WO2001000695A1 - Procede de production de dispersions de polymeres a fines particules - Google Patents

Procede de production de dispersions de polymeres a fines particules Download PDF

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WO2001000695A1
WO2001000695A1 PCT/EP2000/005495 EP0005495W WO0100695A1 WO 2001000695 A1 WO2001000695 A1 WO 2001000695A1 EP 0005495 W EP0005495 W EP 0005495W WO 0100695 A1 WO0100695 A1 WO 0100695A1
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aqueous
radical
polymer dispersion
aqueous polymer
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PCT/EP2000/005495
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German (de)
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Sarah Peach
Bradley Ronald Morrison
Robert Gilbert
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Basf Aktiengesellschaft
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Priority to AU59733/00A priority Critical patent/AU5973300A/en
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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
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate

Definitions

  • the present invention relates to a process of free-radically initiated aqueous emulsion polymerization for producing an aqueous polymer dispersion, the polymer particles of which have a weight-average particle diameter ⁇ 300 nm.
  • Aqueous polymer dispersions are generally known. These are fluid systems which contain, as a disperse phase in aqueous dispersion medium, polymer balls consisting of a plurality of intertwined polymer chains (so-called polymer particles) in a disperse distribution.
  • the diameter of the polymer particles is often in the range from 10 nm to 2000 nm.
  • aqueous polymer dispersions have the potential to form polymer films when evaporating the aqueous dispersion medium, which is why they are used in particular as binders, e.g. can be used for paints or for masses for coating leather, paper or plastic films. Because of their environmentally friendly properties, they are becoming increasingly important.
  • aqueous polymer dispersions An essential feature of aqueous polymer dispersions is the diameter of the polymer particles in disperse distribution, since a number of performance properties of aqueous polymer dispersions are also determined by the size of the polymer particles or their size distribution. For example, films made from finely divided aqueous polymer dispersions have an increased gloss (see, for example, Progress in Organic Coatings 6, 1978, page 22). Furthermore, the penetration capacity of finely divided aqueous polymer dispersions into porous, but nevertheless relatively dense substrates such as paper, leather or plaster base is increased in comparison with coarse-particle aqueous polymer dispersions (cf., for example, dispersions of synthetic high polymers, Part II, application, H. Reinhard, Springer-Verlag , Berlin 1969, page 4).
  • coarse-particle aqueous polymer dispersions with otherwise the same composition and solids concentration have a lower flow resistance than fine-particle aqueous polymer dispersions (cf., for example, synthetic dispersions High polymer, part II, application, H. Reinhard, Springer-Verlag, Berlin 1969, page 5).
  • Aqueous polymer dispersions whose polymer particle diameters are distributed over a larger diameter range also have an advantageous flow behavior (see, for example, DE-A 42 13 965).
  • a key role in the production of an aqueous polymer dispersion is therefore the targeted, reproducible adjustment of the diameter of the dispersed polymer particles, which is tailored to the respective intended use.
  • the most important method for producing aqueous polymer dispersions is the radical emulsion polymerization method, in particular the free radical aqueous emulsion polymerization method.
  • At least one vinyl group-containing monomers are typically polymerized radically under the action of free radical polymerization initiators dissolved in the aqueous medium to polymer particles which are directly dispersed in the aqueous dispersion medium.
  • the aqueous polymer dispersions produced by the free-radical aqueous emulsion polymerization method are usually also referred to as aqueous primary dispersions in order to distinguish them from the so-called aqueous secondary dispersions.
  • the polymerization takes place in a non-aqueous medium. Dispersion into the aqueous medium is only carried out after the polymerization has ended.
