EP2066701A1 - Procédé de fabrication d'une dispersion polymère aqueuse - Google Patents

Procédé de fabrication d'une dispersion polymère aqueuse

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Publication number
EP2066701A1
EP2066701A1 EP07803379A EP07803379A EP2066701A1 EP 2066701 A1 EP2066701 A1 EP 2066701A1 EP 07803379 A EP07803379 A EP 07803379A EP 07803379 A EP07803379 A EP 07803379A EP 2066701 A1 EP2066701 A1 EP 2066701A1
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EP
European Patent Office
Prior art keywords
monomers
monomer
polymerization
host compound
aqueous
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EP07803379A
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German (de)
English (en)
Inventor
Rajan Venkatesh
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BASF SE
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BASF SE
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Publication of EP2066701A1 publication Critical patent/EP2066701A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/02—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to polysaccharides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

  • the present invention is a process for preparing an aqueous polymer dispersion by free-radically initiated aqueous emulsion polymerization of ethylenically unsaturated monomers in the presence of at least one dispersant, at least one free-radical initiator and at least one water-soluble macromolecular host compound, wherein for the emulsion
  • a water-soluble macromolecular host compound which is a hydrophobic
  • the copolymerization takes place essentially in the form of a solution polymerization (see, for example, A. Sen et al., Journal American Chemical Society, 2001, 123, pages 12738 to 12739, B. Klumperman et al., Macromolecules, 2004, 37, pages 4406 to 4416, A. Sen et al., Journal of Polymer Science, Part A: Polymer Chemistry, 2004, 42 (24), pages 6175 to 6192, WO 03/042254, WO 03/091297 or EP-A 1384729) or in the form an aqueous emulsion polymerization, this taking place in particular on the basis of the lowest alkene ethene (see, for example, US Pat. No.
  • a process for the preparation of film-forming aqueous polymer dispersions using vinyl esters and 1-octene is disclosed.
  • the weight ratio of vinyl ester to 1-octene can be from 99: 1 to 70:30.
  • the vinyl esters can be used to a minor extent in admixture with other copolymerizable ethylenically unsaturated compounds for emulsion polymerization.
  • Copolymers with higher molecular weights yielded than when using the customary in the free-radically initiated aqueous emulsion polymerization ethylenically unsaturated compounds vinyl acetate, vinyl chloride, methyl or butyl acrylate. This behavior is based in particular on the hydrogen radical transfer reactions customary in the higher alkenes.
  • the free-radically initiated aqueous emulsion polymerization reactions are usually carried out by dispersing the ethylenically unsaturated monomers dispersively in aqueous medium in the form of monomer droplets and polymerizing them by means of a free-radical polymerization initiator. From this procedure, the present method differs only in the use of a specific monomer composition and a water-soluble macromolecular host compound and their specific use.
  • water often in drinking water quality, but particularly preferably deionized water is used whose
  • Total amount is calculated so that it is> 30 and ⁇ 90 wt .-% and advantageously> 40 and ⁇ 75 wt .-%, each based on the accessible by the process according to the invention aqueous polymer dispersion.
  • any residual amount of water remaining may be metered into the polymerization vessel batchwise in one or more portions or continuously with constant or varying flow rates.
  • the metered addition of water is carried out continuously with constant flow rates, in particular as part of an aqueous monomer emulsion and / or an aqueous solution of the radical initiator.
  • monomers A it is possible to use all linear or cyclic 5 to 40 C atoms, preferably 10 to 30 C atoms and particularly preferably 12 to 24 C atoms, alkenes which can be copolymerized free-radically and which, apart from carbon and hydrogen, are no further elements exhibit.
  • the 1-alkenes are preferably used, for example, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, undecene-1, dodecene-1, 2,4,4-trimethylpentene-1 , 2, 4-dimethylhexene-1, 6,6-dimethylheptene-1, 2-methyloctene-1, tridecen-1, tetradecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecen-1, eicosene-1 , Docosen-1, Tetracosen-1, 2,6-Dimethyldodecen-1, 6-Butyldecen-1, 4,8,12-Trimethyldecen-1 or 2-Methylheptadecen-1.
