EP0422120A1 - Agent tensio-actif polymerisable - Google Patents

Agent tensio-actif polymerisable

Info

Publication number
EP0422120A1
EP0422120A1 EP19890908294 EP89908294A EP0422120A1 EP 0422120 A1 EP0422120 A1 EP 0422120A1 EP 19890908294 EP19890908294 EP 19890908294 EP 89908294 A EP89908294 A EP 89908294A EP 0422120 A1 EP0422120 A1 EP 0422120A1
Authority
EP
European Patent Office
Prior art keywords
group
vinyl
alkyl
mixtures
chloride
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.)
Withdrawn
Application number
EP19890908294
Other languages
German (de)
English (en)
Other versions
EP0422120A4 (en
Inventor
Robert H. Tang
Paritosh M. Chakrabarti
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PPG Industries Inc
Original Assignee
PPG Industries Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by PPG Industries Inc filed Critical PPG Industries Inc
Publication of EP0422120A1 publication Critical patent/EP0422120A1/fr
Publication of EP0422120A4 publication Critical patent/EP0422120A4/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/15—Unsaturated ethers containing only non-aromatic carbon-to-carbon double bonds
    • C07C43/16—Vinyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/326—Polymers modified by chemical after-treatment with inorganic compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/17—Unsaturated ethers containing halogen
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/324—Polymers modified by chemical after-treatment with inorganic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic

Definitions

  • one or more surfactants are employed conventionally to emulsify the monomer reactant(s) and the resulting polymer product latex.
  • surfactants do not become chemically bonded to the polymer product molecule by carbon to carbon bonding (as distinct from a physical mixture, being adsorbed on the polymer product or the like). It has been suggested that the small amount of surfactant which remains in the polymer product latex may interfere with performance of products, e.g., coatings and adhesives, prepared from such latex.
  • Patent 3,941,857 describes incorporating a small amount of an epoxy resin with a vinyl chloride/olefin copolymer resin before casting a film from the resin.
  • U.S. Patent 4,049,608 describes the use of esters of an alkenoic acid selected from the group consisting of cinnamic acid and alkenoic acids of from 4 to 18 carbon atoms with a hydroxyalkane sulfonic acid in the emulsion polymerization of vinyl and other ethylenically unsaturated monomers. These esters serve the dual function of emulsifier and co-monomer.
  • Patent 4,224,455 describes a class of ringed sulfonated half esters of maleic anhydride and alkoxylated alkyl arylols. These esters are reported to be anionic emulsifiers (surfactants) and reactive functional monomers that are copolymerizable under emulsion polymerization conditions.
  • U.S. Patent 4,337,185 describes use of a reactive polymeric surfactant which is a substantially linear synthetic water-soluble surfactant whose polymeric backbone is derived from the polymerization of one or more ethylenically unsaturated monomers and which polymeric surfactant has a number average molecular weight of from about 500 to about 40,000 and contains various functional groups.
  • the polymerizable surfactant compounds of the present invention may be represented by the following graphic formula: wherein R is an organic monovalent radical having alpha-beta olefinic (ethylenic) unsaturation. More particularly, R is an organic radical selected from the group consisting of C 2 -C 18 alkenyl, e.g., vinyl and allyl, acrylyl, acrylyl (C 1 -C 10 ) alkyl, methacrylyl, methacrylyl
  • a is a number between 0 and 16.
  • graphic formula I -R'O- is a bivalent alkyleneoxy
  • -R'O- may be represented by the graphic formula -CH 2 CH(R")-O-, wherein R" is methyl, ethyl, phenyl, phenyloxymethyl,
  • -R'O- may be described as the bivalent radical derived from cyclic ethers selected from the group consisting of propylene oxide, (e.g., 1,2-epoxypropane), butylene oxide (e.g., 1,2-epoxybutane), styrene oxide [(epoxyethyl) benzene], tetrahydrofuran, phenyl glycidyl ether (1,2-epoxy-3-phenoxypropane) and mixtures thereof.
  • -R'O- is the bivalent epoxy group derived from propylene oxide, butylene oxide and mixtures of propylene oxide and butylene oxide.
  • the letter E in graphic formula I is the bivalent ethylene radical, and m and n are each numbers which may vary from about 5 to about 100, preferably between about 5 or 10 and about 50.
  • the ratio of m:n may vary from about 20:1 to about 1:20.
  • the specific ratio of m:n used will depend on the particular polymerization system in which the polymerizable surfactant of the present invention is incorporated. Varying the ratio of m:n will vary the HLB (Hydrophilic-Lipophilic Balance) of the polymerizable surfactant compound.
  • HLB Hydrophilic-Lipophilic Balance
  • n the polymerization system requires a hydrophobic surfactant
  • m the polymerization system requires a hydrophilic surfactant
  • m the polymerization system requires a hydrophilic surfactant
  • the ratio of m:n should be chosen so that the resulting compound is capable of reducing the surface tension of water.
  • the surface tension of a 0.1 weight percent aqueous solution of the polymerizable surfactant compound at 25°C is less than
  • X in graphic formula I is selected from the group consisting of hydroxyl (-OH), chloride (-C1), sulfonate (-SO 3 ), sulfate (-OSO 3 ), phosphate [-O-P(O)(OH) 2 ], acetate (-CH 2 -C(O)OH), isethionate
  • X will be selected from the group consisting of sulfonate, sulfate, phosphate, acetate and isethionate anionic groups, tertiary amino, i.e., -N(R 2 )(R 3 )R 4 , wherein R 2 , R 3 and R 4 are each selected from the group consisting of alkyl and hydroxyalkyl groups, particularly groups containing from 1 to 5 carbon atoms, e.g., a tertiary amine derived from trimethylamine, triethylamine, triethanolamine and diethylmethylamine.
  • X will be selected from the group consisting of sulfonate, sulfate, phosphate, acetate
  • the polymerizable surfactant of the present invention may be prepared by reacting the precursor alcohol, ROH, wherein R is as heretofore defined with respect to graphic formula I, with the desired amount of first cyclic ether (R'O), e.g., propylene oxide, butylene oxide or mixtures thereof, and subsequently reacting the resulting epoxy-containing product with the desired amounts of ethylene oxide (EO).
  • ROH first cyclic ether
  • EO ethylene oxide
  • the product resulting from this reaction sequence is a material corresponding to graphic formula I wherein X is hydroxyl. Such a material may be used as a non-ionic surfactant.
  • Sulfonate terminated polymerizable surfactants of graphic formula I may be prepared by first converting the corresponding non-ionic material to the corresponding chloride by reaction with thionyl chloride or carbonyl chloride (followed by subsequent decarboxylation to the chloride) and then reacting the chloride derivative with sodium sulfite.
  • the pre-formed sulfonate terminated surfactant product may be used as the reaction medium to improve conversions.
  • from 0 to 20 weight percent (based on the total amount of reactants) of pre-formed sulfonate product may be added to the reactor.
  • the precursor alpha-beta ethylenically unsaturated alcohols used to prepare the polymerizable surfactant materials of graphic formula I may be prepared by methods known in the art. Some, such as allyl alcohol, are readily commercially available.