  • the monomers to be polymerized are distributed in droplets in an aqueous medium with the formation of an aqueous monomer emulsion (the droplet diameter is often 2 to 10 ⁇ m).
  • these monomer droplets do not form the polymerization sites but only act as a monomer reservoir. Rather, the formation of the polymerization sites takes place in the aqueous phase, which always contains a limited proportion of the monomers to be polymerized as well as the free radical polymerization initiator.
  • the chemical reaction of these reaction partners in solution leads to the formation of oligomer radicals which precipitate as primary particles above a critical chain length (homogeneous nucleation).
  • This polymer particle formation phase is followed by the polymer growth phase, that is to say that the monomers to be polymerized diffuse from the monomer droplets functioning as reservoirs via the aqueous phase to the primary particles formed (the number and surface area of which is very much larger than that of the monomer droplets) by in same polymerized to (cf. e.g. fiber research and textile technology 1977 (28), volume 7, journal for polymer research, page 309).
  • the monomers to be polymerized diffuse from the monomer droplets functioning as reservoirs via the aqueous phase to the primary particles formed (the number and surface area of which is very much larger than that of the monomer droplets) by in same polymerized to (cf. e.g. fiber research and textile technology 1977 (28), volume 7, journal for polymer research, page 309).
  • suitable protective colloids Through the controlled addition of suitable protective colloids, both the disperse distribution of the monomer droplets and the disperse distribution of the polymer particles formed can be stabilized.
  • the free radical aqueous emulsion polymerization can also be carried out in a controlled manner in that it is present in the presence of an emulsifier dissolved in the aqueous medium
  • aqueous medium in the emulsifier is such that it is above the critical micelle formation concentration thereof (cf., for example, High Polymers, Vol. IX, Emulsion Polymerization, Interscience Publishers, Inc., New York , Third Printing, 1965, page 1 ff.). It is assumed that surfactant micelles in aqueous medium form the nucleus for the formation of polymer primary particles (this is also called micellar nucleation). If the radical emulsion polymerization is initiated in the presence of a low emulsifier concentration, corresponding to a small number of surfactant micelles, an aqueous polymer dispersion is obtained which essentially contains large polymer particles.
  • an aqueous polymer dispersion which essentially contains many small polymer particles (see, for example, dispersions of synthetic high polymers, Part I, F. Hölscher, Springer Verlag, Berlin 1969, page 81).
  • high emulsifier contents are often disadvantageous, for example when the high emulsifier content in the preparation of the polymer dispersion greatly increases the tendency to foam by reducing the surface tension, the formation of closed and resistant polymer films is more difficult or when these polymer dispersions are used in subsequent reactions, e.g. interferes with their use as polymer seeds.
  • JP-A 09 302 004 also discloses the preparation of aqueous polystyrene dispersions in the presence of various alkyl mercaptans, which were used to control the resulting molecular weights.
  • the resulting polystyrene particles had number average particle diameters from about 500 to 600 nm and low molecular weights.
  • the object of the present invention was to provide a process of free-radically initiated aqueous emulsion polymerization for producing a finely divided aqueous polymer dispersion, the polymer particles of which have a weight-average particle diameter of ⁇ 300 nm, which is also suitable for monomers other than styrene and on the other hand, can be carried out with low emulsifier contents.
  • a method of radically initiated aqueous emulsion polymerization for the preparation of an aqueous polymer dispersion, the polymer particles of which have a weight-average particle diameter of ⁇ 300 nm, is provided, which is characterized in that at least one monomer having at least one ethylenically unsaturated group which comprises less than 90% by weight consists of styrene, dispersed in an aqueous medium and polymerized by means of at least one radical polymerization initiator in the presence of at least one radical-chain-transferring compound whose solubility is greater than 10 -5 mol per kilogram of water at 20 ° C. and 1 bar is (absolute).
