG-511B池)。将0.2ml已事先调定到给定浓度的表面活性剂溶液滴加入烧杯，每滴一滴读取一次电导。当滴定溶液中的表面活性剂浓度达xmol/L，滴定体积为yml时，烧杯中表面活性剂浓度C为：C＝x·y/(100+y)。电导对浓度曲线的折点出现在CMC。CMC是在25℃测定的。
用以下单体加入法，用以上制备的表面活性组合物进行了乳液聚合。然后根据以下方法检测所的的聚合物乳液。结果见表1。
(1)聚合时的稳定性(凝固量)
用200目的不锈钢丝网过滤聚合物乳液。而且，在聚合反应后收集黏附在反应器壁和搅拌桨等之上的凝固物，以同样的方式过滤。水洗，并26.6kPa，105℃干燥2小时后，称量凝固物的重量并确定其量。将聚合反应时的稳定性表示为凝固物对所用单体总量的重量％。
(2)机械稳定性
用Maron稳定性测定仪，以10kgf，1000r/min的条件搅拌50g聚合物乳液5分钟，用200目的不锈钢丝网过滤形成的凝固物，过滤后的残留物用水洗涤，26.6kPa，105℃干燥，然后称重。机械稳定性表示为凝固物比之聚合物的重量％。
(3)粘度
在25℃，用Brookfield粘度计以12r/min的速度测定聚合物乳液的粘度。
(4)平均粒径
采用动态光散射法，用Coulter Elactronics Inc.的N-4SD测定乳液的平均粒径。
<单体加入法>
在一拆卸式烧瓶中加入316.25g去离子水，8.75g表面活性组合物和0.35g过硫酸钾。然后，在氮气流下搅拌30分钟。
将0.9g丙烯酸与174.1g丙烯酸丁酯混合，取8.75g该单体混合物加入上述烧瓶，将烧瓶置于60℃水浴中加热。当温度达58℃时，用2小时滴加完剩余的单体混合物。在此期间，将烧瓶的温度维持在60±2℃。滴加完毕后，混合物60℃保温3小时，然后冷却至室温，得到聚合物乳液。
表1
| 表面活性组合物 | 聚合时的稳定性％ | 机械稳定性％ | 粘度(mPa·s) | 平均粒径(nm) | ||||
| 组分(a) | 组分(b) | (a)/(b)摩尔比 | ||||||
| 实施例 | 1 | (a-1) | (b-1) | 20/80 | 0.05 | 2.5 | 4000 | 71 |
| 2 | (a-1) | (b-1) | 50/50 | 0.06 | 3.1 | 2000 | 72 | |
| 3 | (a-1) | (b-2) | 30/70 | 0.05 | 2.7 | 3700 | 71 | |
| 4 | (a-1) | (b-2) | 40/60 | 0.07 | 3.3 | 3800 | 73 | |
| 5 | (a-1) | (b-4) | 20/80 | 0.06 | 3.5 | 4200 | 72 | |
| 6 | (a-2) | (b-1) | 10/90 | 0.05 | 2.4 | 4300 | 70 | |
| 7 | (a-2) | (b-3) | 20/80 | 0.06 | 2.2 | 1500 | 70 | |
| 8 | (a-3) | (b-1) | 70/30 | 0.06 | 1.9 | 9500 | 73 | |
| 比较实施例 | 1 | 无 | (b-1) | - | 0.15 | 10.5 | 12000 | 70 |
| 2 | 无 | (b-2) | - | 0.21 | 9.6 | 600 | 68 | |
| 3 | (a-1) | 无 | - | 0.26 | 15.3 | 900 | 90 | |
| 4 | 无 | (b-1)* | - | 0.68 | 10.2 | 1200 | 75 | |
| 5 | (a-1) | (b-1) | 80/20 | 0.24 | 12.4 | 85 | ||
*：加入1％Na2SO4
实施例9至12和比较实施例6至9
用前述方法制备本发明的和用于比较的表面活性组合物，以上述(a-1)和(a-2)作为组分(a)，以上述(b-1)和(b-2)作为组分(b)，混合比见表2。
采用以下批量法，用所的的表面活性组合物进行乳液聚合。用上述方法评价所的的聚合物乳液，结果见表2。
<批量法>
在拆卸式烧瓶中加316.25g去离子水，8.75g表面活性组合物和0.35g过硫酸钾。然后在氮气流下搅拌30分钟。
向上述烧瓶中，一次性加入175g苯乙烯单体，将烧瓶置于65℃水浴中加热。当烧瓶内温度达62℃时，聚合反应开始。将烧瓶温度在65±2℃维持5小时以完成聚合反应，于是得到聚合物乳液。
表2
| 表面活性组合物 | 聚合时的稳定性％ | 机械稳定性％ | 粘度(mPa.s) | 平均粒径(nm) | ||||
| 组分(a) | 组分(b) | (a)/(b)摩尔比 | ||||||
| 实施例 | 9 | (a-1) | (b-1) | 20/80 | 0.15 | 0.24 | 115 | 87 |
| 10 | (a-1) | (b-2) | 50/50 | 0.11 | 0.28 | 80 | 88 | |
| 11 | (a-2) | (b-1) | 30/70 | 0.13 | 0.22 | 110 | 87 | |
| 12 | (a-2) | (b-2) | 40/60 | 0.14 | 0.23 | 120 | 88 | |
| 比较实施例 | 6 | 无 | (b-1) | - | 0.23 | 0.51 | 270 | 88 |
