CA2192381A1 - Preparation of polymers by emulsion polymerization - Google Patents
Preparation of polymers by emulsion polymerizationInfo
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- CA2192381A1 CA2192381A1 CA002192381A CA2192381A CA2192381A1 CA 2192381 A1 CA2192381 A1 CA 2192381A1 CA 002192381 A CA002192381 A CA 002192381A CA 2192381 A CA2192381 A CA 2192381A CA 2192381 A1 CA2192381 A1 CA 2192381A1
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- Prior art keywords
- monomers
- acrylate
- acid
- water
- cyclodextrin
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- 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
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Polymers of hydrophobic monomers (a) are prepared by emulsion polymerization in the presence of at least one compound which is able to form a supramolecular structure.
Description
- BASF Aktiengesell~chaft 950832 O.Z. 0050/46461 - _ , 2192381 Preparation of polymers by emulsion polymerization The present invention relates to a process for preparing polymers 5 by emulsion polymerization of hydrophobic monomers and, if desired, water-soluble monomers.
The free-radical polymerization of monomers in aqueous solutions is of particular industrial interest. However, a prerequisite for 10 a solution polymerization of the monomers is that the monomers are also dissolved in the solvent used in each case. Thus, for example, it is not possible to polymerize nonpolar monomers by solution polymerization in water. Polymers of water-soluble monomers such as acrylic acid or maleic acid are prepared 15 industrially by the method of solution polymerization in water.
The copolymerization of, for example, acrylic acid with water-insoluble monomers is not possible in an aqueous medium.
Water-soluble monomers are likewise polymerized by the method of 20 o/w emulsion polymerization. However, this method fails when relatively large amounts of water-insoluble comonomers are to be incorporated into the copolymer, because the monomers have to migrate from the monomer droplet via the aqueous phase into the polymerizing latex particles.
In the bulk polymerization of water-soluble and water-insoluble monomers too, it is necessary for the different monomers to be compatible with one another if uniform polymers are to be obtained. However, this is not ensured in the case of comonomers 30 having very different polarity. In the case of other polymerization techniques such as precipitation polymerization, the incompatibility of water-insoluble monomers with the aqueous media is also frequently a decisive disadvantage.
35 It is known from the prior art that cyclodextrins can serve as organic host molecules and are able to accommodate one or two guest molecules to form supramolecular structures, cf. W.
Saenger, Angew. Chem. Int. Ed. Engl. 1980, 19, 344, G. Wenz, Angew. Chem. Int. Ed. Engl. 1994, 33, 803-822 and F. Vogtle:
40 Supramolekulare Chemie, B.G. Teubner, Stuttgart, 1989. Thus, for example, crystalline complexes of ethylene and cyclodextrin are known.
J. Macromol.Sci.-Chem., A13, 87-109 (1979) discloses inclusion 45 compounds of polymers which are prepared by free-radical polymerization of monomers in a ~-cyclodextrin matrix in ` BASF Aktiengesell~chaft 950832 O.Z.0050/46461 ~ 950982 21 9~38 1 _ 2 dimethylformamide solution. Monomers mentioned are vinylidene chloride, methyl acrylate, styrene and methacr~rlonitrile.
DE-A-4 009 621 discloses quick-setting adhesive compositions 5 based on a-cyano acrylates which contain cyclodextrin derivatives which are at least partially soluble in a-cyano acrylates.
EP-A-460 896 describes the action of cyclodextrins on the viscosity of hydrophobic thickeners in aqueous systems.
It is an object of the present invention to provide a process for preparing polymers of hydrophobic monomers whose solubility in water is not sufficient for the monomer to be able to diffuse through the aqueous phase and, if desired, water-soluble monomers 15 by polymerization of the monomers in an aqueous solvent.
We have found that this object is achieved by a process for preparing polymers by emulsion polymerization of hydrophobic monomers (a) and, if desired, water-soluble monomers, wherein the 20 polymerization is carried out in the presence of at least one compound (b) which is able to form a supramolecular structure.
Suitable compounds (b) are able to enter into an association with the monomer (a) so that the water-diffusability of the monomer 25 (a) is improved. Compounds ~b) include guest-host complexes such as clathrates, cryptands, podands, spherands and speleands (see F. Vogtle, Supramolekulare Chemie, B.G. Teubner, Stuttgart 1989) and, in particular, compounds having a cyclodextrin structure.
30 Apart from the a-, ~ - and ~-cyclodextrins described in the abovementioned literature references, compounds having cyclodextrin structures also include chemically modified cyclodextrins. The cyclodextrins themselves are obtained, for example, by enzymatic degradation of starch and consist of, for 35 example, from 6 to 9 D-glucose units which are linked to one another via an a-1,4-glycoside bond. a-Cyclodextrin consists of 6 glucose molecules, ~-cyclodextrin consists of 7 glucose molecules.
For the purposes of the present invention, chemically modified cyclodextrins are reaction products of cyclodextrins with 40 reactive compounds, eg. reaction products of cyclodextrins with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide or styrene oxide, reaction products of cyclodextrins with alkylating agents, eg. C1-C22-alkyl halides such as methyl chloride, ethyl chloride, butyl chloride, ethyl bromide, butyl 45 bromide, benzyl chloride, lauryl chloride, stearyl chloride or behenyl chloride and dimethyl sulfate. Further modification of cyclodextrins is also possible by reaction with chloroacetic sASF Aktiengesellschaft 950832 O.Z.0050/46461 ~, 3 21~2381 acid. Derivatives of cyclodextrins containing cyclodextrin structures are also obtainable by enzymatic linkage with maltose oligomers. Reaction products of the abovementioned type are alkylated (methylated), hydroxyalkylated and sulfonatoalkylated 5 cyclodextrins such as dimethyl-~-cyclodextrin, hydroxypropyl-~-cyclodextrin and sulfonatopropylhydroxypropyl-~-cyclodextrin. Among the compounds of the group (a), preference is given to using a-cyclodextrin, ~-cyclodextrin, y-cyclodextrin and/or methylated cyclodextrins, 10 eg. 2,6-dimethyl-~-cyclodextrin or its isomers and homologues.
The compounds (b) can be employed as complexes with the hydrophobic monomer (a), ie. the molar ratio of (a):(b) is in the ran~e from 1:1 to 1:5, in particular from 1:1 to 1:3. However, 15 preference is given to using the compounds (b) in substoichiometric amounts, ie. the molar ratio of (a):(b) is in the range from 5000:1 to 2:1, preferably from 1000:1 to 2:1, in particular from 500:1 to 10:1 and from 100:1 to 10:1 and particularly preferably from 80:1 to 20:1.
Examples of compounds (a) are C2-C40 (in particular C2-C30)-alkyl esters of acrylic acid or Cl-C40 (in particular Cl-C30)-alkyl esters of methacrylic acid, for example methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, i-propyl 25 methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, pentyl acrylate, pentyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, n-heptyl acrylate, n-heptyl methacrylate, n-octyl acrylate, n-octyl 30 methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, decyl acrylate, decyl methacrylate, lauryl acrylate, lauryl methacrylate, palmityl acrylate, palmityl methacrylate, stearyl acrylate, stearyl methacrylate, hydrenol (meth)acrylate, behenyl (meth)acrylate, polyisobutene (meth)acrylate, phenoxyethyl 35 acrylate, phenoxyethyl methacrylate, phenyl acrylate and phenyl methacrylate.
Further monomers of the group (a) are a-olefins having from 2 to 30 carbon atoms and also polyisobutylenes having from 3 to 50, 40 preferably from 15 to 35, isobutene units. Examples of a-olefins are ethylene, propylene, n-butene, isobutene, l-pentene, cyclopentene, l-hexene, cyclohexene, l-octene, diisobutylene (2,4,4-trimethyl-1-pentene, possibly in admixture with 2,4,4-trimethyl-2-pentene), l-decene, l-dodecene, l-octadecene, 45 Cl2/Cl4-olefins, C20/C2~-olefins, vinylaromatic compounds, such as styrene, a-methylstyrene, vinylpyridines such as 4-vinylpyridine, polypropylenes having a terminal vinyl or vinylidene group and ~ BASF Aktiengesellschaft 950B32 O.Z.0050/46461 95~982 21 92381 _ 4 having from 3 to 100 propylene units, polyisobutene having from to 35 isobutene units and having a terminal vinyl or vinylidene group, oligohexene or oligooctadecene.
5 Other suitable monomers (a~ are butadiene and isoprene. When these monomers are used, the polymerization is carried out under pressure.
A further class of monomers of group (a) comprises 10 N-alkyl-substituted acrylamides and methacrylamides, for example N-tert-butylacrylamide, N-hexylmethacrylamide, N-octylacrylamide, N-nonylmethacrylamide, N-dodecylmethacrylamide, N-hexadecylmethacrylamide, N-methacrylamidocaproic acid, N-methacrylamidoundecanoic acid, N,N-dibutylacrylamide, 15 N-hydroxyethylacrylamide and N hydroxyethylmethacrylamide.