  • the process of the invention differs by a zusharm - asking the presence of at least one radical chain transfer compound whose solubility is greater lxlO -5 mol per kilogram water at 20 ° C and 1 bar (absolute) and in that the at least one monomer consists of less than 90% by weight of styrene.
  • Monomers different from styrene and having at least one ethylenically unsaturated group are particularly suitable for the process according to the invention, in particular in a simple manner free-radically polymerizable monomers, such as ethylene, vinyl aromatic monomers such as ⁇ -methylstyrene, o-chlorostyrene or vinyltoluenes, Esters of vinyl alcohol and monocarboxylic acids having 1 to 18 carbon atoms, such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate, esters of ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids preferably having 3 to 6 carbon atoms , such as, in particular, acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, with alkanols which generally have 1 to 12, preferably 1 to 8 and in particular 1 to 4, carbon atoms, such as, in particular, acrylic acid and me
  • the monomers mentioned generally form the main monomers which, based on the total amount of the monomers to be polymerized by the free-radical aqueous emulsion polymerization process according to the invention, normally comprise a proportion of more than 50% by weight. As a rule, these monomers have only moderate to low solubility in water under normal conditions (25 ° C., 1 bar).
  • Monomers which have an increased water solubility under the abovementioned conditions are, for example, ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids and their amides, such as e.g. Acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, acrylamide and methacrylamide, also vinylsulfonic acid and its water-soluble salts and N-vinylpyrrolidone.
  • ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids and their amides such as e.g. Acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, acrylamide and methacrylamide, also vinylsulfonic acid and its water-soluble salts and N-vinylpyrrolidone.
  • the abovementioned monomers are only used as modifying monomers in amounts, based on the total amount of the monomers to be polymerized, of less than 50% by weight, generally 0.5 to 20% by weight, preferably 1 to 10% by weight. -% polymerized.
  • Monomers which usually increase the internal strength of the films of the aqueous polymer dispersions normally have at least one epoxy, hydroxyl, N-methylol or carbonyl group, or at least two non-conjugated ethylenically unsaturated double bonds.
  • these are N-alkylolamides of ⁇ , ⁇ -monoethylenically and 3 to 10 carbon atoms.
  • saturated carboxylic acids among which the N-methylolacrylamide and the N-methylolmethacrylamide are very particularly preferred, and their esters with C 1 -C 4 -alkanols.
  • two monomers having vinyl residues two monomers having vinylidene residues and two monomers having alkenyl residues are also suitable.
  • the di-esters of dihydric alcohols with ⁇ , ⁇ -monoethylenically unsaturated monocarboxylic acids are particularly advantageous, among which acrylic and methacrylic acid are preferred.
  • monomers having two non-conjugated ethylenically unsaturated double bonds are alkylene glycol diacrylates and dimethacrylates, such as ethylene glycol diacrylate, 1, 2-propylene glycol diacrylate, 1, 3-propylene glycol diacrylate, 1, 3-butylene glycol diacrylate diacrylate, and 1, 3-butylene glycol diacrylate diacrylate - koldimethacrylate, 1, 2-propylene glycol dimethacrylate, 1, 3-propylene glycol dimethacrylate, 1, 3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate and divinylbenzene, vinyl methacrylate, vinyl acrylate, allyl methacrylate, diallyl acrylate, methlyl acrylate
  • methacrylic acid and acrylic acid Ci-Cs-hydroxyalkyl esters such as n-hydroxyethyl, n-hydroxypropyl or n-hydroxybutyl acrylate and methacrylate as well as compounds such as diacetone acrylic amide and acetylacetoxyethyl acrylate or . methacrylate.
  • the abovementioned monomers based on the total amount of the monomers to be polymerized, are generally copolymerized in amounts of from 0.5 to 10% by weight.
  • the proportion by weight of styrene in the at least one monomer to be polymerized is ⁇ 90% by weight. However, it can also be ⁇ 80% by weight, ⁇ 70% by weight, ⁇ 60% by weight, ⁇ 50% by weight, ⁇ 40% by weight, ⁇ 30% by weight, ⁇ 20% by weight % or ⁇ 10% by weight. It is also possible that the monomer contains no styrene at all.