| 7 | 无 | (b-2) | - | 0.48 | 未测定* | 450 | 84 | |
| 8 | (a-1) | 无 | - | 0.21 | 0.42 | 30 | 92 | |
| 9 | (a-1) | (b-1)* | 80/20 | 0.22 | 0.48 | 50 | 92 | |
*：Maron测试中，前5分钟内产生的凝固量太大以至于无法继续搅拌。
实施例13至20和比较实施例10至13
用前述方法制备本发明的和用于比较的表面活性组合物，以上述(a-1)至(a-3)作为组分(a)，以上述(b-1)至(b-4)作为组分(b)，混合比见表3。
采用以下乳液加入法，用所的的表面活性组合物进行乳液聚合。用上述方法评价所的的聚合物乳液，结果见表3。
<乳液加入法>
混合2.5g丙烯酸，123.75g丙烯酸丁酯和123.75g甲基丙烯酸甲酯，制备成单体混合物。将5.0g表面活性组合物和0.50g过硫酸钾溶于107.1g去离子水，与上述单体混合物混合，用匀浆混合机(T.K.HOMO Mixer，Tokusyu KikaKogyo Co.Ltd.)，以5000r/min乳化10分钟，得到均匀的单体乳液。
在拆卸式烧瓶中加137.9g去离子水和36.2g上述单体乳液，在氮气流下搅拌30分钟。然后，将烧瓶置于80℃水浴中加热。先进行30分钟的初期聚合，然后用2小时加入剩余单体乳液。期间，烧瓶温度维持于80±2℃。滴加完毕后，混合物80℃保温3小时，然后冷却至室温，得到聚合物乳液。
表3
| 表面活性组合物 | 聚合时的稳定性％ | 机械稳定性％ | 粘度(mPa·s) | 平均粒径(nm) | ||||
| 组分(a) | 组分(b) | (a)/(b)摩尔比 | ||||||
| 实施例 | 13 | (a-1) | (b-1) | 20/80 | 0.08 | 0.12 | 650 | 177 |
| 14 | (a-1) | (b-1) | 50/50 | 0.06 | 0.25 | 410 | 185 | |
| 15 | (a-1) | (b-2) | 30/70 | 0.05 | 0.31 | 750 | 175 | |
| 16 | (a-1) | (b-2) | 40/60 | 0.06 | 0.27 | 530 | 182 | |
| 17 | (a-1) | (b-4) | 20/80 | 0.08 | 0.22 | 570 | 178 | |
| 18 | (a-2) | (b-1) | 10/90 | 0.07 | 0.13 | 870 | 174 | |
| 19 | (a-2) | (b-3) | 20/80 | 0.06 | 0.18 | 680 | 177 | |
| 20 | (a-3) | (b-1) | 70/30 | 0.06 | 0.34 | 330 | 185 | |
| 比较实施例 | 10 | 无 | (b-1) | - | 0.32 | 1.2 | 1200 | 163 |
| 11 | 无 | (b-2) | - | 0.35 | 2.5 | 1400 | 160 | |
| 12 | (a-1) | 无 | - | 0.28 | 15.3 | 220 | 205 | |
| 13 | (a-1) | (b-1) | 80/20 | 0.31 | 13.8 | 250 | 205 | |
Claims (7)
1.用于乳液聚合的表面活性组合物，它包含作为主要成分的：以通式(I)表示的化合物a，其临界胶团浓度(CMC)为0.007mol/L至0.1mol/L；和以通式(II)表示的化合物b，其临界胶团浓度(CMC)为1×10-5mol/L至0.007mol/L；组分(a)与(b)的摩尔比(a)/(b)为5/95至75/25：
R1O-(A1O)m-SO3M1 (I)
R2O-(A2O)n-SO3M2 (II)其式中，R1和R2都是一价脂肪烃基团；A1和A2都是2至4碳的亚烷基；m和n表示所加烯化氧的平均摩尔数，选自1至50；M1和M2都是一价阳离子；如果A1的数量为m，A2的数量为n，则多个A1和多个A2可以彼此相同或不同。
2.根据权利要求1所述的组合物，其中组分(a)的临界胶团浓度为0.01mol/L至0.06mol/L；组分(b)的CMC为0.001mol/L至0.005mol/L。
3.根据权利要求1所述的组合物，其中的m和n选自3至30。
4.根据权利要求1所述的组合物，其中A1和A2都是亚乙基。
5.根据权利要求1所述的组合物，其中的(a)/(b)为10/90至50/50。
6.一种乳液聚合方法，是在权利要求1所述组合物的存在下聚合不饱和单体。
7.权利要求1所述组合物的用途，它被用作乳液聚合不饱和单体的乳化剂。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11057128A JP3025763B1 (ja) | 1999-03-04 | 1999-03-04 | 乳化重合用界面活性剤組成物 |
| JP57128/1999 | 1999-03-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1266065A true CN1266065A (zh) | 2000-09-13 |
| CN1137901C CN1137901C (zh) | 2004-02-11 |