  • the precursor alcohol is charged to a suitable autoclave and heated to a temperature in the range of from about 110°C. to about 130°C.
  • Propylene oxide and/or 1,2-epoxybutane are metered into the autoclave and reacted with the unsaturated alcohol in the presence of an alkaline reagent such as sodium hydroxide.
  • ethylene oxide is substituted for the propylene oxide and/or 1,2-epoxybutane reactant(s) and metered into the reactor until the desired level of ethoxylation is achieved. Pressures in the reactor will usually remain at less than 100 pounds per square inch gage during these reactions.
  • the resulting poly(alkyleneoxy) material is removed from the reactor, the alkaline reagent neutralized with acid, and the product recovered by filtration. This non-ionic material maybe converted to the sulfate, sulfonate, phosphate ester, acetate, or isethionate (or their salts), or the chloride or quaternary ammonium derivative by the methods heretofore described.
  • the number of epoxy, e.g., alkyleneoxy, groups present in the polymerizable surfactant material will vary as described with respect to graphic formula I.
  • the number of epoxy units present per mole of surfactant of graphic formula I i.e., the letters "m” and "n" is the average number of moles of cyclic ether present per mole of surfactant and hence the value of m and n may be a fractional number between 5 and 100.
  • Such polymerizations may be carried out by free radical initiated polymerization using batch, continuous, or controlled monomer feed processes, known conditions of stirring time and temperature, and known kinds of additives such as initiators, surfactants, electrolytes, pH adjusting agents, buffering agents and the like.
  • additives such as initiators, surfactants, electrolytes, pH adjusting agents, buffering agents and the like.
  • the emulsion or solution polymerization will be carried out from about
  • the polymerizable surfactant of the present invention may be added batchwise, semicontinuously or continuously to the polymerizable reaction mixture.
  • the quantity of polymerizable surfactant used in the polymerization of ethylenically unsaturated monomers, particularly when used as the sole emulsion polymerization surfactant, may range from about 1.0 to about 10 weight percent based on the total reactant monomer content employed in the given emulsion polymerization system.
  • the amount of such polymerizable surfactant material employed ranges from about 3.0 to about 6 weight percent, similarly based on total monomer.
  • polymerizable surfactants of the present invention may be used as comonomers with the ethylenically unsaturated monomer(s) to modify the physical properties of the resulting polymer.
  • the amount of polymerizable surfactant that may be so used may vary, e.g., from about 1 to about 25 weight percent, but will commonly be in the range of from about 1 to about 10, e.g., 3 to 6, weight percent, based on the total reactant monomer content.
  • conventional emulsion polymerization surfactants also may be used as additives to the polymerization, e.g., in amounts of from about 3 to 6 weight percent, based on the total amount of monomeric reactants to be polymerized.
  • ethylenically unsaturated monomer(s) and from 1-25 weight percent (as described hereinbefore) of the polymerizable reactive compounds represented by graphic formula I are copolymerized by solution polymerization.
  • Any conventional organic solvent which may be a solvent for both the monomer(s) and polymer, or just the monomer(s) may be used.
  • Organic free-radical initiators as described herein, may be used to initiate the solution polymerization.
  • Conventional cationic nonpolymerizable surfactants include the classes of salts of aliphatic amines, especially the fatty amines, quaternary ammonium salts and hydrates, fatty amides derived from disubstituted diamines, fatty chain derivatives of pyridinium compounds, ethylene oxide condensation products of fatty amines, sulfonium compounds, isothiouronium compounds and phosphonium compounds.
  • cationic surfactants are dodecylamine acetate, dodecylamine hydrochloride, tetradecylamine hydrochloride, hexadecylamine acetate, lauryl dimethylamine citrate, octadecylamine sulfate, dodecylamine lactate, cetyl trimethyl ammonium bromide, cetyl pyridinium chloride, an ethanolated alkyl guanidine amine complex, stearyl dimethyl benzyl ammonium chloride, cetyl dimethyl amine oxide, cetyl dimethyl benzyl ammonium chloride, tetradecylpyridinium bromide, diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, 1-(2-hydroxyethyl)-2-(mixed pentadecyl and heptadecyl)-2-imidazoline, resin
  • Typical nonionic emulsifiers are compounds formed by the reaction of an alkylene oxide, such as ethylene oxide, propylene oxide or butylene oxide, with long chain fatty alcohols, long chain fatty acids, alkylated phenols, long chain alkyl mercaptans, long chain alkyl primary amines, for example, cetylamine, the alkylene oxides being reacted in a ratio of from about 5 moles to 20 moles or higher, e.g., up to 50 moles, per mole of the coreactant.
  • an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide
  • long chain fatty alcohols long chain fatty acids
  • alkylated phenols alkylated phenols
  • long chain alkyl mercaptans long chain alkyl primary amines
  • cetylamine long chain alkyl primary amine
  • Other representative compounds are monoesters, e.g., the reaction products of a polyethylene glycol with a long chain fatty acid, for example, glycerol monostearate, sorbitan, trioleate and partial and complete esters of long chain carboxylic acids with polyglycol ethers of polyhydric alcohols.
  • long chain in the above description is meant an aliphatic group having from six carbon atoms to 20 carbon atoms or more.
  • a further additive that may be introduced into the polymerization reaction media is a conventional chain transfer agent such as an alkyl polyhalide or mercaptan.
  • hydrocarbon monomers include compounds such as the styrene compounds, e.g., styrene, carboxylated styrene, and alpha-methyl styrene, and conjugated dienes, for example, butadiene, isoprene and copolymers of butadiene and isoprene.