  • Monomer mixtures are often used as monomers, which esters of ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids preferably having 3 to 6 carbon atoms, such as in particular acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, with generally 1 to 12, preferably 1 up to 8 and in particular 1 to 4 alkanols, such as especially acrylic acid and methacrylic acid, methyl, ethyl, n-butyl, isobutyl and -2-ethylhexyl ester, maleic acid di-methyl ester or maleic acid di-n -butyl ester included.
  • esters of ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids preferably having 3 to 6 carbon atoms, such as in particular acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, with generally 1 to 12, preferably 1 up
  • Preferred monomers are monomer mixtures which contain> 50% by weight, based on the total weight of the monomers to be polymerized, of esters of ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids, preferably having 3 to 6 carbon atoms,
  • the free radical aqueous emulsion polymerization particularly efficiently from the point of view of the desired properties and in relation to a high level of economy, the use of inorganic peroxides, such as, for example, di-sodium and / or di-potassium peroxodisulfate, as the radical starter is preferred.
  • the amount of the radical polymerization initiator used is preferably 0.1 to 2% by weight, based on the total amount of the monomers to be polymerized.
  • the manner in which the radical polymerization initiator is added to the polymerization vessel in the course of the radical aqueous emulsion polymerization according to the invention is of minor importance.
  • the polymerization initiator can either be completely introduced into the polymerization vessel or, depending on its consumption, can be added continuously or in stages in the course of the free-radical aqueous emulsion polymerization. In particular, this depends in a manner known per se to the person skilled in the art, inter alia. on the chemical nature of the polymerization initiator, the monomer system to be polymerized, the reactor pressure and the polymerization temperature.
  • reaction temperature for the radical aqueous emulsion polymerization according to the invention is the entire range from 0 to 170 ° C, temperatures from 70 to 120 ° C, preferably 80 to 100 ° C and particularly preferably> 85 to 100 ° C, however, are preferably used.
  • the free radical aqueous emulsion polymerization according to the invention can be carried out at a pressure of less than, equal to or greater than 1 bar (absolute), so that the polymerization temperature can exceed 100 ° C. and be up to 170 ° C.
  • Volatile monomers such as ethylene, butadiene or vinyl chloride are preferably polymerized under elevated pressure.
  • the pressure can be 1.2, 1.5, 2, 5, 10, 15 bar or even higher. If emulsion polymerizations are carried out under reduced pressure, pressures of 950 mbar, often 900 mbar and often 850 mbar (absolute) are set.
  • the free radical aqueous emulsion polymerization is advantageously carried out at 1 bar (absolute) under an inert gas atmosphere, such as, for example, under nitrogen or argon.
  • dispersants are used which keep both the monomer droplets and polymer particles dispersed in the aqueous phase and thus ensure the stability of the aqueous polymer dispersion produced.
  • protective colloids usually used to carry out free-radical aqueous emulsion polymerizations and emulsifiers are suitable as such.
  • Suitable protective colloids are, for example, polyvinyl alcohols, cellulose derivatives or copolymers containing vinyl pyrrolidone.
  • a detailed description of other suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg-Thieme-Verlag, Stuttgart, 1961, pages 411 to 420.
  • mixtures of emulsifiers and / or protective colloids are used.
  • emulsifiers are used as dispersants, the relative molecular weights of which, in contrast to the protective colloids, are usually below 1000. They can be anionic, cationic or nonionic in nature.
  • anionic emulsifiers are compatible with one another and with nonionic emulsifiers.
  • cationic emulsifiers while anionic and cationic emulsifiers are usually not compatible with one another.