Other monomers of the group (a) are vinyl alkyl ethers having from 1 to 40 carbon atoms in the alkyl radical, for example methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, 20 isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether, 2-(diethylamino)ethyl vinyl ether, 2-(di-n-butylamino)ethyl vinyl ether, methyl diglycol vinyl ether and also the corresponding allyl ethers such as allyl methyl 25 ether, allyl ethyl ether, allyl n-propyl ether, allyl isobutyl ether and allyl 2-ethylhexyl ether. Additional compounds suitable as monomers of group (a) are the water-insoluble acids, or esters having a solubility of at most 20 g/l in water, of maleic acid and fumaric acid which are derived from monohydric alcohols 30 having from 1 to 22 carbon atoms, for example mono-n-butyl maleate, dibutyl maleate, monodecyl maleate, didodecyl maleate, monooctadecyl maleate and dioctadecyl maleate. Also suitable are vinyl esters of saturated C3-C40-carboxylic acids such as vinyl propionate, vinyl butyrate, vinyl valerate, vinyl 3S 2-ethylhexanoate, vinyl decanoate, vinyl palmitate, vinyl stearate and vinyl laurate. Other monomers of group (a) are methacrylonitrile, vinyl chloride, vinylidene chloride, isoprene and butadiene.
40 The abovementioned monomers of group (a) can be used alone or as a mixture of two or more for preparing the complexes or in the polymerization. Preferred monomers (a) are C2-C30-alkyl esters of acrylic acid, C1-C30-alkyl esters of methacrylic acid, C2-C30-~-olefins, C1-C20-alkyl vinyl ethers, vinyl esters of 45 C2-C20-carboxylic acids, vinylaromatic compounds, in particular styrene, butadiene, isoprene or their mixtures, in particular mixtures of at least one of said esters of acrylic and/or ~ BASF Aktienge~ellschaft 950832 O-Z.0050/46461 methacrylic acid and at least one vinylaromatic compound, preferably styrene. Particularly preferred monomers (a) are methyl methacrylate, ethyl acrylate, butyl acrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, lauryl 5 acrylate, stearyl acrylate, hydrenol acrylate, behenyl acrylate, polyisobutene (meth)acrylate, vinyl a~etate, vinyl stearate, isobutene, 1-hexene, diisobutene, 1-dodecene, 1-octadecene, polyisobutenes having from 15 to 35 isobutene units, styrene, methyl vinyl ether, ethyl vinyl ether, stearyl vinyl ether or 10 mixtures thereof.
The hydrophobic monomers (a) can be free-radically polymerized alone or in admixture with one another. In addition, it is possible to copolymerize the monomers (a) with water-soluble 15 monomers. Suitable water-soluble monomers, which are hereinafter referred to as monomers of group (c), have a water solubility of more than 20 g/l. Examples are monoethylenically unsaturated C3-Cs-carboxylic acids, their amides and esters with amino alcohols of the formula Rl HO R - N - R2 X~ (I), where R = C2-Cs-alkylene, Rl, R2, R3 = H, CH3, C2Hs, C3H7 and X~ is an anion. Also suitable are amides of these carboxylic acids which are derived from amines of the formula / Rl H2N R - N - R2 X~ (II~.
The substituents in formula II and X~ are as defined for formula I.
Examples of these compounds (c) are acrylic acid, methacrylic 40 acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, acrylonitrile, acrylamide, methacrylamide, crotonamide, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoneopentyl acrylate and dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate, 45 dimethylaminoneopentyl acrylate and dimethylaminoneopentyl methacrylate.
~ ' BASF Aktiengesellschaft 950832 O.Z.0050/46461 2~92381 _ 6 The carboxylic acids mentioned can be used as free acid or in partially or completely neutralized form, eg. as alkali metal or ammonium salts.
5 The basic esters or basic amides derived from the compounds of the formula II are used in the form of their salts with strong mineral acids, sulfonic acids or carboxylic acids or in quaternized form. The anion X~ in the compounds of the formula I
is the corresponding anion of the mineral acids or the carboxylic 10 acids or is methosulfate, ethosulfate or halide from a quaternizing agent.
Further water-soluble monomers of group (c) are N-vinylpyrrolidone, N-vinylformamide, acrylamidopropanesulfonic 15 acid, vinylphosphonic acid andtor alkali metal or ammonium salts of vinylsulfonic acid. These acids can likewise be used either in unneutralized form or in partially to 100% neutralized form in the polymerization. Other suitable water-soluble monomers of group (c) are diallylammonium compounds such as 20 dimethyldiallylammonium chloride, diethyldiallylammonium chloride or diallylpiperidinium bromide, N-vinylimidazolium compounds such as salts or quaternization products of N-vinylimidazole and 1-vinyl-2-methylimidazole, and N-vinylimidazolines such as N-vinylimidazoline, 1-vinyl-2-methylimidazoline, 25 1-vinyl-2-ethylimidazoline or 1-vinyl-2-n-propylimidazoline, which are likewise used in quaternized form or as a salt in the polymerization.
Preferred monomers of group (c) are monoethylenically unsaturated 30 C3-Cs-carboxylic acids, vinylsulfonic acid, acrylamidomethylpropanesulfonic acid, vinylphosphonic acid, N-vinylformamide, dimethylaminoethyl (meth)acrylates, alkali metal, ammonium or quaternary ammonium salts of the specified monomers containing an acid or amino group or mixtures of the 35 monomers with one another. Of particular economic importance is the use of acrylic acid or mixtures of acrylic acid and maleic acid or their alkali metal salts in the preparation of hydrophobically modified water-soluble copolymers, with particular preference being given to using n-butyl acrylate, 40 n-stearyl acrylate and/or styrene as monomers (a).
To prepare crosslinked polymers which are used, for example, as thickeners for aqueous systems, hydrophobic monomers of group (a) and, if desired, at least one monomer of group (c) are 45 polymerized in the presence of compounds containing cyclodextrin structures and at least one class of crosslinking monomers.
Customary crosslinkers are used for this purpose, examples being . BASF Aktiengesellschaft 950832 O.Z.0050/46461 divinylbenzene, diallyl phthalate, allyl vinyl ether and/or diallyl fumarate, etc. The preparation of the crosslinked polymers can, if desired, additionally be carried out in the presence of crosslinkers which are soluble in water. Examples of 5 such monomers are acrylamidoglycolic acid, N-methylolacrylamide, N-methylolmethacrylamide, 1,4-bisaminooxybutane, adipic dihydrazide, eg. in the presence of a ketone, N,N'-methylenebisacrylamide, polyethylene glycol diacrylates and polyethylene glycol dimethacrylates which are each derived from 10 polyethylene glycols having a molecular weight of from 126 to 8500, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, hexanediol dimethacrylate, diacrylates and dimethacrylates of 15 block copolymers of ethylene oxide and propylene oxide, polyhydric alcohols such as glycerol or pentaerythritol diesterified or triesterified with acrylic acid or methacrylic acid, triallylamine, tetraallylethylenediamine, trimethylolpropane diallyl ether, pentaerythritol triallyl ether 20 and/or N,N'-divinylethyleneurea. The crosslinkers are preferably used in amounts of from 0.01 to 40% by weight, in particular from 0.5 to 5% by weight, based on the total amount of monomers used in the copolymerization. However, the crosslinkers can also be polymerized alone to give homopolymers.
The polymerization of the water-insoluble monomers and, if desired, the water-soluble monomers is carried out by emulsion polymerization in an aqueous medium, preferably in water. The term aqueous medium here also includes mixtures of water and 30 organic liquids miscible therewith. Examples of water-miscible organic liquids are polyols, in particular glycols such as ethylene glycol, propylene glycol, 1,3-butylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and glycerol, block copolymers of ethylene oxide and propylene oxide, 35 alkoxylated C1-C20-alcohols, acetic esters of glycols and polyglycols, alcohols such as methanol, ethanol, isopropanol and butanol, acetone, tetrahydrofuran, dimethylformamide, N-methylpyrrolidone or mixtures of these. If the polymerization is carried out in mixtures of water and water-miscible solvents, 40 the proportion of water-miscible solvents in the mixture is up to 75% by weight.
The emulsion polymerization of the monomers is usually carried out with exclusion of oxygen at, for example, from 20 to 200 C, 45 preferably from 35 to 140 C. The polymerization can be carried out batchwise or continuously. Preferably, at least one part of the monomers, initiators and, if used, regulators is metered BASF Aktiengesellschaft 950832 O.Z.0050/46461 ~ 8 2192381 uniformly during the polymerization into the reaction vessel containing the aqueous solvent in which t:he compounds containing cyclodextrin structures are dissolved. However, in the case of relatively small hatches, the monomers and the polymerization 5 initiator can also be placed in the reactor at the beginning and then polymerized. In this case it may be necessary to cool the reactor to provide sufficiently rapid removal of the heat of polymerization.
10 The polymerization is preferably carried out by a free-radical mechanism. In this case, suitable polymerization initiators are the compounds which are customarily used in free-radical polymerizations and which produce free radicals under the polymerization conditions, eg. peroxides, hydroperoxides, 15 peroxodisulfates, percarbonates, peroxyesters, hydrogen peroxide and azo compounds. Examples of initiators are hydrogen peroxide, dibenzoyl peroxide, dicyclohexyl peroxydicarbonate, dilauryl peroxide, methyl ethyl ketone peroxide, acetylacetone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl 20 perneodecanoate, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perneohexanoate, tert-butyl per-2-ethylhexanoate, tert-butyl perbenzoate, lithium, sodium, potassium and ammonium peroxodisulfate, azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, 25 2-(carbamoylazo)isobutyronitrile and 4,4'-azobis(4-cyanovaleric acid). The initiators are usually used in amounts of up to 15~ by weight, preferably from 0.02 to 10% by weight, based on the monomers to be polymerized.
30 The initiators can be used alone or in admixture with one another. It is also possible to use the known redox catalysts in which the reducing component is used in a molar deficiency. Known redox catalysts are, for example, salts of transition metals such as iron(II) sulfate, cobalt(II) chloride, nickel(II) sulfate, 35 copper(I) chloride, manganese(II) acetate, ~anadium(III) acetate.