  • monomer A is an alkene having from 10 to 30 carbon atoms, preferably a 1-alkene having from 12 to 24 carbon atoms. Particular preference is given to using dodecene-1, tridecene-1, tetradecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecen-1, eicosene-1, docosen-1 or tetracosen-1. Of course, mixtures of the aforementioned monomers A can be used.
  • monomers B are esters based on a 3 to 6 C-atoms, in particular a 3, or 4 C-containing ⁇ , ß-monoethylenically unsaturated mono- or dicarboxylic acid, in particular acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid and a 1 to 12 carbon atoms alkanols, preferably an alkanol having 1 to 8 carbon atoms and in particular a 1 to 4 C Atoms containing alkanol, in particular methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methylpropanol-1, tert-butanol, n-pentanol, 3-methylbutanol-1, n-hexanol, 4-methylpentanol -1, n-heptanol, 5-methylhexanol-1, n-octanol, 6-methylheptanol-1, n
  • esters can be used.
  • monomers C are optionally 3 to 6 carbon atoms having ⁇ , ß-monoethylenically unsaturated mono- or dicarboxylic acids and / or their amides, in particular acrylic acid, methacrylic acid, maleic acid, fumaric acid or itaconic acid or acrylamide or methacrylamide used.
  • monomers C can be used.
  • monomers D which differ from the monomers A to C, find, for example, ⁇ , ß-ethylenically unsaturated compounds such as vinyl aromatic monomers such as styrene, ⁇ -methyl styrene, o-chlorostyrene or vinyl toluenes, vinyl halides such as vinyl chloride or vinylidene chloride , Esters of vinyl alcohol and monocarboxylic acids having 1 to 18 C atoms, such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate, nitriles of ⁇ , ⁇ -mono- or diethylenically unsaturated carboxylic acids, such as acrylonitrile, methacrylonitrile, fumaronitrile, maleic acid acid dinitrile and 4 to 8 C-atoms having conjugated dienes, such as 1, 3-butadiene and isoprene, moreover vinylsulfonic acid, 2-acrylamido-2-methylprop
  • Other monomers D have at least one epoxy, hydroxyl, N-methylol or carbonyl group, or at least two non-conjugated ethylenically unsaturated double bonds.
  • Examples thereof are monomers having two vinyl radicals, monomers having two vinylidene radicals and two alkenyl radicals.
  • Particularly advantageous are the diesters of dihydric alcohols with ⁇ , ß-monoethylenically unsaturated monocarboxylic acids, among which acrylic and methacrylic acid are preferred.
  • alkylene glycol diacrylates and dimethacrylates such as ethylene glycol, 1, 2-propylene glycol diacrylate, 1, 3-propylene glycol diacrylate,
  • methacrylic acid and acrylic acid C 1 -C 8 -hydroxyalkyl esters such as n-hydroxyethyl, n-hydroxypropyl or n-hydroxybutyl acrylate and methacrylate, and also compounds such as glycidyl acrylate or methacrylate, diacetone acrylamide and acetylacetoxyethyl acrylate or methacrylate.
  • monomers D can be used.
  • the amount of monomers D is from 0.1 to 20% by weight and often from 0.2 to 10% by weight, in each case based on the total amount of monomers.
  • monomers A in particular dodecene-1, tridecene-1, tetradecene-1, hexadecene-1, heptadecene-1 and / or octadecene-1
  • monomers B in particular n-butyl acrylate, methyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate and / or tert-butyl acrylate and used as monomers C in particular acrylic acid, methacrylic acid and / or itaconic acid.
  • At least one water-soluble macromolecular host compound having a hydrophobic cavity and a hydrophilic shell is present.
  • water-soluble macromolecular host compounds for example, calixarenes, cyclic oligosaccharides, noncyclic oligosaccharides and / or their derivatives can be advantageously used.
  • mixtures of the aforementioned macromolecular host compounds can also be used.
  • Calixarenes which can be used according to the invention are described in US Pat. No. 4,699,966, International Patent Application WO 89/08092 and Japanese Pat. Nos. 1988/197544 and 1989/007837.
  • cyclic oligosaccharides for example, the Cycloinulohe- xose and heptose described by Takai et al., Journal of Organic Chemistry, 1994, 59 (1 1), pages 2967 to 2975, but also cyclodextrins and / or derivatives thereof can be used.