  • Common emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (EO grade: 3 to 50, alkyl radical: C 4 to C ⁇ 2 ), ethoxylated fatty alcohols (EO degree: 3 to 50; alkyl radical: C ⁇ to C 6 ) as well as alkali metal and ammonium salts of alkyl sulfates (alkyl radical: Cs to C ⁇ 2 ), of sulfuric acid half-star ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: C ⁇ 2 to C ⁇ 8 ) and ethoxylated alkylphenols (EO degree: 3 to 50 , Alkyl radical: C 4 to C ⁇ ), of alkyl sulfonic acids (alkyl radical: C ⁇ to Ci ⁇ ) and of alkylarylsulfonic acids (alkyl radical: Cg to Ci ⁇ ). Further suitable emulsifiers can be found in Houben-Weyl, Method
  • R 1 and R 2 are C to C alkyl and one of the radicals R 1 or R 2 can also be hydrogen, and A and B can be alkali metal ions and / or ammonium ions.
  • R 1 and R 2 are preferably linear or branched alkyl radicals having 6 to 18 carbon atoms, in particular having 6, 12 and 16 carbon atoms or hydrogen atoms, where R 1 and R 2 are not both at the same time Are H atoms.
  • a and B are preferably sodium, potassium or ammonium ions, with sodium ions being particularly preferred.
  • R 1 is a branched alkyl radical having 12 C atoms and R 2 is an H atom or R 1 are particularly advantageous.
  • Industrial mixtures are used which have a share of 50 to 90 wt .-% of the monoalkylated product, for example Dowfax ® 2A1 (trademark of Dow Chemical Company).
  • the compounds I are generally known, for example from US Pat. No. 4,269,749, and are commercially available.
  • the aforementioned dispersants are generally suitable for carrying out the process according to the invention.
  • the process according to the invention also includes the preparation of aqueous polymer dispersions of self-emulsifying polymers in which monomers which have ionic groups bring about stabilization due to repulsion of charges of the same sign.
  • Nonionic and / or anionic dispersants are preferably used for the process according to the invention. However, cationic dispersants can also be used.
  • the amount of dispersant used is 0.1 to 5% by weight, preferably 1 to 3% by weight, in each case based on the total amount of the monomers to be polymerized by free radicals.
  • Free-radical chain-transferring compounds are usually used to reduce or control the molecular weight of the polymers accessible by a free-radical aqueous emulsion polymerization.
  • Essentially aliphatic and / or araliphatic halogen compounds such as, for example, n-butyl chloride, n-butyl bromide, n-butyl iodide, methylene chloride, ethylene dichloride, chloroform, bromoform, bromotrichloromethane, dibromodichloromethane, carbon tetrachloride, tetrabromide, organic carbonyl, benzyl bromide, benzyl chloride, benzyl chloride, benzyl chloride, benzyl such as primary, secondary or tertiary aliphatic thiols, such as, for example, ethanethiol, n-propanethiol, 2-propanethiol, n-butane
  • ⁇ ß ⁇ O ⁇ tr ⁇ z cn ⁇ ⁇ 3> P a> q cn ⁇ ⁇ a>r> q ⁇ ⁇ cn> Q a cn
  • Chen auxiliaries and additives are added continuously or discontinuously and then, if necessary, kept at the reaction temperature.
  • the polymer particles of the aqueous polymer dispersions which are accessible according to the invention all have weight-average particle diameters of ⁇ 300 nm, preferably ⁇ 200 nm, particularly preferably ⁇ 100 nm and particularly preferably ⁇ 50 nm.
  • weight-average particle diameters are understood to mean the so-called Dso values, which are above a determination by means of analytical ultracentrifuge is accessible (cf. SE Harding et al., Analytical Ultracentrifugation in Biochemistry and Polymer Science, Royal Society of Chemistry, Cambridge, Great Britain 1992, Chapter 10, Analysis of Polymer Dispersions with an Eight-Cell -AUC multiplexer: High Resolution Particle Size Distribution and Density Gradient Techniques, W.
  • the particle diameter D can be calculated with a known viscosity of the dispersant ⁇ DM and a known difference between the density of the dispersion particles ⁇ PM and the density of the dispersant ⁇ DM .
  • the so-called Dso value indicates the average diameter of the particles, which results when 50% by weight of all particles are sedimented.
  • the polymer particles obtained generally have a monodisperse particle size distribution.
  • a monodisperse particle size distribution is to be understood if the particle size distribution function can be approximately described with a Gaussian distribution.
  • Aqueous polymer dispersions with narrow monodisperse particle size distributions are frequently obtained according to the invention.
  • a narrow particle size distribution is understood in this document if the standard softening of the particle diameter from the weight-average particle diameter is ⁇ 30%.