Other suitable redox catalysts are ascorbic acid, reducing sulfur compounds such as sulfites, bisulfites, thiosulfates, dithionites and tetrathionates of alkali metals and ammonium compounds or reducing phosphorus compounds in which phosphorus has an 40 oxidation state of 1 to 4, for example sodium hypophosphite, phosphorous acid and phosphites.
To control the molecular weight of the polymers, the polymerization can, if desired, be carried out in the presence of 45 regulators. Suitable regulators are, for example, aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde, formic acid, ammonium formate, , BASF Aktiengesellschaft 950832 0.Z0050/46461 hydroxylammonium sulfate and hydroxylammonium phosphate. It is also possible to use regulators which contain sulfur in organically bound form, for example organic compounds containing SH groups, eg. thiomalic acid, thioglycoloacetic acid, 5 mercaptoacetic acid, mercaptopropionic acid, mercaptoethanol, mercaptopropanol, mercaptobutanols, mercaptohexanol, dodecyl mercaptan and tert-dodecyl mercaptan. Other regulators which can be used are hydrazine salts such as hydrazinium sulfate. The amounts of regulator, based on the monomers to be polymerized, 10 are from 0 to 20~ by weight, preferably from 0.5 to 15% by weight.
The polymerization can be carried out in the presence of an emulsifier and/or protective colloid customary for these 15 purposes. Suitable protective colloids are, for example, polyvinyl alcohols, cellulose derivatives or polyvinylpyrrolidones. The emulsifiers can be anionic, cationic or nonionic in nature. Suitable emulsifiers are, for example, ethoxylated monoalkylphenols, dialkylphenols and trialkylphenols 20 (EO content: 3-50, alkyl radical: C4-Cg), ethoxylated fatty alcohols (EO content: 3-50, alkyl radical: C8-C36), and also alkali metal and ammonium salts of alkyl sulfates (alkyl radical:
C8-Cl2), of sulfuric monoesters of ethoxylated alkanols (EO
content: 4-30, alkyl radical Cl2-Cl8) and ethoxylated alkylphenols 25 (EO content: 3-50, alkyl radical: C4-Cg), of alkylsulfonic acids (alkyl radical: Cl2-Clg), of ligninsulfonic acid and of alkylarylsulfonic acids (alkyl radical: Cg-Cl8). Particuarly suitable emulslfiers have been found to be compounds of the general formula I
Rl R2 ~ O ~ (I) where Rl and R2 are hydrogen or C4-C24-alkyl and are not simultaneously hydrogen, and X and Y can be alkali metal ions 40 and/or ammonium ions. In the formula I, Rl and R2 are preferably linear or branched alkyl radicals having from 6 to 18 carbon atoms, with Rl and R2 not both simultaneously being hydrogen. X
and Y are preferably sodium, potassium or ammonium ions.
BASF AXtiengesellschaft 950832 O.Z.0050/46461 _ 950982 21 ~ 238 It has been found that the polymerization can also be carried out without emulsifier or protective colloid, particularly when using amphiphilic cyclodextrins such as dimethylcyclodextrins.
5 The polymers may be in the form of inclusion compounds or can be obtained therefrom. The formation of inclusion compounds from the polymers and the compounds of the component (a) is reversible.
After the polymerization, the polymers are usually present in the latex particles separate from the compounds (a). If the polymers 10 are present in the form of inclusion compounds after the preparation, they can be set free from the inclusion compounds and isolated by, for example, addition of wetting agents such as ethoxylated long-chain alcohols to the reaction mixture.
15 If desired, the dispersion obtained can be diluted with a water-miscible organic liquid. The amount of organic liquid in - the dispersion can be up to 75~ by weight, based on the total weight of the liquid phase. Suitable organic liquids have already been mentioned above, with the specified polyols being preferred, 20 particularly if the dispersion is used for oil treatment.
The polymers hydrophobically modified by the process of the present invention can, for example, be used as thickeners, eg. in cosmetic creams or lotions, as components in surface coating 25 formulations, as sizes in paper manufacture, as coating composition, as raw material for adhesives, as additive for laundry detergents or as dispersant for pigments. Furthermore, such polymers can be used as tanning agent, retanning agent, fat liquoring agent or hydrophobicizing agent for leather production.
30 Hydrophobically modified polymers also serve as polymeric emulsifiers which stabilize a fine dispersion of a nonpolar material in a polar phase. Crosslinked polyacrylic acids, which are obtainable, for example, by copolymerization of acrylic acid and hydrophobic monomers in the presence of a cyclodextrin and a 35 water-insoluble crosslinker such as divinylbenzene, are used as superabsorbers or thickeners for aqueous systems. In addition, the dispersion of the present invention can be used for oil treatment, particularly for lowering the pour point, for example of crude oil, heating oil or diesel oil.
The following examples illustrate the invention without limiting it.
General procedure for the atmospheric pressure copolymerization 45 of the monomers specified in the tables below:
sAsF Aktiengesellschaft 950832 O.Z.0050/46461 2192~81 The cyclodextrin derivative was placed in a flask together with 360 g of water. The flask was flushed with nitrogen and heated to 80 C. To this mixture was added 0.6 g of sodium persulfate in the form of a 2% strength aqueous solution. 600 g of the desired 5 monomer mixture were prepared and admixed with 3 g of emulsifier (sodium dodecylbenzenesulfonate) in the form of a 15% strength aqueous solution. 3 g of this mixture were added to the flask.
Polymerization was carried out for 15 minutes at 80 C. The remaining amount of monomer and 2.4 g of sodium persulfate were 10 subsequently metered in over a period of 4 hours and 1.9 g of Rongalit~ ~hydroxymethanesulfinic acid) and 2.4 g of t-butyl hydroperoxide were then added to the reaction mixture. Stirring was continued for a further 90 minutes, the reaction mixture was then cooled to room temperature and filtered through a 125 ~m 15 filter to remove any coagulum formed. The solids content of the dispersion obtained was 43.4%. The monomer composition is given in the tables below.
A film was produced from the polymer dispersion by casting onto 20 aluminum foil and drying at 110 C, and this film was examined by means of DSC. The glass transition temperatures and melting points measured are given in the following tables, in which the following abbreviations are used:
25 n-BA n-butyl acrylate SA stearyl acrylate S styrene A acrylic acid CD1 ~-cyclodextrin 30 CD2 ~-cyclodextrin containing 1.8 methyl units per glucose ring Tg glass transition temperature Mp. melting point Coag. coagulum 35 C comparative experiment The amount of the individual monomers is based on the total amount of monomers. The amount of cyclodextrins is likewise based on the total amount of monomers.
BASF Aktiengesellschaft 950832 Z.0050/46461 - _ 12 21 g 23 8 Exam~les 1 to 3 and Com~arative Exam~les 1 to 3 (V1 to V3):
Table 1 ExampleMonomers CyclodextrinsPolymer film (% by weight) (% by weight) n-BA S A SA CD1 Tg Mp. Coag.
~ C] [ C] (%) C1 49.5 49.5 1.0 0 - 22 0.2 C2 44.5 44.5 1.0 10.0 - 22 48 0.5 C3 39.5 39.5 1.0 20.0 - 22 48 >15 1 44.5 44.5 1.0 10.0 5.0 14 2 39.5 39.5 1.0 20.0 5.0 6 3 34.5 34.5 1.0 30.0 5.0 -9 - -It can be seen from the Comparative Examples that even when using stearyl acrylate the glass transition temperature does not decrease and a melting peak can be observed at 48 C in the DSC
20 (Differential Scanning Calorimetry). In addition, the proportion of coagulum rises with an increasing proportion of stearyl acrylate in the monomer mixture. It can be concluded therefrom that no stearyl acrylate has been incorporated into the copolymer. Rather, part of the polystearyl acrylate formed is 25 precipitated as coagulum. This proportion of coagulum increases after a number of days.
In contrast, it can be seen in Examples 1 to 3 that the glass transition temperature of the polymer drops with an increasing 30 proportion of stearyl acrylate. Neither a melting peak nor the formation of coagulum was able to be observed. This means that the total amount of stearyl acrylate used has been incorporated into the copolymer.
35 Examples 4 to 6 and Com~arative ExamDles 4 and 5 Table 2 ExampleMonomers Cyclodextrins Polymer film (% by weight) (% by weight~
n-BA S A SA CD1 Tg Mp. Coag.
[C] [C] (%) C4 99.0 01.0 0 - -44 C5 89.0 01.0 10.0 - -44 44 2%
~5 4 89.0 o1.0 10.0 5.0 -45 45 79.0 01.0 20.0 5.0 -46 45 6 69.0 01.0 30.0 5.0 -46 45 BASF Aktiengesellschaft 950832 O.Z.0050/46461 _ 13 21923~1 Comparative Examples 4 and 5 show that a melting peak at 44 C
occurs when using stearyl acrylate as comonomer. This means that there has been additional formation of almost pure polystearyl acrylate which is not present in stable dispersed form but partly 5 precipitates immediately (2%) and precipitates almost quantitatively after storage for a number of hours.
In turn, Examples 4 to 6 show that although no copolymer of n-butyl acrylate and stearyl acrylate has been formed, the total 10 amount of stearyl acrylate and n-butyl acrylate has homopolymerized and the two polymers are quantitatively present in finely divided dispersed form. This is an industrially particularly attractive method of preparing dispersions comprising mixtures of two homopolymers having complementary 15 properties, without the respective dispersions having to be synthesized separately and subsequently mixed.