  • Particularly suitable cyclodextrins are ⁇ -cyclodextrin, ⁇ -cyclodextrin or ⁇ -cyclodextrin and their methyl, triacetyl, hydroxypropyl or hydroxyethyl derivatives.
  • starches and / or their degradation products are used as noncyclic oligosaccharides.
  • the water-soluble starches or starch degradation products are often native starches made water soluble by cooking with water, or starch degradation products derived from the native starches by hydrolysis, especially acid catalyzed hydrolysis, enzymatically catalyzed hydrolysis, or oxidation become.
  • Such degradation products are also referred to as dextrins, roasted dextrins or saccharified starches.
  • Their preparation from native starches is known to the person skilled in the art and is described, for example, in G. Tegge, nurse and
  • Starch derivatives EAS Verlag, Hamburg 1984, pages 173ff. and pages 220ff. as well as in EP-A 0441 197.
  • native starches virtually all starches of vegetable origin, such as starches from corn, wheat, potatoes, tapioca, rice, sago and sorghum millet can be used.
  • Chemically modified starches or starch degradation products are also used according to the invention.
  • chemically modified starches or starch degradation products are to understand such starches or starch degradation products in which the OH groups are at least partially derivatized, z. B. in etherified or esterified form.
  • the chemical modification can be carried out on both the native starches and the degradation products. Likewise, it is possible to subsequently convert the chemically modified starches into their chemically modified degradation products.
  • esterification of starch or starch degradation products can be carried out both with inorganic and organic acids, their anhydrides or their chlorides. Common esterified starches are phosphated and / or acetylated starches or starch degradation products.
  • An etherification of the OH groups can be carried out, for example, with organic halogen compounds, epoxides or sulfates in aqueous alkaline solution.
  • Suitable ethers are alkyl ethers, hydroxyalkyl ethers, carboxyalkyl ethers, allyl ethers and cationically modified ethers, for example (trisalkylammonium) alkyl ethers and (trisalkylammonium) hydroxyalkyl ethers.
  • the starches or starch degradation products may be neutral, cationic, anionic or amphiphilic. The production of modified starches and starch degradation products is the most professional (see. Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., Vol. 25, pages 12 to 21 and references therein).
  • water-soluble starch degradation products and their chemically modified derivatives obtainable by hydrolysis, oxidation or enzymatic degradation of native starches or chemically modified starch derivatives are used.
  • Such starch degradation products are also referred to as “saccharified starches” (see G. Tegge, pages 220ff.).
  • Sugared starches and their derivatives as such are commercially available (eg., C * Pur ® products 01906, 01908, 01910, 01912, 01915, 01921, 01924, 01932 or 01934 of Cerestar Germany GmbH, Krefeld) or can by degradation commercial starches are prepared by known methods, for example by oxidative hydrolysis with peroxides or enzymatic hydrolysis of the starches or chemically modified starches. Particularly preferred are hydrolytically accessible starch degradation products which are not chemically modified further.
  • starch degradation products or chemically modified starch degradation products having a weight-average molecular weight Mw in the range from 1000 to 30,000 daltons and more preferably in the range from 3000 to 10,000 daltons are used.
  • Such starches are at 25 0 C and 1 bar completely soluble in water, the solubility limit is generally above 50 wt .-%, which proves to be particularly favorable for the production of erfindungsgemä- SEN copolymers in an aqueous medium.
  • C * Pur ® are advantageous according to the invention 01906 (Mw about 20,000), and C * Pur 01934 ® (Mw approximately 3000) was used.
  • Data on the molecular weight of the saccharified starches to be used according to the invention are based on determinations by gel permeation chromatography under the following conditions:
  • Valve (e.g., VICI 6-way valve)
  • Calibration The calibration was carried out in the low molecular weight range with glucose, raffinose, maltose and maltopentose. For the higher molecular weight range, pullulan standards with a polydispersity ⁇ 1.2 were used.
  • the amount of water-soluble macro-molecular host compound used in the process according to the invention is from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and particularly preferably from 0.5 to 10% by weight, based in each case on Total monomer amount.