  • the process according to the invention advantageously provides access to aqueous polymer dispersions whose polymer solids content, based on the weight of the aqueous polymer dispersion, is generally> 20% by weight, often> 25% by weight and often> 30% by weight .-% is.
  • the residual monomers remaining in the aqueous polymer dispersion after completion of the main polymerization reaction can be stripped by steam and / or inert gas and / or by chemical deodorization, as described, for example, in documents DE-A 4 419 518, EP-A 767 180 or DE-A 3 834 734 are removed without the polymer properties of the aqueous polymer dispersion being adversely affected.
  • the at least one radical chain-transferring compound which may not be completely incorporated into the polymer can also be removed from the aqueous polymer dispersion obtainable according to the invention if necessary.
  • the disperse polymer can be separated from the aqueous serum by centrifugation, redispersed by adding neutral, acidic and / or basic water, centrifuged again, etc., the at least one radical-chain-transferring compound not incorporated into the polymer accumulating in the serum.
  • the at least one radical-chain-transferring compound which may not be completely incorporated into the polymer can also be separated off from the aqueous polymer dispersion according to the invention by coagulation and repeated washing of the coagulated polymer with neutral, acidic and / or basic water.
  • aqueous polymer dispersions which are prepared by the process according to the invention are particularly suitable as starting material (seed) for producing other aqueous polymer dispersions and for producing adhesives, such as, for example, pressure-sensitive adhesives, construction adhesives or industrial adhesives, binders, such as, for example for paper coating, emulsion paints or for printing inks and varnishes for printing on plastic films, for the production of nonwovens as well as for the production of protective layers and water vapor barriers, such as for primers.
  • adhesives such as, for example, pressure-sensitive adhesives, construction adhesives or industrial adhesives
  • binders such as, for example for paper coating, emulsion paints or for printing inks and varnishes for printing on plastic films, for the production of nonwovens as well as for the production of protective layers and water vapor barriers, such as for primers.
  • aqueous polymer dispersions obtainable according to the invention can be dried easily with or without additional auxiliaries to give redispersible polymer powders (for example freeze drying or spray drying).
  • the glass transition temperature of the polymer particles obtainable according to the invention is> 50 ° C, preferably> 60 ° C, particularly preferably> 70 ° C, very particularly preferably> 80 ° C and particularly preferably> 90 ° C or> 100 ° C is.
  • the polymer particles obtained in the polymer dispersion had a weight-average particle diameter of 29 nm.
  • the solids content was generally determined by drying about 1 g of the aqueous polymer dispersion in an open aluminum crucible with an inside diameter of about 3 cm in a drying cabinet at 120 ° C. for 2 hours. To determine the solids content, two separate measurements were carried out and the mean value was calculated.
  • the polymer solids content was obtained by subtracting the content of the emulsifier used from the solids content of the final sample.
  • the weight-average particle diameters were generally determined using an analytical ultracentrifuge (cf. SE Harding et al., Analytical Ultracentrifugation in Biochemistry and Polymer Science, Royal Society of Chemistry, Cambridge, Great Britain 1992, Chapter 10, Analysis of Polymer Dispersions with an eight-cell AUC multiplexer: high resolution Particle Size Distribution and Density Gradient Techniques, W. Gurchtle, pages 147 to 175).
  • the particle diameters were determined using a Beck-5 man-Coulter XL-I ultracentrifuge.
  • the aqueous polymer dispersion to be examined with an aqueous solution containing 0.05 wt .-%, based on its total weight, at a CIO to C ⁇ 8 -alkylsulphonate sodium salt (emulsifier K30 ®, trademark of Bayer AG), diluted to such an extent that the resulting disc
  • 10 persion had a solids content of 0.2 wt .-%, based on their total weight.
  • the measurement was carried out in measuring cells with a layer thickness of 12 mm and a sample volume of 1.2 ml. The distance from the axis of rotation was 6 cm at the meniscus and 7.2 cm at the bottom of the measuring cell. The speed during the determination was