Exam~les 7 to 11 and Com~arative Exam~le 6 20 Table 3 ExampleMonomers Cyclodextrins Polymer film (~ by weight) (~ by weight) n-BA S A SA CD2 Tg Mp. Coag.
[C] [C] (%) C6 99.0 0 1.0 0 - 107 7 99.0 0 1.0 0 5.0 107 8 89.0 0 1.010.0 5.0 78 9 79.0 0 1.020.0 5.0 57 69.0 0 1.030.0 6.0 36 11 59.0 0 1.040.0 8.0 19 Examples 7 to 11 show that incorporation of increasing amounts of 35 stearyl acrylate causes a continuous fall in the glass transition temperature, ie. the entire stearyl acrylate is incorporated into the polymer.
Exam~le 12 40 Copolymer containing behenyl acrylate 30.0 g of dimethyl-~-cyclodextrin having 1.8 methyl units per glucose ring were placed in a flask together with 400 g of water.
The flask was flushed with nitrogen and heated to 80 C. To this 45 mixture was added 0.6 g of sodium persulfate in the form of a 2%
strength aqueous solution. Separately, a mixture of 474.0 g of styrene, 120.0 g of behenyl acrylate and 6.0 g of acrylic acid BASF Aktiengesellschaft 950832 O.Z.0050~46461 _ 14 2192381 was emulsified in 160 g of water using 20.0 g of emulsifier solution (15% strength aqueous sodium dodecylbenzenesulfonate).
3.g g of the emulsion was added to the initial charge and partial polymerization was allowed to proceed for 15 minutes at 18 C. The 5 remainder of the emulsion was then allowed to run in over a period of 225 minutes and, in parallel thereto, 2.4 g of sodium persulfate in the form of a 2% strength aqueous solution were allowed to run in over a period of 240 minutes. Further polymerization was allowed to proceed for 10 minutes at 80 C and 10 1.9 g of hydroxymethanesulfinic acid and 2.4 g of t-butyl hydroperoxide were then added. Stirring was continued for a further 90 minutes, the reaction mixture was then cooled to room temperature and filtered through a 125 ~m filter. The solids content of the dispersion obtained was 45.7%, coagulum formation 15 could not be observed. The glass transition temperature (determined as described above) was 54 C.
Exam~le 13 Copolymer containing a-dodecene A copolymer of 534.0 g of styrene, 60.0 g of a-dodecene and 6.0 g of acrylic acid was prepared using the method described in Example 12. The amount of coagulum was < 1 g and the glass transition temperature of the copolymer obtained was 63 C.
Exam~le 14 and Com~arative ExamDle 7 General procedure or the pressure copolymerization using butadiene:
30 An initial charge of 4000 g of water and 150 g of cyclodextrin was heated to 90 C. 3 g of sodium persulfate and, if appropriate, some seed material were added.
3000 g of the monomer mixture indicated in Table 4 below were 35 emulsified in 4000 g of water using 30 g of Dowfax~ (sulfonated alkyl(diphenyl oxide), supplied by Dow Chemical Company) and 30 g of sodium lauryl sulfate. 30 g of p-dodecyl mercaptan were added as regulator. This mixture together with 2700 g of a 10% strength sodium persulfate solution was allowed to run into the initial 40 charge over a period of 4.5 hours in such a way that the pressure did not exceed 6 bar. After a further polymerization time of 3 hours, the mixture was further treated chemically for 4 hours using 4 g of t-butyl hydroperoxide and 3 g of hydroxymethanesulfinic acid. The solids content of the dispersion 45 obtained was 17.7%.
BASF Aktiengesellschaft 950832 O-Z-0050/46461 _ 15 The production and characterization of the films was carried out as described above. The results obtained are shown in Table 4 below.
Example Monomers Cyclodextrin Polymer film (% by weight) (% by weight) - Bu S A SA CDl Tg Mp.
C7 30.0 68.5 1.5 0.0 0.0 33.1 14 24.0 54.8 1.2 20.0 5.0 11.2 The DSC analysis shows a significant reduction in the glass transition temperature in Example 14 compared with Comparative 20 Example 7. A melting peak cannot be observed. This means that stearyl acrylate has been copolymerized.
The free-radical polymerization of monomers in aqueous solutions is of particular industrial interest. However, a prerequisite for 10 a solution polymerization of the monomers is that the monomers are also dissolved in the solvent used in each case. Thus, for example, it is not possible to polymerize nonpolar monomers by solution polymerization in water. Polymers of water-soluble monomers such as acrylic acid or maleic acid are prepared 15 industrially by the method of solution polymerization in water.
The copolymerization of, for example, acrylic acid with water-insoluble monomers is not possible in an aqueous medium.
Water-soluble monomers are likewise polymerized by the method of 20 o/w emulsion polymerization. However, this method fails when relatively large amounts of water-insoluble comonomers are to be incorporated into the copolymer, because the monomers have to migrate from the monomer droplet via the aqueous phase into the polymerizing latex particles.
In the bulk polymerization of water-soluble and water-insoluble monomers too, it is necessary for the different monomers to be compatible with one another if uniform polymers are to be obtained. However, this is not ensured in the case of comonomers 30 having very different polarity. In the case of other polymerization techniques such as precipitation polymerization, the incompatibility of water-insoluble monomers with the aqueous media is also frequently a decisive disadvantage.
35 It is known from the prior art that cyclodextrins can serve as organic host molecules and are able to accommodate one or two guest molecules to form supramolecular structures, cf. W.
Saenger, Angew. Chem. Int. Ed. Engl. 1980, 19, 344, G. Wenz, Angew. Chem. Int. Ed. Engl. 1994, 33, 803-822 and F. Vogtle:
40 Supramolekulare Chemie, B.G. Teubner, Stuttgart, 1989. Thus, for example, crystalline complexes of ethylene and cyclodextrin are known.
J. Macromol.Sci.-Chem., A13, 87-109 (1979) discloses inclusion 45 compounds of polymers which are prepared by free-radical polymerization of monomers in a ~-cyclodextrin matrix in ` BASF Aktiengesell~chaft 950832 O.Z.0050/46461 ~ 950982 21 9~38 1 _ 2 dimethylformamide solution. Monomers mentioned are vinylidene chloride, methyl acrylate, styrene and methacr~rlonitrile.
DE-A-4 009 621 discloses quick-setting adhesive compositions 5 based on a-cyano acrylates which contain cyclodextrin derivatives which are at least partially soluble in a-cyano acrylates.
EP-A-460 896 describes the action of cyclodextrins on the viscosity of hydrophobic thickeners in aqueous systems.
It is an object of the present invention to provide a process for preparing polymers of hydrophobic monomers whose solubility in water is not sufficient for the monomer to be able to diffuse through the aqueous phase and, if desired, water-soluble monomers 15 by polymerization of the monomers in an aqueous solvent.
We have found that this object is achieved by a process for preparing polymers by emulsion polymerization of hydrophobic monomers (a) and, if desired, water-soluble monomers, wherein the 20 polymerization is carried out in the presence of at least one compound (b) which is able to form a supramolecular structure.
Suitable compounds (b) are able to enter into an association with the monomer (a) so that the water-diffusability of the monomer 25 (a) is improved. Compounds ~b) include guest-host complexes such as clathrates, cryptands, podands, spherands and speleands (see F. Vogtle, Supramolekulare Chemie, B.G. Teubner, Stuttgart 1989) and, in particular, compounds having a cyclodextrin structure.
30 Apart from the a-, ~ - and ~-cyclodextrins described in the abovementioned literature references, compounds having cyclodextrin structures also include chemically modified cyclodextrins. The cyclodextrins themselves are obtained, for example, by enzymatic degradation of starch and consist of, for 35 example, from 6 to 9 D-glucose units which are linked to one another via an a-1,4-glycoside bond. a-Cyclodextrin consists of 6 glucose molecules, ~-cyclodextrin consists of 7 glucose molecules.
For the purposes of the present invention, chemically modified cyclodextrins are reaction products of cyclodextrins with 40 reactive compounds, eg. reaction products of cyclodextrins with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide or styrene oxide, reaction products of cyclodextrins with alkylating agents, eg. C1-C22-alkyl halides such as methyl chloride, ethyl chloride, butyl chloride, ethyl bromide, butyl 45 bromide, benzyl chloride, lauryl chloride, stearyl chloride or behenyl chloride and dimethyl sulfate. Further modification of cyclodextrins is also possible by reaction with chloroacetic sASF Aktiengesellschaft 950832 O.Z.0050/46461 ~, 3 21~2381 acid. Derivatives of cyclodextrins containing cyclodextrin structures are also obtainable by enzymatic linkage with maltose oligomers. Reaction products of the abovementioned type are alkylated (methylated), hydroxyalkylated and sulfonatoalkylated 5 cyclodextrins such as dimethyl-~-cyclodextrin, hydroxypropyl-~-cyclodextrin and sulfonatopropylhydroxypropyl-~-cyclodextrin. Among the compounds of the group (a), preference is given to using a-cyclodextrin, ~-cyclodextrin, y-cyclodextrin and/or methylated cyclodextrins, 10 eg. 2,6-dimethyl-~-cyclodextrin or its isomers and homologues.
The compounds (b) can be employed as complexes with the hydrophobic monomer (a), ie. the molar ratio of (a):(b) is in the ran~e from 1:1 to 1:5, in particular from 1:1 to 1:3. However, 15 preference is given to using the compounds (b) in substoichiometric amounts, ie. the molar ratio of (a):(b) is in the range from 5000:1 to 2:1, preferably from 1000:1 to 2:1, in particular from 500:1 to 10:1 and from 100:1 to 10:1 and particularly preferably from 80:1 to 20:1.