  • vinyl and vinylidene halides include: vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride.
  • the aforesaid monomers may be homopolymerized or copolymerized with other of the described monomers, i.e., one or more different monomers capable of addition type polymerization.
  • 1,2-epoxybutane was introduced slowly and continuously into the autoclave while the reactor contents were maintained between about 110°C. and 130°C.
  • the maximum operating pressure during addition of the 1,2-epoxybutane was less than 100 psig.
  • EXAMPLE 2 A two liter, jacketed round-bottom flask equipped with a phosgene inlet tube, dry ice cooled condenser, stirrer and dropping funnel was charged with 20 grams of liquid phosgene. The reaction flask was then charged simultaneously with 477 grams of product Sample 1-B described in Example 1 and 40 grams of additional phosgene. The reaction mixture was stirred at 15-20°C. for several hours before excess phosgene was removed by degassing the reaction product. The resulting chloroformate was converted to the corresponding chloride by heating it in the presence of 1.23 grams of trioctyl methyl ammonium chloride at 120-140°C. for 4 hours. 480 grams of product were recovered. The product was confirmed as the corresponding chloride by proton-NMR and infrared spectroscopy, and total chloride analysis.
  • a 0.5 liter magnetically stirred autoclave was charged with 100.7 grams of the chloride product of Example 2, 12.3 grams of sodium sulfite (98 percent), 265.1 grams of deionized water and 1.2 grams of a 50 percent aqueous solution of sodium hydroxide.
  • the autoclave was sealed and the contents heated to 155°C. and maintained at temperature overnight. The pressure within the autoclave stabilized at about 60 psig. The contents of the autoclave were cooled subsequently to less than 5°C.
  • the product, i.e., the corresponding sulfonate of the chloride product of Example 2 was a light yellow liquid containing 28.3 percent solids with 7.2 percent (as is) anionic surfactant activity.
  • Example 4 The procedure of Example 3 was repeated except that 77.4 grams of the pre-formed sulfonate product produced in Example 3 was added to the autoclave with the reactants. 423.7 grams of a light yellow clear liquid product was recovered from the autoclave. The product was treated with 1.00 grams of hydrogen peroxide (49.5 percent) for removal of residual sulfite anion. The product contained about 30 percent solids and analyzed about 14.6 percent anionic surfactant activity.
  • Example 5 The procedure of Example 3 was repeated except that 113.2 grams of the pre-formed sulfonate product from Example 4 was added to the autoclave with the reactants. The product was a light yellow clear liquid. It was treated with 1.33 grams of hydrogen peroxide (49.5 percent) for removal of residual sulfite anion. The sulfonate product was combined with the product of
  • Example 4 The resultant mixture had a solids content of about 28.3 percent and analyzed about 16.2 percent anionic surfactant activity.
  • the surface tension of a 0.1 weight percent aqueous solution of the product was found to be 35.6 dynes/centimeter at 25°C.
  • Example 2 Using the procedure of Example 2, 401 grams of Sample 1-A were reacted with phosgene and the resulting chloroformate decarboxylated to the corresponding chloride with 1.1 grams of trioctyl methyl ammonium chloride. 77.7 grams of the resulting chloride product were converted to the sulfonate by the procedure of Example 3 utilizing 15.4 grams of sodium sulfite, 174.3 grams of deionized water and 1.54 grams of a 50 percent aqueous solution of sodium hydroxide. A milky light yellow liquid containing 33.3 percent solids with 9.6 percent anionic surfactant activity was obtained.
  • Example 6 77.7 grams of the chloride product of Example 6, 15.4 grams of sodium sulfite, 1.54 grams of sodium hydroxide, 218.3 grams of deionized water and 135.9 grams of the pre-formed sulfonate product produced in Example 6.
  • the product contained about 29.3 percent solids and analyzed about
  • Example 7 The procedure of Example 7 was repeated except that 149.8 grams of the top layer of the sulfonate product of Example 7 was used as the pre-formed sulfonate in the sulfonation reaction.
  • the sulfonate product was treated with 1.33 grams of hydrogen peroxide (49.5 percent) to remove residual sulfite anion, and then combined with the remainder of the sulfonate product from Example 7. The combined product had
  • Example 10 The sulfonation procedure of Example 9 was repeated except that 57.1 grams of the pre-formed sulfonate product of Example 9 was added to the autoclave with the reactants. The product was a clear light yellow liquid which was treated with 1.76 grams of hydrogen peroxide to remove residual sulfite anion. The sulfonate product contained about 31.9 percent solids and analyzed 18.7 percent anionic surfactant activity.
  • the sulfonate product was combined with the remainder of the product from Example 9.
  • the resulting mixture contained about 32.6 percent solids and analyzed about 16.1 percent anionic surfactant activity.
  • the surface tension of a 0.1 weight percent aqueous solution of the product was found to be 35.1 dynes/centimeter at 25°C.
  • a vinyl acetate homopolymer was prepared utilizing the sulfonate product of Example 10 as the sole surfactant.
  • a one liter resin kettle was charged with a solution of 20.0 grams of the sulfonate product of Example 10 in 238 grams of deionized water. The solution was heated to 80°C. under a nitrogen atmosphere and 0.5 grams of potassium persulfate (K 2 S 2 O 8 ) added to the solution. 50 grams of vinyl acetate was added slowly to the resin kettle. The reaction temperature was maintained at 75-80°C. for 30 minutes after completing the initial charge of vinyl acetate. Subsequently, 150 grams of vinyl acetate was added to the kettle over 3-4 hours while maintaining the polymerization temperature at about 80°C.
  • K 2 S 2 O 8 potassium persulfate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