  • the total amount of water-soluble macromolecular host compound and of monomers A after initiation of the free-radical polymerization reaction can be carried out batchwise in one batch, batchwise in several portions and continuously with constant or changing flow rates.
  • the total amounts of water-soluble macromolecular host compound and of monomers A in the polymerization vessel are preferably initially introduced before initiation of the polymerization reaction.
  • the total amounts of monomers B to D in the polymerization vessel can be initially introduced before the initiation of the polymerization reaction.
  • no monomers B to D are introduced into the polymerization vessel.
  • the residual amounts remaining or the total amounts of monomers B to D can be added to the polymerization vessel after initiation of the free-radical polymerization reaction, batchwise in one portion, batchwise in several portions and continuously with constant or varying flow rates.
  • the addition of the monomers B to D is carried out continuously with constant flow rates.
  • the addition of the monomers B to D takes place in the form of a monomer mixture and particularly advantageously in the form of an aqueous monomer emulsion.
  • dispersants are used in the context of the present process which keep both the monomer droplets and the polymer particles formed dispersed in the aqueous medium and thus ensure the stability of the aqueous polymer dispersion produced.
  • Suitable dispersants are both the protective colloids commonly used for carrying out free-radical aqueous emulsion polymerizations and emulsifiers.
  • Suitable protective colloids are, for example, polyvinyl alcohols, polyalkylene glycols, alkali metal salts of polyacrylic acids and polymethacrylic acids, gelatin derivatives or acrylic acid, methacrylic acid, maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and / or 4-styrenesulfonic acid-containing copolymers and their alkali metal salts but also N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylcarbazole, 1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, acrylamide, methacrylamide, amines group-bearing acrylates, methacrylates, acrylamides and / or methacrylamides containing homo- and copolymers.
  • suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromo
  • mixtures of protective colloids and / or emulsifiers can be used.
  • dispersants used are exclusively emulsifiers whose relative molecular weights, in contrast to the protective colloids, are usually below 1000. They may be anionic, cationic or nonionic in nature.
  • anionic emulsifiers are compatible with each other and with nonionic emulsifiers.
  • cationic emulsifiers while anionic and cationic emulsifiers are usually not compatible with each other lent.
  • An overview of suitable emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg-Thieme-Verlag, Stuttgart, 1961, pages 192 to 208.
  • emulsifiers are used in particular as dispersants.
  • Nonionic emulsifiers are z.
  • B ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 to C 12) and ethoxylated fatty alcohols (EO degree: 3 to 80, alkyl radical: Cs to C36).
  • Lutensol ® A grades C 2 Ci4-fatty alcohol ethoxylates, EO units: 3 to 8
  • Lutensol ® AO-marks C13C15- oxo alcohol ethoxylates, EO units: 3 to 30
  • Lutensol ® AT-marks Ci 6 CI8 fatty alcohol EO 11 to 80
  • Lutensol ® ON brands Cio-oxo alcohol ethoxylates, EO units: 3 to 11
  • Lutensol ® tO brands cis-oxo alcohol ethoxylates, EO units: 3 to 20
  • Usual anionic emulsifiers are z.
  • R 1 and R 2 are H atoms or C 4 - to C 24 -alkyl and are not simultaneously H atoms, and M 1 and M 2 may be alkali metal ions and / or ammonium ions, has been found to be suitable.
  • R 1 and R 2 are preferably linear or branched alkyl radicals having 6 to 18 C atoms, in particular having 6, 12 and 16 C atoms or hydrogen, where R 1 and R 2 are not both simultaneously H and Atoms are.
  • M 1 and M 2 are preferably sodium, potassium or ammonium, wherein
  • Particularly advantageous compounds (I) are those in which M 1 and M 2 are sodium, R 1 is a branched alkyl radical having 12 C atoms and R 2 is an H atom or R 1 .
  • technical mixtures are used which have a proportion of 50 to 90 wt .-% of the monoalkylated product, such as Dowfax ® 2A1 (trademark of the Dow Chemical Company).
  • the compounds (I) are well known, for. Example, from US-A 4269749, and commercially available.