Examples of compounds (a) are C2-C40 (in particular C2-C30)-alkyl esters of acrylic acid or Cl-C40 (in particular Cl-C30)-alkyl esters of methacrylic acid, for example methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, i-propyl 25 methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, pentyl acrylate, pentyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, n-heptyl acrylate, n-heptyl methacrylate, n-octyl acrylate, n-octyl 30 methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, decyl acrylate, decyl methacrylate, lauryl acrylate, lauryl methacrylate, palmityl acrylate, palmityl methacrylate, stearyl acrylate, stearyl methacrylate, hydrenol (meth)acrylate, behenyl (meth)acrylate, polyisobutene (meth)acrylate, phenoxyethyl 35 acrylate, phenoxyethyl methacrylate, phenyl acrylate and phenyl methacrylate.
Further monomers of the group (a) are a-olefins having from 2 to 30 carbon atoms and also polyisobutylenes having from 3 to 50, 40 preferably from 15 to 35, isobutene units. Examples of a-olefins are ethylene, propylene, n-butene, isobutene, l-pentene, cyclopentene, l-hexene, cyclohexene, l-octene, diisobutylene (2,4,4-trimethyl-1-pentene, possibly in admixture with 2,4,4-trimethyl-2-pentene), l-decene, l-dodecene, l-octadecene, 45 Cl2/Cl4-olefins, C20/C2~-olefins, vinylaromatic compounds, such as styrene, a-methylstyrene, vinylpyridines such as 4-vinylpyridine, polypropylenes having a terminal vinyl or vinylidene group and ~ BASF Aktiengesellschaft 950B32 O.Z.0050/46461 95~982 21 92381 _ 4 having from 3 to 100 propylene units, polyisobutene having from to 35 isobutene units and having a terminal vinyl or vinylidene group, oligohexene or oligooctadecene.
5 Other suitable monomers (a~ are butadiene and isoprene. When these monomers are used, the polymerization is carried out under pressure.
A further class of monomers of group (a) comprises 10 N-alkyl-substituted acrylamides and methacrylamides, for example N-tert-butylacrylamide, N-hexylmethacrylamide, N-octylacrylamide, N-nonylmethacrylamide, N-dodecylmethacrylamide, N-hexadecylmethacrylamide, N-methacrylamidocaproic acid, N-methacrylamidoundecanoic acid, N,N-dibutylacrylamide, 15 N-hydroxyethylacrylamide and N hydroxyethylmethacrylamide.
Other monomers of the group (a) are vinyl alkyl ethers having from 1 to 40 carbon atoms in the alkyl radical, for example methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, 20 isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether, 2-(diethylamino)ethyl vinyl ether, 2-(di-n-butylamino)ethyl vinyl ether, methyl diglycol vinyl ether and also the corresponding allyl ethers such as allyl methyl 25 ether, allyl ethyl ether, allyl n-propyl ether, allyl isobutyl ether and allyl 2-ethylhexyl ether. Additional compounds suitable as monomers of group (a) are the water-insoluble acids, or esters having a solubility of at most 20 g/l in water, of maleic acid and fumaric acid which are derived from monohydric alcohols 30 having from 1 to 22 carbon atoms, for example mono-n-butyl maleate, dibutyl maleate, monodecyl maleate, didodecyl maleate, monooctadecyl maleate and dioctadecyl maleate. Also suitable are vinyl esters of saturated C3-C40-carboxylic acids such as vinyl propionate, vinyl butyrate, vinyl valerate, vinyl 3S 2-ethylhexanoate, vinyl decanoate, vinyl palmitate, vinyl stearate and vinyl laurate. Other monomers of group (a) are methacrylonitrile, vinyl chloride, vinylidene chloride, isoprene and butadiene.
40 The abovementioned monomers of group (a) can be used alone or as a mixture of two or more for preparing the complexes or in the polymerization. Preferred monomers (a) are C2-C30-alkyl esters of acrylic acid, C1-C30-alkyl esters of methacrylic acid, C2-C30-~-olefins, C1-C20-alkyl vinyl ethers, vinyl esters of 45 C2-C20-carboxylic acids, vinylaromatic compounds, in particular styrene, butadiene, isoprene or their mixtures, in particular mixtures of at least one of said esters of acrylic and/or ~ BASF Aktienge~ellschaft 950832 O-Z.0050/46461 methacrylic acid and at least one vinylaromatic compound, preferably styrene. Particularly preferred monomers (a) are methyl methacrylate, ethyl acrylate, butyl acrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, lauryl 5 acrylate, stearyl acrylate, hydrenol acrylate, behenyl acrylate, polyisobutene (meth)acrylate, vinyl a~etate, vinyl stearate, isobutene, 1-hexene, diisobutene, 1-dodecene, 1-octadecene, polyisobutenes having from 15 to 35 isobutene units, styrene, methyl vinyl ether, ethyl vinyl ether, stearyl vinyl ether or 10 mixtures thereof.
The hydrophobic monomers (a) can be free-radically polymerized alone or in admixture with one another. In addition, it is possible to copolymerize the monomers (a) with water-soluble 15 monomers. Suitable water-soluble monomers, which are hereinafter referred to as monomers of group (c), have a water solubility of more than 20 g/l. Examples are monoethylenically unsaturated C3-Cs-carboxylic acids, their amides and esters with amino alcohols of the formula Rl HO R - N - R2 X~ (I), where R = C2-Cs-alkylene, Rl, R2, R3 = H, CH3, C2Hs, C3H7 and X~ is an anion. Also suitable are amides of these carboxylic acids which are derived from amines of the formula / Rl H2N R - N - R2 X~ (II~.
The substituents in formula II and X~ are as defined for formula I.
Examples of these compounds (c) are acrylic acid, methacrylic 40 acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, acrylonitrile, acrylamide, methacrylamide, crotonamide, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoneopentyl acrylate and dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate, 45 dimethylaminoneopentyl acrylate and dimethylaminoneopentyl methacrylate.
~ ' BASF Aktiengesellschaft 950832 O.Z.0050/46461 2~92381 _ 6 The carboxylic acids mentioned can be used as free acid or in partially or completely neutralized form, eg. as alkali metal or ammonium salts.
5 The basic esters or basic amides derived from the compounds of the formula II are used in the form of their salts with strong mineral acids, sulfonic acids or carboxylic acids or in quaternized form. The anion X~ in the compounds of the formula I
is the corresponding anion of the mineral acids or the carboxylic 10 acids or is methosulfate, ethosulfate or halide from a quaternizing agent.
Further water-soluble monomers of group (c) are N-vinylpyrrolidone, N-vinylformamide, acrylamidopropanesulfonic 15 acid, vinylphosphonic acid andtor alkali metal or ammonium salts of vinylsulfonic acid. These acids can likewise be used either in unneutralized form or in partially to 100% neutralized form in the polymerization. Other suitable water-soluble monomers of group (c) are diallylammonium compounds such as 20 dimethyldiallylammonium chloride, diethyldiallylammonium chloride or diallylpiperidinium bromide, N-vinylimidazolium compounds such as salts or quaternization products of N-vinylimidazole and 1-vinyl-2-methylimidazole, and N-vinylimidazolines such as N-vinylimidazoline, 1-vinyl-2-methylimidazoline, 25 1-vinyl-2-ethylimidazoline or 1-vinyl-2-n-propylimidazoline, which are likewise used in quaternized form or as a salt in the polymerization.
Preferred monomers of group (c) are monoethylenically unsaturated 30 C3-Cs-carboxylic acids, vinylsulfonic acid, acrylamidomethylpropanesulfonic acid, vinylphosphonic acid, N-vinylformamide, dimethylaminoethyl (meth)acrylates, alkali metal, ammonium or quaternary ammonium salts of the specified monomers containing an acid or amino group or mixtures of the 35 monomers with one another. Of particular economic importance is the use of acrylic acid or mixtures of acrylic acid and maleic acid or their alkali metal salts in the preparation of hydrophobically modified water-soluble copolymers, with particular preference being given to using n-butyl acrylate, 40 n-stearyl acrylate and/or styrene as monomers (a).
To prepare crosslinked polymers which are used, for example, as thickeners for aqueous systems, hydrophobic monomers of group (a) and, if desired, at least one monomer of group (c) are 45 polymerized in the presence of compounds containing cyclodextrin structures and at least one class of crosslinking monomers.
Customary crosslinkers are used for this purpose, examples being . BASF Aktiengesellschaft 950832 O.Z.0050/46461 divinylbenzene, diallyl phthalate, allyl vinyl ether and/or diallyl fumarate, etc. The preparation of the crosslinked polymers can, if desired, additionally be carried out in the presence of crosslinkers which are soluble in water. Examples of 5 such monomers are acrylamidoglycolic acid, N-methylolacrylamide, N-methylolmethacrylamide, 1,4-bisaminooxybutane, adipic dihydrazide, eg. in the presence of a ketone, N,N'-methylenebisacrylamide, polyethylene glycol diacrylates and polyethylene glycol dimethacrylates which are each derived from 10 polyethylene glycols having a molecular weight of from 126 to 8500, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, hexanediol dimethacrylate, diacrylates and dimethacrylates of 15 block copolymers of ethylene oxide and propylene oxide, polyhydric alcohols such as glycerol or pentaerythritol diesterified or triesterified with acrylic acid or methacrylic acid, triallylamine, tetraallylethylenediamine, trimethylolpropane diallyl ether, pentaerythritol triallyl ether 20 and/or N,N'-divinylethyleneurea. The crosslinkers are preferably used in amounts of from 0.01 to 40% by weight, in particular from 0.5 to 5% by weight, based on the total amount of monomers used in the copolymerization. However, the crosslinkers can also be polymerized alone to give homopolymers.