Family
ID=13046937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001038362A Expired - Lifetime CN1137901C (zh) | 1999-03-04 | 2000-03-02 | 用于乳液聚合的表面活性组合物 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US6380302B1 (zh) |
| EP (1) | EP1033166B1 (zh) |
| JP (1) | JP3025763B1 (zh) |
| CN (1) | CN1137901C (zh) |
| DE (1) | DE60016992T2 (zh) |
| ES (1) | ES2234464T3 (zh) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103906804A (zh) * | 2011-08-24 | 2014-07-02 | 萨索尔烯烃及表面活性剂有限公司 | 用于乳液聚合的伸展的表面活性剂 |
| WO2014134826A1 (en) * | 2013-03-08 | 2014-09-12 | Dow Global Technologies Llc | Anionic surfactant compositions and use thereof |
| US10016733B2 (en) | 2012-09-29 | 2018-07-10 | Dow Global Technologies Llc | Anionic surfactant compositions and use thereof |
| CN109890495A (zh) * | 2016-09-29 | 2019-06-14 | 第一工业制药株式会社 | 表面活性剂组合物 |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4536193B2 (ja) * | 2000-02-10 | 2010-09-01 | 花王株式会社 | 乳化重合用界面活性剤組成物 |
| DE10161273A1 (de) * | 2001-12-13 | 2003-06-26 | Cognis Deutschland Gmbh | Verwendung von Ethersulfaten als Emulgatoren für die Emulsionspolymerisation |
| US6998051B2 (en) * | 2002-07-03 | 2006-02-14 | Ferro Corporation | Particles from supercritical fluid extraction of emulsion |
| US6966990B2 (en) | 2002-10-11 | 2005-11-22 | Ferro Corporation | Composite particles and method for preparing |
| US7083748B2 (en) * | 2003-02-07 | 2006-08-01 | Ferro Corporation | Method and apparatus for continuous particle production using supercritical fluid |
| EP1464656A1 (en) * | 2003-04-04 | 2004-10-06 | Ucb S.A. | Emulsifier composition |
| US20060008531A1 (en) * | 2003-05-08 | 2006-01-12 | Ferro Corporation | Method for producing solid-lipid composite drug particles |
| EP1860122A1 (en) * | 2006-05-24 | 2007-11-28 | Rhodia Recherches et Technologies | Process of making aqueous dispersions of polymers, emulsions polymers and use thereof |
| JP5281277B2 (ja) * | 2007-12-11 | 2013-09-04 | 花王株式会社 | 乳化重合用界面活性剤組成物 |
| JP5281278B2 (ja) * | 2007-12-11 | 2013-09-04 | 花王株式会社 | 乳化重合用界面活性剤組成物 |
| JP2009221257A (ja) * | 2008-03-13 | 2009-10-01 | Nippon Shokubai Co Ltd | ポリアルキレングリコール系化合物とその用途 |
| CN105377903B (zh) * | 2013-07-18 | 2017-03-29 | 旭硝子株式会社 | 含氟聚合物水性分散液的制造方法、含氟聚合物水性分散液和含氟聚合物 |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE586366A (zh) * | 1959-01-12 | |||