Des composés poly(alkylèneoxy)alpha-béta éthyléniquement insaturés sont tensio-actifs et se polymérisent lorsqu'ils sont utilisés pour polymériser par émulsion des monomères éthyléniquement insaturés, y compris des monomères de vinyle.
EP19890908294 1988-06-20 1989-06-16 Polymerizable surfactant Withdrawn EP0422120A4 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US20924988A 1988-06-20 1988-06-20
US209249 1988-06-20

Publications (2)

Publication Number Publication Date
EP0422120A1 true EP0422120A1 (fr) 1991-04-17
EP0422120A4 EP0422120A4 (en) 1991-08-21

Family

ID=22777997

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19890908294 Withdrawn EP0422120A4 (en) 1988-06-20 1989-06-16 Polymerizable surfactant

Country Status (5)

Country Link
EP (1) EP0422120A4 (fr)
JP (1) JP2672385B2 (fr)
KR (1) KR920003118B1 (fr)
AU (1) AU621916B2 (fr)
WO (1) WO1989012618A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9017520B2 (en) 2010-03-23 2015-04-28 Basf Se Paper coating or binding formulations and methods of making and using same
US9102848B2 (en) 2011-02-28 2015-08-11 Basf Se Environmentally friendly, polymer dispersion-based coating formulations and methods of preparing and using same