The polymerization of the water-insoluble monomers and, if desired, the water-soluble monomers is carried out by emulsion polymerization in an aqueous medium, preferably in water. The term aqueous medium here also includes mixtures of water and 30 organic liquids miscible therewith. Examples of water-miscible organic liquids are polyols, in particular glycols such as ethylene glycol, propylene glycol, 1,3-butylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and glycerol, block copolymers of ethylene oxide and propylene oxide, 35 alkoxylated C1-C20-alcohols, acetic esters of glycols and polyglycols, alcohols such as methanol, ethanol, isopropanol and butanol, acetone, tetrahydrofuran, dimethylformamide, N-methylpyrrolidone or mixtures of these. If the polymerization is carried out in mixtures of water and water-miscible solvents, 40 the proportion of water-miscible solvents in the mixture is up to 75% by weight.
The emulsion polymerization of the monomers is usually carried out with exclusion of oxygen at, for example, from 20 to 200 C, 45 preferably from 35 to 140 C. The polymerization can be carried out batchwise or continuously. Preferably, at least one part of the monomers, initiators and, if used, regulators is metered BASF Aktiengesellschaft 950832 O.Z.0050/46461 ~ 8 2192381 uniformly during the polymerization into the reaction vessel containing the aqueous solvent in which t:he compounds containing cyclodextrin structures are dissolved. However, in the case of relatively small hatches, the monomers and the polymerization 5 initiator can also be placed in the reactor at the beginning and then polymerized. In this case it may be necessary to cool the reactor to provide sufficiently rapid removal of the heat of polymerization.
10 The polymerization is preferably carried out by a free-radical mechanism. In this case, suitable polymerization initiators are the compounds which are customarily used in free-radical polymerizations and which produce free radicals under the polymerization conditions, eg. peroxides, hydroperoxides, 15 peroxodisulfates, percarbonates, peroxyesters, hydrogen peroxide and azo compounds. Examples of initiators are hydrogen peroxide, dibenzoyl peroxide, dicyclohexyl peroxydicarbonate, dilauryl peroxide, methyl ethyl ketone peroxide, acetylacetone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl 20 perneodecanoate, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perneohexanoate, tert-butyl per-2-ethylhexanoate, tert-butyl perbenzoate, lithium, sodium, potassium and ammonium peroxodisulfate, azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, 25 2-(carbamoylazo)isobutyronitrile and 4,4'-azobis(4-cyanovaleric acid). The initiators are usually used in amounts of up to 15~ by weight, preferably from 0.02 to 10% by weight, based on the monomers to be polymerized.
30 The initiators can be used alone or in admixture with one another. It is also possible to use the known redox catalysts in which the reducing component is used in a molar deficiency. Known redox catalysts are, for example, salts of transition metals such as iron(II) sulfate, cobalt(II) chloride, nickel(II) sulfate, 35 copper(I) chloride, manganese(II) acetate, ~anadium(III) acetate.
Other suitable redox catalysts are ascorbic acid, reducing sulfur compounds such as sulfites, bisulfites, thiosulfates, dithionites and tetrathionates of alkali metals and ammonium compounds or reducing phosphorus compounds in which phosphorus has an 40 oxidation state of 1 to 4, for example sodium hypophosphite, phosphorous acid and phosphites.
To control the molecular weight of the polymers, the polymerization can, if desired, be carried out in the presence of 45 regulators. Suitable regulators are, for example, aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde, formic acid, ammonium formate, , BASF Aktiengesellschaft 950832 0.Z0050/46461 hydroxylammonium sulfate and hydroxylammonium phosphate. It is also possible to use regulators which contain sulfur in organically bound form, for example organic compounds containing SH groups, eg. thiomalic acid, thioglycoloacetic acid, 5 mercaptoacetic acid, mercaptopropionic acid, mercaptoethanol, mercaptopropanol, mercaptobutanols, mercaptohexanol, dodecyl mercaptan and tert-dodecyl mercaptan. Other regulators which can be used are hydrazine salts such as hydrazinium sulfate. The amounts of regulator, based on the monomers to be polymerized, 10 are from 0 to 20~ by weight, preferably from 0.5 to 15% by weight.
The polymerization can be carried out in the presence of an emulsifier and/or protective colloid customary for these 15 purposes. Suitable protective colloids are, for example, polyvinyl alcohols, cellulose derivatives or polyvinylpyrrolidones. The emulsifiers can be anionic, cationic or nonionic in nature. Suitable emulsifiers are, for example, ethoxylated monoalkylphenols, dialkylphenols and trialkylphenols 20 (EO content: 3-50, alkyl radical: C4-Cg), ethoxylated fatty alcohols (EO content: 3-50, alkyl radical: C8-C36), and also alkali metal and ammonium salts of alkyl sulfates (alkyl radical:
C8-Cl2), of sulfuric monoesters of ethoxylated alkanols (EO
content: 4-30, alkyl radical Cl2-Cl8) and ethoxylated alkylphenols 25 (EO content: 3-50, alkyl radical: C4-Cg), of alkylsulfonic acids (alkyl radical: Cl2-Clg), of ligninsulfonic acid and of alkylarylsulfonic acids (alkyl radical: Cg-Cl8). Particuarly suitable emulslfiers have been found to be compounds of the general formula I
Rl R2 ~ O ~ (I) where Rl and R2 are hydrogen or C4-C24-alkyl and are not simultaneously hydrogen, and X and Y can be alkali metal ions 40 and/or ammonium ions. In the formula I, Rl and R2 are preferably linear or branched alkyl radicals having from 6 to 18 carbon atoms, with Rl and R2 not both simultaneously being hydrogen. X
and Y are preferably sodium, potassium or ammonium ions.
BASF AXtiengesellschaft 950832 O.Z.0050/46461 _ 950982 21 ~ 238 It has been found that the polymerization can also be carried out without emulsifier or protective colloid, particularly when using amphiphilic cyclodextrins such as dimethylcyclodextrins.
5 The polymers may be in the form of inclusion compounds or can be obtained therefrom. The formation of inclusion compounds from the polymers and the compounds of the component (a) is reversible.
After the polymerization, the polymers are usually present in the latex particles separate from the compounds (a). If the polymers 10 are present in the form of inclusion compounds after the preparation, they can be set free from the inclusion compounds and isolated by, for example, addition of wetting agents such as ethoxylated long-chain alcohols to the reaction mixture.
15 If desired, the dispersion obtained can be diluted with a water-miscible organic liquid. The amount of organic liquid in - the dispersion can be up to 75~ by weight, based on the total weight of the liquid phase. Suitable organic liquids have already been mentioned above, with the specified polyols being preferred, 20 particularly if the dispersion is used for oil treatment.
The polymers hydrophobically modified by the process of the present invention can, for example, be used as thickeners, eg. in cosmetic creams or lotions, as components in surface coating 25 formulations, as sizes in paper manufacture, as coating composition, as raw material for adhesives, as additive for laundry detergents or as dispersant for pigments. Furthermore, such polymers can be used as tanning agent, retanning agent, fat liquoring agent or hydrophobicizing agent for leather production.
30 Hydrophobically modified polymers also serve as polymeric emulsifiers which stabilize a fine dispersion of a nonpolar material in a polar phase. Crosslinked polyacrylic acids, which are obtainable, for example, by copolymerization of acrylic acid and hydrophobic monomers in the presence of a cyclodextrin and a 35 water-insoluble crosslinker such as divinylbenzene, are used as superabsorbers or thickeners for aqueous systems. In addition, the dispersion of the present invention can be used for oil treatment, particularly for lowering the pour point, for example of crude oil, heating oil or diesel oil.
The following examples illustrate the invention without limiting it.
General procedure for the atmospheric pressure copolymerization 45 of the monomers specified in the tables below:
sAsF Aktiengesellschaft 950832 O.Z.0050/46461 2192~81 The cyclodextrin derivative was placed in a flask together with 360 g of water. The flask was flushed with nitrogen and heated to 80 C. To this mixture was added 0.6 g of sodium persulfate in the form of a 2% strength aqueous solution. 600 g of the desired 5 monomer mixture were prepared and admixed with 3 g of emulsifier (sodium dodecylbenzenesulfonate) in the form of a 15% strength aqueous solution. 3 g of this mixture were added to the flask.
Polymerization was carried out for 15 minutes at 80 C. The remaining amount of monomer and 2.4 g of sodium persulfate were 10 subsequently metered in over a period of 4 hours and 1.9 g of Rongalit~ ~hydroxymethanesulfinic acid) and 2.4 g of t-butyl hydroperoxide were then added to the reaction mixture. Stirring was continued for a further 90 minutes, the reaction mixture was then cooled to room temperature and filtered through a 125 ~m 15 filter to remove any coagulum formed. The solids content of the dispersion obtained was 43.4%. The monomer composition is given in the tables below.
A film was produced from the polymer dispersion by casting onto 20 aluminum foil and drying at 110 C, and this film was examined by means of DSC. The glass transition temperatures and melting points measured are given in the following tables, in which the following abbreviations are used:
25 n-BA n-butyl acrylate SA stearyl acrylate S styrene A acrylic acid CD1 ~-cyclodextrin 30 CD2 ~-cyclodextrin containing 1.8 methyl units per glucose ring Tg glass transition temperature Mp. melting point Coag. coagulum 35 C comparative experiment The amount of the individual monomers is based on the total amount of monomers. The amount of cyclodextrins is likewise based on the total amount of monomers.