  • the first example was repeated with the exception that no 2-butanethiol was added to the reaction mixture.
  • the aqueous polymer dispersion obtained had polymer particles with a weight-average particle diameter of 47 nm.
  • the solids content was 24.4% by weight and the polymer solids content
  • the first example was repeated with the exception that 0.5 g of 2-butanethiol was added to the reaction mixture instead of 1 g of 2-butanethiol. Polymer particles with a weight-average particle diameter of 35 nm were obtained. The solids content was 23.4% by weight and the polymer solids content was 21.2
  • the first example was repeated with the exception that 0.1 g of 2-butanethiol was added to the reaction mixture instead of 1 g of 2-butanethiol. Polymer particles with a weight-average particle diameter of 42 nm were obtained. The solids content was 24.2% by weight and the polymer solids content was 21.8
  • the first example was repeated with the exception that 100 g of methyl methacrylate instead of 60 g of methyl methacrylate and 40 g of n-butyl acrylate were added to the reaction mixture. Polymer particles with a weight-average particle diameter of 27 nm were obtained. The solids content was 24.4% by weight and the polymer solids content was 22.3% by weight, based in each case on the weight of the aqueous polymer dispersion.
  • the fourth example was repeated with the exception that no 2-butanethiol was added to the reaction mixture.
  • Polymer particles with a weight-average particle diameter of 43 nm were obtained.
  • the solids content was 24.5% by weight and the polymer solids content was 22.3% by weight, in each case based on the weight of the aqueous polymer dispersion.
  • the first example was repeated with the exception that 100 g of n-butyl acrylate instead of 60 g of methyl methacrylate and 40 g of n-butyl acrylate were added to the reaction mixture. With a solids content of 23.6% by weight and a polymer solids content of 21.4% by weight, based in each case on the weight of the aqueous polymer dispersion, polymer particles with a weight-average particle diameter of 42 nm were obtained.
  • the fifth example was repeated with the exception that no 2-butanethiol was added to the reaction mixture.
  • the aqueous polymer dispersion had polymer particles with a weight-average particle diameter of 47 nm and a solids content of 23.2% by weight and a polymer solids content of 21.0% by weight, in each case based on the weight of the aqueous polymer dispersion.
  • the first example was repeated with the exception that 2.24 g of 1,1-dimethyl-1-decanethiol was added to the reaction mixture instead of 1 g of 2-butanethiol.
  • the solids content of the resulting aqueous polymer dispersion was 24.0% by weight and the polymer solids content was 21.8% by weight, based in each case on the weight of the aqueous polymer dispersion.
  • the polymer particles of the aqueous polymer dispersion had a weight-average particle diameter of 20 nm.
  • the dry residue was 23.1% by weight and the polymer solids content was 21.1% by weight, based in each case on the total amount of the aqueous polymer dispersion.
  • 35 mixture prepared from 60 g of methyl methacrylate, 40 g of n-butyl acrylate and 1 g of 2-butanethiol, to the stirred reaction medium for 120 minutes. After the addition had ended, the aqueous polymer dispersion was stirred for a further 30 minutes at the reaction temperature, then cooled to room temperature and dried over a
  • the polymer particles of the aqueous polymer dispersion had a weight-average particle diameter of 18 nm.
  • the dry residue was 24.0% by weight and the polymer solids content was 21.8% by weight, based in each case on the total amount of the aqueous polymer dispersion.
  • PD2 The example described under PD1 was repeated with the exception that a total of 9 g of the aqueous polymer dispersion PS was used instead of 1.8 g.
  • the aqueous polymer dispersion obtained had a solids content of 30% by weight, based on its weight, and polymer particles with a weight-average particle diameter of 134 nm.
  • PD3 The example described under PD1 was repeated with the exception that a total of 18 g of the aqueous polymer dispersion PS was used instead of 1.8 g.
  • the aqueous polymer dispersion obtained had a solids content of 29% by weight, based on its weight, and polymer particles with a weight-average particle diameter of 109 nm.