Families Citing this family (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0403718A3 (fr) * 1989-06-20 1991-12-27 Ciba-Geigy Ag Produits dérivés de l'oxyde de styrène
ZA909267B (en) * 1990-03-09 1991-09-25 Ici Australia Operations Fatty alcohol alkoxylate
DE4135399A1 (de) * 1991-10-26 1993-04-29 Goldschmidt Ag Th Copolymerisate auf der basis von vinylethern und propenylpolyethern und deren verwendung als entlueftungsmittel fuer waessrige anstrichsysteme
US6048611A (en) * 1992-02-03 2000-04-11 3M Innovative Properties Company High solids moisture resistant latex pressure-sensitive adhesive
US5514122A (en) * 1994-05-16 1996-05-07 Minnesota Mining And Manufacturing Company Feminine hygiene pad
US5599601A (en) * 1994-07-20 1997-02-04 Minnesota Mining And Manufacturing Company Diaper fastening tape
WO1998051713A1 (fr) * 1997-05-16 1998-11-19 The Dow Chemical Company Emulsions a phase interne elevee et matieres poreuses preparees a partir de ces emulsions
US6242526B1 (en) 1997-01-28 2001-06-05 Stepan Company Antimicrobial polymer latexes derived from unsaturated quaternary ammonium compounds and antimicrobial coatings, sealants, adhesives and elastomers produced from such latexes
DE69821337T2 (de) 1997-01-28 2004-12-02 Stepan Co., Northfield Emulsionspolymerisationsverfahren unter verwendung von ethylenisch ungesättigten aminsalzen von sulfonsäure,phosphorsäure und carbonsäure
US7423167B2 (en) 1997-01-28 2008-09-09 Stepan Company Ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids
US20020161108A1 (en) 2000-03-09 2002-10-31 Stepan Company, A Corporation Of The State Of Delaware Emulsion polymerization process utilizing ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids
US5900451A (en) * 1997-05-15 1999-05-04 Reichhold Chemicals, Inc. Collaidally stabilized butadiene emulsions
MY130724A (en) * 1998-10-09 2007-07-31 Union Carbide Chem Plastic Latex polymer compositions
JP4027548B2 (ja) * 1999-10-22 2007-12-26 株式会社Ａｄｅｋａ 界面活性剤
DE60117571T2 (de) 2000-09-11 2007-01-18 Kao Corp. Oberflächenaktiver stoff für die emulsionspolymerisation
JP4498569B2 (ja) * 2000-09-13 2010-07-07 花王株式会社 反応性界面活性剤組成物
JP3621346B2 (ja) * 2000-12-26 2005-02-16 中央理化工業株式会社 水性下地塗料
DE10163258A1 (de) * 2001-12-21 2003-07-10 Clariant Gmbh Olefinisch ungesättigte Ethercarbonsäuren und ihre Verwendung in der Emulsionspolymerisation
EP1605026B1 (fr) * 2004-06-10 2010-04-07 Kao Corporation Dispersants polymères
US7531595B2 (en) 2006-03-08 2009-05-12 3M Innovative Properties Company Pressure-sensitive adhesive containing silica nanoparticles
US7645827B2 (en) 2006-03-08 2010-01-12 3M Innovative Properties Company High shear pressure-sensitive adhesive
US7989581B2 (en) 2006-05-19 2011-08-02 Dow Corning Toray Company, Ltd. Polyether from ring-opening of glycidyl ether with (C2-C5 alkylene oxide) monohydric alcohol
US7393901B1 (en) 2007-02-16 2008-07-01 3M Innovative Properties Company Acrylate adhesives containing silica nanoparticles crosslinked with polyfunctional aziridines
TWI437009B (zh) 2007-04-24 2014-05-11 Solvay Solexis Spa １，１－二氟乙烯共聚物類
US7652095B2 (en) 2007-06-20 2010-01-26 3M Innovative Properties Company Pressure-sensitive adhesive containing aziridinyl silanes
JP4556146B2 (ja) 2008-04-11 2010-10-06 ソニー株式会社 情報処理装置および方法、プログラム、並びに情報処理システム
CN104995020B (zh) 2012-02-03 2017-12-08 3M创新有限公司 用于保护性膜中的压敏粘合剂共混物
US20170283669A1 (en) 2014-09-04 2017-10-05 3M Innovative Properties Company Pressure-sensitive adhesive containing nanocrystalline cellulose
CA2970632A1 (fr) 2014-12-24 2016-06-30 Valspar Sourcing, Inc. Compositions de revetement exemptes de styrene pour des articles d'emballage tels que les recipients pour aliments et pour boissons
US11981822B2 (en) 2014-12-24 2024-05-14 Swimc Llc Crosslinked coating compositions for packaging articles such as food and beverage containers
CN107109100B (zh) 2014-12-24 2020-08-25 宣伟投资管理有限公司 用于包装制品例如食品和饮料容器的涂料组合物
WO2017213888A1 (fr) 2016-06-06 2017-12-14 3M Innovative Properties Company Procédés de production de polymères dans des réacteurs à écoulement
CN111278942A (zh) 2017-10-26 2020-06-12 3M创新有限公司 包含有机硅基粘合剂和纤维素纳米晶体的组合物以及方法和制品
CN107793447B (zh) * 2017-11-01 2020-01-03 贵州师范学院 一种p2o5分散法制备磷酸酯功能单体的方法、用途
CN114195927B (zh) * 2020-09-18 2023-08-22 中国石油天然气集团有限公司 稠化剂、形成其的组合物、乳状液聚合物、压裂液体系及其应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2996538A (en) * 1957-11-25 1961-08-15 Dow Chemical Co Preparation of monomeric polyglycol acrylate and methacrylate esters
EP0084227A1 (fr) * 1981-12-10 1983-07-27 The Valspar Corporation Compositions acryloyl et alkylacryloyl polyalkoxycarbamates et leur utilisation dans des enduits radiodurcissables
EP0102707A1 (fr) * 1982-07-29 1984-03-14 Imperial Chemical Industries Plc Procédé de préparation de dispersions aqueuses stabilisées stériquement non chargées de polymères
EP0107300A1 (fr) * 1982-10-01 1984-05-02 Imperial Chemical Industries Plc Procédé de polymérisation initié par un système Rédox pour la production de dispersions aqueuses, stabilisées stériquement, non chargées de polymères
EP0216479B1 (fr) * 1985-08-12 1991-02-13 Ciba Specialty Chemicals Water Treatments Limited Agents épaississants polymères et leur préparation