BASF Aktiengesellschaft 950832 Z.0050/46461 - _ 12 21 g 23 8 Exam~les 1 to 3 and Com~arative Exam~les 1 to 3 (V1 to V3):
Table 1 ExampleMonomers CyclodextrinsPolymer film (% by weight) (% by weight) n-BA S A SA CD1 Tg Mp. Coag.
~ C] [ C] (%) C1 49.5 49.5 1.0 0 - 22 0.2 C2 44.5 44.5 1.0 10.0 - 22 48 0.5 C3 39.5 39.5 1.0 20.0 - 22 48 >15 1 44.5 44.5 1.0 10.0 5.0 14 2 39.5 39.5 1.0 20.0 5.0 6 3 34.5 34.5 1.0 30.0 5.0 -9 - -It can be seen from the Comparative Examples that even when using stearyl acrylate the glass transition temperature does not decrease and a melting peak can be observed at 48 C in the DSC
20 (Differential Scanning Calorimetry). In addition, the proportion of coagulum rises with an increasing proportion of stearyl acrylate in the monomer mixture. It can be concluded therefrom that no stearyl acrylate has been incorporated into the copolymer. Rather, part of the polystearyl acrylate formed is 25 precipitated as coagulum. This proportion of coagulum increases after a number of days.
In contrast, it can be seen in Examples 1 to 3 that the glass transition temperature of the polymer drops with an increasing 30 proportion of stearyl acrylate. Neither a melting peak nor the formation of coagulum was able to be observed. This means that the total amount of stearyl acrylate used has been incorporated into the copolymer.
35 Examples 4 to 6 and Com~arative ExamDles 4 and 5 Table 2 ExampleMonomers Cyclodextrins Polymer film (% by weight) (% by weight~
n-BA S A SA CD1 Tg Mp. Coag.
[C] [C] (%) C4 99.0 01.0 0 - -44 C5 89.0 01.0 10.0 - -44 44 2%
~5 4 89.0 o1.0 10.0 5.0 -45 45 79.0 01.0 20.0 5.0 -46 45 6 69.0 01.0 30.0 5.0 -46 45 BASF Aktiengesellschaft 950832 O.Z.0050/46461 _ 13 21923~1 Comparative Examples 4 and 5 show that a melting peak at 44 C
occurs when using stearyl acrylate as comonomer. This means that there has been additional formation of almost pure polystearyl acrylate which is not present in stable dispersed form but partly 5 precipitates immediately (2%) and precipitates almost quantitatively after storage for a number of hours.
In turn, Examples 4 to 6 show that although no copolymer of n-butyl acrylate and stearyl acrylate has been formed, the total 10 amount of stearyl acrylate and n-butyl acrylate has homopolymerized and the two polymers are quantitatively present in finely divided dispersed form. This is an industrially particularly attractive method of preparing dispersions comprising mixtures of two homopolymers having complementary 15 properties, without the respective dispersions having to be synthesized separately and subsequently mixed.
Exam~les 7 to 11 and Com~arative Exam~le 6 20 Table 3 ExampleMonomers Cyclodextrins Polymer film (~ by weight) (~ by weight) n-BA S A SA CD2 Tg Mp. Coag.
[C] [C] (%) C6 99.0 0 1.0 0 - 107 7 99.0 0 1.0 0 5.0 107 8 89.0 0 1.010.0 5.0 78 9 79.0 0 1.020.0 5.0 57 69.0 0 1.030.0 6.0 36 11 59.0 0 1.040.0 8.0 19 Examples 7 to 11 show that incorporation of increasing amounts of 35 stearyl acrylate causes a continuous fall in the glass transition temperature, ie. the entire stearyl acrylate is incorporated into the polymer.
Exam~le 12 40 Copolymer containing behenyl acrylate 30.0 g of dimethyl-~-cyclodextrin having 1.8 methyl units per glucose ring were placed in a flask together with 400 g of water.
The flask was flushed with nitrogen and heated to 80 C. To this 45 mixture was added 0.6 g of sodium persulfate in the form of a 2%
strength aqueous solution. Separately, a mixture of 474.0 g of styrene, 120.0 g of behenyl acrylate and 6.0 g of acrylic acid BASF Aktiengesellschaft 950832 O.Z.0050~46461 _ 14 2192381 was emulsified in 160 g of water using 20.0 g of emulsifier solution (15% strength aqueous sodium dodecylbenzenesulfonate).
3.g g of the emulsion was added to the initial charge and partial polymerization was allowed to proceed for 15 minutes at 18 C. The 5 remainder of the emulsion was then allowed to run in over a period of 225 minutes and, in parallel thereto, 2.4 g of sodium persulfate in the form of a 2% strength aqueous solution were allowed to run in over a period of 240 minutes. Further polymerization was allowed to proceed for 10 minutes at 80 C and 10 1.9 g of hydroxymethanesulfinic acid and 2.4 g of t-butyl hydroperoxide were then added. Stirring was continued for a further 90 minutes, the reaction mixture was then cooled to room temperature and filtered through a 125 ~m filter. The solids content of the dispersion obtained was 45.7%, coagulum formation 15 could not be observed. The glass transition temperature (determined as described above) was 54 C.
Exam~le 13 Copolymer containing a-dodecene A copolymer of 534.0 g of styrene, 60.0 g of a-dodecene and 6.0 g of acrylic acid was prepared using the method described in Example 12. The amount of coagulum was < 1 g and the glass transition temperature of the copolymer obtained was 63 C.
Exam~le 14 and Com~arative ExamDle 7 General procedure or the pressure copolymerization using butadiene:
30 An initial charge of 4000 g of water and 150 g of cyclodextrin was heated to 90 C. 3 g of sodium persulfate and, if appropriate, some seed material were added.
3000 g of the monomer mixture indicated in Table 4 below were 35 emulsified in 4000 g of water using 30 g of Dowfax~ (sulfonated alkyl(diphenyl oxide), supplied by Dow Chemical Company) and 30 g of sodium lauryl sulfate. 30 g of p-dodecyl mercaptan were added as regulator. This mixture together with 2700 g of a 10% strength sodium persulfate solution was allowed to run into the initial 40 charge over a period of 4.5 hours in such a way that the pressure did not exceed 6 bar. After a further polymerization time of 3 hours, the mixture was further treated chemically for 4 hours using 4 g of t-butyl hydroperoxide and 3 g of hydroxymethanesulfinic acid. The solids content of the dispersion 45 obtained was 17.7%.
BASF Aktiengesellschaft 950832 O-Z-0050/46461 _ 15 The production and characterization of the films was carried out as described above. The results obtained are shown in Table 4 below.
Example Monomers Cyclodextrin Polymer film (% by weight) (% by weight) - Bu S A SA CDl Tg Mp.
C7 30.0 68.5 1.5 0.0 0.0 33.1 14 24.0 54.8 1.2 20.0 5.0 11.2 The DSC analysis shows a significant reduction in the glass transition temperature in Example 14 compared with Comparative 20 Example 7. A melting peak cannot be observed. This means that stearyl acrylate has been copolymerized.
Claims (12)
1. A process for preparing polymers by emulsion polymerization of hydrophobic monomers (a) and, if desired, water-soluble monomers, wherein the polymerization is carried out in the presence of at least one compound (b) which is capable of forming a supramolecular structure.
2. A process as claimed in claim 1, wherein a compound having a cyclodextrin structure is used as compound (b).
3. A process as claimed in claim 1 or 2, wherein the molar ratio of (a):(b) is in the range from 5000:1 to 1:5.
4. A process as claimed in claim 2 or 3, wherein the compound having a cyclodextrin structure is .alpha.-, .beta.-, .gamma.- or .delta.-cyclodextrin and/or a chemically modified cyclodextrin, in particular methylated cyclodextrin.
5. A process as claimed in any of the preceding claims, wherein the aqueous medium comprises not only water but also a water-miscible organic liquid.
6. A process as claimed in any of the preceding claims, wherein monomers (a) used are C2-C30-alkyl esters of acrylic acid, C1-C30-alkyl esters of methacrylic acid, C2-C30-.alpha.-olefins, C1-C20-alkyl vinyl ethers, vinyl esters of C2-C20-alkanoic acids, N-C1-C30-alkyl-substituted acrylamides and methacrylamides, styrene, butadiene, isoprene or mixtures thereof.
7. A process as claimed in claim 6 wherein monomers (a) used are at least one C2-C30-alkyl ester of acrylic acid and/or at least one C1-C30-alkyl-ester of methacrylic acid together with styrene.
8. A process as claimed in claim 6 or 7, wherein monomers (a) used are methyl methacrylate, ethyl acrylate, butyl acrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, hydrenol acrylate, behenyl acrylate, polyisobutene (meth)acrylate, vinyl acetate, vinyl stearate, isobutene, 1-hexene, diisobutene, 1-dodecene, 1-octadecene, polyisobutenes having from 3 to 35 isobutene units, styrene, methyl vinyl ether, ethyl vinyl ether, stearyl vinyl ether or mixtures thereof.