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Abstract

L'invention concerne un procédé de polymérisation en émulsion aqueuse initiée radicalement. Ce procédé permet de produire une dispersion polymérique aqueuse dont les particules de polymère ont, en poids pondéré, un diamètre < 300 nm. Au moins un monomère présentant au moins un groupe éthyléniquement insaturé est dispersé dans un milieu aqueux et polymérisé en présence d'au moins un composé transférant la chaîne radical à l'aide d'au moins un initiateur radical de polymérisation. Leur solubilité de cette dispersion est supérieure à 1x10-5 moles par kilogramme d'eau à 20 °C et vaut 1 bar (absolu).
PCT/EP2000/005495 1999-06-26 2000-06-15 Procede de production de dispersions de polymeres a fines particules WO2001000695A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU59733/00A AU5973300A (en) 1999-06-26 2000-06-15 Method for producing fine-particle polymer dispersions

Applications Claiming Priority (2)

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DE19929395.3 1999-06-26
DE19929395A DE19929395A1 (de) 1999-06-26 1999-06-26 Verfahren zur Herstellung feinteiliger Polymerisatdispersionen

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US6794466B2 (en) 2001-10-19 2004-09-21 Air Products Polymers, L.P. Shear thinning vinyl acetate based polymer latex composition, especially for adhesives

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DE102006058203A1 (de) 2006-12-11 2008-06-19 Wacker Chemie Ag Radikalisches Polymerisationsverfahren

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GB2244713A (en) * 1990-06-07 1991-12-11 Dow Italia Copolymer beads of a monovinyl aromatic monomer and monomer containing two active vinyl groups and process for its preparation
EP0529927A1 (fr) * 1991-08-19 1993-03-03 MITSUI TOATSU CHEMICALS, Inc. Procédé de préparation de résine pour révélateur
US5521268A (en) * 1995-03-29 1996-05-28 Eastman Kodak Company Odor reduction in toner polymers
JPH09302004A (ja) * 1996-05-14 1997-11-25 Sekisui Chem Co Ltd 単分散微粒子の合成方法

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GB2244713A (en) * 1990-06-07 1991-12-11 Dow Italia Copolymer beads of a monovinyl aromatic monomer and monomer containing two active vinyl groups and process for its preparation
EP0529927A1 (fr) * 1991-08-19 1993-03-03 MITSUI TOATSU CHEMICALS, Inc. Procédé de préparation de résine pour révélateur
US5521268A (en) * 1995-03-29 1996-05-28 Eastman Kodak Company Odor reduction in toner polymers
JPH09302004A (ja) * 1996-05-14 1997-11-25 Sekisui Chem Co Ltd 単分散微粒子の合成方法

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DATABASE WPI Week 9806, Derwent World Patents Index; AN 1998-059191, XP002146092, "PREPARATION OF MONO-DISPERSED FINE POLYMER PARTICLES - INCLUDES ADDITION OF ALKYL MERCAPTAN CHAIN-TRANSFER AGENT TO POLYMERISATION MIXTURE." *

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6794466B2 (en) 2001-10-19 2004-09-21 Air Products Polymers, L.P. Shear thinning vinyl acetate based polymer latex composition, especially for adhesives

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DE19929395A1 (de) 2000-12-28

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