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE523059A (fr) * 1950-10-27 1953-10-15
NL272723A (fr) * 1951-05-31
CA715522A (en) * 1962-06-29 1965-08-10 Wyandotte Chemicals Corporation Polyether hydroxysulfonate surface active agents
JPS5778936A (en) * 1980-11-04 1982-05-17 Kao Corp Surfactant for polymer emulsion
US4436672A (en) * 1982-08-16 1984-03-13 Texaco, Inc. Oil recovery method utilizing glyceryl ether sulfonates
ZA836922B (en) * 1982-10-01 1984-06-27 Ici Plc Polymerisation process
DE3331513A1 (de) * 1983-09-01 1985-03-21 Henkel KGaA, 4000 Düsseldorf Ethersulfonate
DE3407563C1 (de) * 1984-03-01 1985-04-25 Th. Goldschmidt Ag, 4300 Essen Sulfonierte Polyoxyalkylenether von 1.2- oder 1.3-Diolen,deren Herstellung und Verwendung
DE3433593A1 (de) * 1984-09-13 1986-03-20 Henkel KGaA, 4000 Düsseldorf Verwendung von ethersulfonaten als schaumarme netzmittel in waessrigen, sauren und alkalischen technischen behandlungsmitteln
JPS61223011A (ja) * 1985-03-28 1986-10-03 Sanyo Chem Ind Ltd 重合体の製造方法
JPS62221432A (ja) * 1986-03-24 1987-09-29 Dai Ichi Kogyo Seiyaku Co Ltd 乳化重合用乳化剤
JPS6383109A (ja) * 1986-09-26 1988-04-13 Sanyo Chem Ind Ltd 重合体用改質剤および改質方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2996538A (en) * 1957-11-25 1961-08-15 Dow Chemical Co Preparation of monomeric polyglycol acrylate and methacrylate esters
EP0084227A1 (fr) * 1981-12-10 1983-07-27 The Valspar Corporation Compositions acryloyl et alkylacryloyl polyalkoxycarbamates et leur utilisation dans des enduits radiodurcissables
EP0102707A1 (fr) * 1982-07-29 1984-03-14 Imperial Chemical Industries Plc Procédé de préparation de dispersions aqueuses stabilisées stériquement non chargées de polymères
EP0107300A1 (fr) * 1982-10-01 1984-05-02 Imperial Chemical Industries Plc Procédé de polymérisation initié par un système Rédox pour la production de dispersions aqueuses, stabilisées stériquement, non chargées de polymères
EP0216479B1 (fr) * 1985-08-12 1991-02-13 Ciba Specialty Chemicals Water Treatments Limited Agents épaississants polymères et leur préparation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO8912618A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9017520B2 (en) 2010-03-23 2015-04-28 Basf Se Paper coating or binding formulations and methods of making and using same
US9102848B2 (en) 2011-02-28 2015-08-11 Basf Se Environmentally friendly, polymer dispersion-based coating formulations and methods of preparing and using same