| US3120505A (en) * | 1959-08-21 | 1964-02-04 | Diamond Alkali Co | Ethers in paste resin production |
| NL136303C (zh) * | 1962-02-27 | |||
| US3317495A (en) * | 1964-01-06 | 1967-05-02 | Diamond Alkali Co | Emulsion polymerization of vinyl chloride with hydrogen peroxide, an alkali metal formaldehyde sulfoxylate and a fatty acid sulfate salt |
| US3697466A (en) * | 1966-09-16 | 1972-10-10 | Staley Mfg Co A E | Polymer composition |
| US3432455A (en) * | 1967-02-08 | 1969-03-11 | Standard Brands Chem Ind Inc | Emulsion polymerization of unsaturated monomers |
| US3565939A (en) * | 1967-06-09 | 1971-02-23 | Standard Chem Products Inc | Partial neutralization of sulfates of ethoxylated alcohols |
| US4218553A (en) * | 1974-06-14 | 1980-08-19 | Chemische Werke Huls Aktiengesellschaft | Polymerization of vinyl chloride with Sx Oy containing emulsifiers |
| US4285356A (en) * | 1979-10-12 | 1981-08-25 | Conoco, Inc. | Method of transporting viscous hydrocarbons |
| JPS5778936A (en) * | 1980-11-04 | 1982-05-17 | Kao Corp | Surfactant for polymer emulsion |
| US5539021A (en) * | 1995-06-05 | 1996-07-23 | The Dow Chemical Company | Process for preparing high internal phase ratio emulsions and latexes derived thereof |
| DE19621843A1 (de) | 1996-05-30 | 1997-12-04 | Basf Ag | Blockförmige iso-Tridecanolalkoxylate als schaumarme oder schaumdämpfende Tenside |
| TW391981B (en) | 1996-12-02 | 2000-06-01 | Kao Corp | Surfactant formulation |
| TW519535B (en) | 1996-12-06 | 2003-02-01 | Nippon Catalytic Chem Ind | Higher secondary alcohol alkoxylate compound composition, method for production thereof, and detergent and emulsifier using the composition |
-
1999
- 1999-03-04 JP JP11057128A patent/JP3025763B1/ja not_active Expired - Fee Related
-
2000
- 2000-02-28 US US09/517,003 patent/US6380302B1/en not_active Expired - Lifetime
- 2000-03-02 CN CNB001038362A patent/CN1137901C/zh not_active Expired - Lifetime
- 2000-03-03 EP EP00104421A patent/EP1033166B1/en not_active Expired - Lifetime
- 2000-03-03 DE DE60016992T patent/DE60016992T2/de not_active Expired - Lifetime
- 2000-03-03 ES ES00104421T patent/ES2234464T3/es not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103906804A (zh) * | 2011-08-24 | 2014-07-02 | 萨索尔烯烃及表面活性剂有限公司 | 用于乳液聚合的伸展的表面活性剂 |