9. A process as claimed in any of the preceding claims, wherein the monomers (a) also include crosslinking monomers.
10. A process as claimed in any of the preceding claims, wherein water-soluble monomers used are monoethylenically unsaturated C3-C5-carboxylic acids, acrylonitrile, vinylsulfonic acid, acrylamidomethylpropanesulfonic acid, vinylphosphonic acid, N-vinylformamide, dialkylaminoethyl (meth)acrylates, alkali metal, ammonium or quaternary ammonium salts of said monomers containing an acid or amino group, or mixtures of the monomers with one another.
11. An aqueous polymer dispersion obtainable by a process as claimed in any of the preceding claims.
12. An aqueous polymer dispersion as claimed in claim 11 which includes an organic liquid miscible with water, in particular a polyol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19548038A DE19548038A1 (en) | 1995-12-21 | 1995-12-21 | Process for the preparation of polymers by emulsion polymerization |
| DE19548038.4 | 1995-12-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2192381A1 true CA2192381A1 (en) | 1997-06-22 |
Family
ID=7780952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002192381A Abandoned CA2192381A1 (en) | 1995-12-21 | 1996-12-06 | Preparation of polymers by emulsion polymerization |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0780401A1 (en) |
| JP (1) | JPH09183806A (en) |
| KR (1) | KR970042609A (en) |
| CN (1) | CN1156727A (en) |
| BR (1) | BR9606081A (en) |
| CA (1) | CA2192381A1 (en) |
| DE (1) | DE19548038A1 (en) |
| MX (1) | MX9606466A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8613834B2 (en) | 2008-04-03 | 2013-12-24 | Basf Se | Paper coating or binding formulations and methods of making and using same |
| US9914797B2 (en) | 2013-11-13 | 2018-03-13 | Rohm And Haas Chemicals Llc | Alkali-swellable crosslinked acrylate copolymer, methods of manufacture thereof, and composition comprising the same |
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|---|---|---|---|---|
| MX200986B (en) * | 1997-07-29 | 2001-03-07 | Rohm & Haas | Solubilized hydrophobically-modified alkali-soluble emulsion polymers |
| DE19806745A1 (en) † | 1998-02-18 | 1999-08-19 | Bayer Ag | Aqueous polymer dispersion useful as surface sizing agent for paper, cardboard etc. |
| DE19825486C2 (en) | 1998-06-08 | 2000-07-06 | Stockhausen Chem Fab Gmbh | Water-absorbing polymers with supramolecular cavity molecules, process for their preparation and their use |
| DE19956326A1 (en) * | 1999-11-23 | 2001-05-31 | Bayer Ag | Production of 1,3-diene based polymers, useful for tires, shoe soles and sealants, comprises radical polymerization of cyclodextrin complexed 1,3-dienes and optionally other unsaturated monomers |
| DE19963586A1 (en) * | 1999-12-29 | 2001-07-12 | Dupont Performance Coatings | Process for the preparation of lacquer binders and their use in coating compositions |
| FR2831464B1 (en) * | 2001-10-26 | 2004-07-16 | Collano Sa | USE OF LIGNIN SULFONATE(S) AS POLYMERIZATION STABILIZER(S) IN EMULSION, DISPERSION, CORRESPONDING USES AND METHOD |
| DE10158839A1 (en) * | 2001-11-30 | 2003-06-26 | Henkel Kgaa | Marked polymer dispersion and adhesives available from it |
| DE10212899A1 (en) * | 2002-03-23 | 2003-10-02 | Tesa Ag | Production of polyacrylate adhesive material for use on adhesive tape involves emulsion or dispersion polymerisation of acrylate monomers in presence of a cyclodextrin, preferably methylated beta-cyclodextrin |
| US20060094844A1 (en) * | 2004-10-29 | 2006-05-04 | Council Of Scientific And Industrial Research | Inclusion complexes of unsaturated monomers, their polymers and process for preparation thereof |
| US7598303B2 (en) * | 2005-02-17 | 2009-10-06 | Rohm And Haas Company | Process for making an aqueous dispersion |
| KR101393969B1 (en) * | 2006-06-26 | 2014-05-12 | 바스프 에스이 | Method for producing aqueous polymer dispersion |
| JP5122215B2 (en) * | 2006-08-31 | 2013-01-16 | ローム アンド ハース カンパニー | Aqueous amphiphilic copolymer emulsion having adjusted viscosity and method for producing the same |
| EP1900756A1 (en) * | 2006-09-14 | 2008-03-19 | Basf Se | Process for the preparation of an aqueous polymer dispersion |
| EP2264079B1 (en) | 2008-03-12 | 2015-05-27 | Asahi Glass Company, Limited | Copolymer and method for producing the same |
| WO2009135812A1 (en) * | 2008-05-08 | 2009-11-12 | Basf Se | Method for preparing an aqueous polymer dispersion |
| EP2147717A1 (en) | 2008-07-25 | 2010-01-27 | Basf Se | Auxiliary dispersing agent for emulsion and suspension polymerisation |
| CN101368110B (en) * | 2008-09-28 | 2011-12-28 | 中国海洋石油总公司 | Process for producing pre-dehydrating agent cationic polymer for crude oil |
| EP2177563A1 (en) | 2008-10-15 | 2010-04-21 | Basf Se | Aqueous adhesive for fibrous and/or granular substrates |
| CN102161729B (en) * | 2011-02-25 | 2013-01-16 | 上海交通大学 | Preparation method of water-soluble polysaccharide/hydrophobic monomer formed nanoparticles |
| JP2012236797A (en) * | 2011-05-12 | 2012-12-06 | Adeka Corp | Complex and method for producing the same |
| WO2013075293A1 (en) * | 2011-11-23 | 2013-05-30 | Evonik Industries Ag | Process for emulsion polymerizing hydrophobic monomers |
| CN102675527B (en) * | 2012-05-18 | 2013-12-25 | 华南理工大学 | Preparation method of water-borne long-chain acrylate separant |
| FR3000080B1 (en) | 2012-12-20 | 2015-01-30 | Oreal | WATER INSOLUBLE CYCLODEXTRIN POLYCONDENSATE; USES AS CAPTURE AGENT |
| FR2999916B1 (en) | 2012-12-20 | 2015-01-30 | Oreal | COMPOSITION FOR RELEASING A BENEFICIAL AGENT COMPRISING A WATER-INSOLUBLE CYCLODEXTRIN POLYCONDENSATE AND AT LEAST ONE BENEFICATED AGENT |
| CN103396519B (en) * | 2013-07-18 | 2015-12-02 | 北京化工大学 | A kind of copolymerization immobilized beta-cyclodextrin porous parting material, preparation method and application |
| MX2018006918A (en) * | 2015-12-08 | 2018-11-09 | Kemira Oyj | Liquid polymer compositions. |
| US10035946B2 (en) * | 2016-02-23 | 2018-07-31 | Ecolab Usa Inc. | Hydrazide crosslinked polymer emulsions for use in crude oil recovery |
| JP6114868B1 (en) * | 2016-09-29 | 2017-04-12 | 第一工業製薬株式会社 | Surfactant composition |
| CN112934198B (en) * | 2021-01-29 | 2022-07-08 | 浙江理工大学 | Cyclodextrin porous adsorption material and preparation method and application thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB932389A (en) * | 1959-08-24 | 1963-07-24 | Vinyl Products Ltd | Improvements in or relating to polymer emulsions or dispersions |
| JPH0233722B2 (en) * | 1982-03-30 | 1990-07-30 | Nippon Starch Refining | MONOMAANORAJIKARUJUGOHOHO |
| GB8806692D0 (en) * | 1988-03-21 | 1988-04-20 | Cerestar Holding Bv | Acrylate polymer compositions |
| DE4009621A1 (en) | 1990-03-26 | 1991-10-02 | Henkel Kgaa | (ALPHA) -CYANACRYLATE ADHESIVE COMPOSITIONS |
| US5137571A (en) | 1990-06-05 | 1992-08-11 | Rohm And Haas Company | Method for improving thickeners for aqueous systems |
| US5521266A (en) * | 1994-10-28 | 1996-05-28 | Rohm And Haas Company | Method for forming polymers |
-
1995
- 1995-12-21 DE DE19548038A patent/DE19548038A1/en not_active Withdrawn
-
1996
- 1996-12-06 CA CA002192381A patent/CA2192381A1/en not_active Abandoned
- 1996-12-16 MX MX9606466A patent/MX9606466A/en unknown
- 1996-12-18 JP JP8337774A patent/JPH09183806A/en not_active Withdrawn
- 1996-12-19 BR BR9606081A patent/BR9606081A/en not_active Application Discontinuation
- 1996-12-19 EP EP96120521A patent/EP0780401A1/en not_active Withdrawn
- 1996-12-20 KR KR1019960069189A patent/KR970042609A/en not_active Application Discontinuation
- 1996-12-20 CN CN96117911A patent/CN1156727A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8613834B2 (en) | 2008-04-03 | 2013-12-24 | Basf Se | Paper coating or binding formulations and methods of making and using same |
| US9074322B2 (en) | 2008-04-03 | 2015-07-07 | Basf Se | Paper coating or binding formulations and methods of making and using same |
| US9914797B2 (en) | 2013-11-13 | 2018-03-13 | Rohm And Haas Chemicals Llc | Alkali-swellable crosslinked acrylate copolymer, methods of manufacture thereof, and composition comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR970042609A (en) | 1997-07-24 |
| BR9606081A (en) | 1998-09-01 |
| MX9606466A (en) | 1997-06-28 |
| DE19548038A1 (en) | 1997-06-26 |
| JPH09183806A (en) | 1997-07-15 |
| CN1156727A (en) | 1997-08-13 |
| EP0780401A1 (en) | 1997-06-25 |
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