Also Published As

Publication number Publication date
JP2672385B2 (ja) 1997-11-05
EP0422120A4 (en) 1991-08-21
WO1989012618A1 (fr) 1989-12-28
KR920003118B1 (ko) 1992-04-20
KR900701714A (ko) 1990-12-04
AU621916B2 (en) 1992-03-26
AU3877989A (en) 1990-01-12
JPH03503168A (ja) 1991-07-18

Similar Documents

Publication Publication Date Title
EP0422120A1 (fr) Agent tensio-actif polymerisable
US5296627A (en) Ethylenically unsaturated poly(alkyleneoxy) surfactants
US5162475A (en) Polymerizable surfactant
US7026418B2 (en) Emulsion polymerization process utilizing ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids
US7812114B2 (en) Block copolymer by reacting alkylene oxide and glycidyl ether in presence of unsaturated monomer
US3673142A (en) Preparation of stable latexes from ethylenically unsaturated polymerizable surfactant and solution of preformed water insoluble polymer of an ethylenically unsaturated compound
US7098250B2 (en) Surfactant for emulsion polymerization
US4587290A (en) Polymerization process using nonionic surfactant and copolymerizable unsaturated polyethylene glycol
US7462660B2 (en) Copolymers containing styrene oxide and use thereof as emulsifiers and dispersing agents
WO2000020463A1 (fr) Utilisation de derives d'acide polyaspartique en tant qu'emulsifiants et stabilisateurs dans la polymerisation radicalaire en emulsion aqueuse
US4760152A (en) Pyrrolidonyl acrylate block polymers
JP2003261605A (ja) 反応性界面活性剤
JP4271849B2 (ja) 重合方法
KR100409038B1 (ko) 계면활성제,유화중합용유화제,현탁중합용분산제및수지개질제
US4806609A (en) Pyrrolidonyl acrylate block polymers
JP2002080506A (ja) 乳化重合用界面活性剤組成物
EP0102707B1 (fr) Procédé de préparation de dispersions aqueuses stabilisées stériquement non chargées de polymères
US20030124261A1 (en) Olefinically unsaturated ether carboxylic acids and their use in emulsion polymerization
JP3868834B2 (ja) 乳化重合用反応性界面活性剤組成物
US3640922A (en) Stable aqueous dispersions
US20110245414A1 (en) Copolymerizable (Meth)Acrylic Acid Esters
KR930011528B1 (ko) 가교결합성 비이온 계면활성제를 사용하여 제조한 수성 유화 중합체
US3879447A (en) Monomeric emulsion stabilizers comprising a lipophilic diallyl or dimethallyl quaternary ammonium compound
US4689366A (en) Surface active tertiary alkylamine emulsifiers for polymerization
JP3995763B2 (ja) 界面活性剤

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19901220

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE CH DE FR GB IT LI NL SE

RIN1 Information on inventor provided before grant (corrected)

Inventor name: TANG, ROBERT, H.

Inventor name: CHAKRABARTI, PARITOSH, M.

RIN1 Information on inventor provided before grant (corrected)

Inventor name: CHAKRABARTI, PARITOSH, M.

Inventor name: TANG, ROBERT, H.

A4 Supplementary search report drawn up and despatched

Effective date: 19910628

AK Designated contracting states

Kind code of ref document: A4

Designated state(s): BE CH DE FR GB IT LI NL SE

17Q First examination report despatched

Effective date: 19930406

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Withdrawal date: 19940303