| US10016733B2 (en) | 2012-09-29 | 2018-07-10 | Dow Global Technologies Llc | Anionic surfactant compositions and use thereof |
| WO2014134826A1 (en) * | 2013-03-08 | 2014-09-12 | Dow Global Technologies Llc | Anionic surfactant compositions and use thereof |
| CN105008328A (zh) * | 2013-03-08 | 2015-10-28 | 陶氏环球技术有限责任公司 | 阴离子表面活性剂组合物和其用途 |
| US9555385B2 (en) | 2013-03-08 | 2017-01-31 | Dow Global Technologies Llc | Anionic surfactant compositions and use thereof |
| CN105008328B (zh) * | 2013-03-08 | 2018-03-23 | 陶氏环球技术有限责任公司 | 阴离子表面活性剂组合物和其用途 |
| CN109890495A (zh) * | 2016-09-29 | 2019-06-14 | 第一工业制药株式会社 | 表面活性剂组合物 |
| CN109890495B (zh) * | 2016-09-29 | 2021-04-20 | 第一工业制药株式会社 | 表面活性剂组合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1033166B1 (en) | 2004-12-29 |
| DE60016992D1 (de) | 2005-02-03 |
| EP1033166A2 (en) | 2000-09-06 |
| EP1033166A3 (en) | 2001-05-30 |
| CN1137901C (zh) | 2004-02-11 |
| ES2234464T3 (es) | 2005-07-01 |
| JP3025763B1 (ja) | 2000-03-27 |
| US6380302B1 (en) | 2002-04-30 |
| DE60016992T2 (de) | 2005-12-29 |
| JP2000256548A (ja) | 2000-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1137901C (zh) | 用于乳液聚合的表面活性组合物 | |
| CN1039349C (zh) | 含有硅氧烷防沫剂的液体洗涤剂组合物 | |
| CN1021053C (zh) | 疏水性改进的羟乙基纤维存在下聚合物水乳胶的制备方法 | |
| CN1206721A (zh) | 氟化聚合物的制备 | |
| FI72528C (fi) | Foerfarandet foer framstaellning av en steriskt stabiliserad polymer-vattendispersion. | |
| CN1226564A (zh) | 含有基于含疏水单元的阳离子聚合物的两亲分散剂水溶性聚合物的盐水分散体 | |
| CN1639313A (zh) | 用于硬表面的防污洗涤剂 | |
| CN102391547A (zh) | 玻璃纤维制品和玻璃纤维增强塑料 | |
| CN1134437A (zh) | 接枝的聚合物组合物 | |
| EP1182217A2 (en) | Novel water-soluble copolymer and its production process and use | |
| CN1894284A (zh) | 反相乳液聚合物的转化的改进 | |
| JP3756391B2 (ja) | 乳化重合用界面活性剤組成物 | |
| CN1052869A (zh) | 阳离子聚合物的油包水乳状液 | |
| JP4166369B2 (ja) | 界面活性剤 | |
| JP4794946B2 (ja) | 乳化液の製造方法 | |
| CN1458172A (zh) | 含醚膦酸磺羧酸多元封端共聚物及多功能水处理剂的制备方法 | |
| JP4086998B2 (ja) | 乳化重合用界面活性剤組成物 | |
| CN1328582A (zh) | 胶乳聚合物的组合物 | |
| JP4080105B2 (ja) | 乳化重合用界面活性剤組成物 | |
| CN108822264A (zh) | 一种具有消泡功能的羧酸盐聚合物分散剂 | |
| JP3429705B2 (ja) | 乳化重合用界面活性剤組成物 | |
| JP4112164B2 (ja) | 乳化重合用反応性界面活性剤組成物 | |
| JP4118450B2 (ja) | 乳化重合用界面活性剤組成物 | |
| JP4080094B2 (ja) | 乳化重合用界面活性剤組成物 | |
| JP4907177B2 (ja) | 乳化重合用乳化剤 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20040211 |