  • Suitable cationic emulsifiers are generally primary, secondary, tertiary or quaternary ammonium salts having C ⁇ -Cis-alkyl, -alkylaryl or heterocyclic radicals, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolinium salts and salts of amine oxides, Quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts.
  • Examples include dodecylammonium acetate or the corresponding sulfate, the sulfates or acetates of the various 2- (N, N, N-trimethylammonium) ethylparaffinklaer, N-Cetylpyridiniumsulfat,
  • N-laurylpyridinium sulfate and N-cetyl-N N, N-trimethylammonium sulfate, N-dodecyl-N, N, N-trimethylammonium sulfate, N-octyl-N, N, N-trimethylammonium sulfate, N, N-distearyl-N, N- dimethylammonium sulfate, and also the gemini surfactant N, N (lauryl) ethylendiamindisulfat, methyl ammonium sulfate ethoxylated tallow alkyl-N, and ethoxylated oleyl amine (for example, Uniperol ® AC from.
  • BASF AG about 12 ethylene oxide units.
  • Numerous other examples can be found in H. Stumblee, Tensid-Taschenbuch, Carl-Hanser-Verlag, Kunststoff, Vienna, 1981 and in McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989.
  • anionic counterparts are as low as possible nucleophilic, such as perchlorate, sulfate, phosphate, nitrate and carboxylates, such as acetate, trifluoroacetate, trichloroacetate, propionate, oxalate , Citrate, benzoate, and conjugated anions of organosulfonic acids, such as methylsulfonate, trifluoromethylsulfonate and para-toluenesulfonate, furthermore tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-trifluoromethyl) phenyl] borate, hexafluo - Phosphorus, Hexafluoroarsenat or Hexafluoroantimonat.
  • nucleophilic such as perchlorate, sulfate, phosphate, nit
  • the emulsifiers preferably used as dispersants are advantageously in a total amount> 0.005 and ⁇ 10 wt .-%, preferably> 0.01 and ⁇ 5 wt .-%, in particular> 0.1 and ⁇ _ 3 wt .-%, respectively to the total amount of monomers used.
  • the total amount of the protective colloids used as dispersing agents in addition to or instead of the emulsifiers is often> 0.1 and 5% by weight and frequently> 0.2 and ⁇ 7% by weight, in each case based on the total amount of monomer.
  • anionic and / or nonionic emulsifiers preference is given to using anionic and / or nonionic emulsifiers and particularly preferably anionic emulsifiers as dispersants.
  • free-radical initiator a free-radical polymerization initiator
  • these can be both peroxides and azo compounds.
  • redox initiator systems come into consideration.
  • inorganic peroxides such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-alkali metal or ammonium salts of peroxodisulfuric acid, such as, for example, their mono- and di-sodium, potassium or ammonium salts or organic peroxides, can be used as the peroxides.
  • alkyl hydroperoxides for example tert-butyl, p-menthyl or cumyl hydroperoxide, and also dialkyl or diaryl peroxides, such as di-tert-butyl or di-cumyl peroxide.
  • dialkyl or diaryl peroxides such as di-tert-butyl or di-cumyl peroxide.
  • Suitable oxidizing agents for redox initiator systems are essentially the abovementioned peroxides.
  • Suitable reducing agents may be sulfur compounds having a low oxidation state, such as alkali metal sulphites, for example potassium and / or sodium sulphite, alkali hydrogen sulphites, for example potassium and / or sodium hydrogen sulphite, alkali metal metabisulphites, for example potassium and / or sodium metabisulphite, formaldehyde sulphoxylates, for example potassium and / or sodium formaldehyde.
  • alkali metal sulphites for example potassium and / or sodium sulphite
  • alkali hydrogen sulphites for example potassium and / or sodium hydrogen sulphite
  • alkali metal metabisulphites for example potassium and / or sodium metabisulphite
  • formaldehyde sulphoxylates for example potassium and / or sodium formaldehyde.
  • dehydesulfoxylate alkali salts, especially potassium and / or sodium salts, aliphatic sulfinic acids and alkali metal hydrogen sulfides, such as, for example, potassium and / or sodium hydrosulfide, salts of polyvalent metals, such as iron (II) sulfate, iron (II) Ammonium sulfate, iron (II) phosphate, endiols such as dihydroxymaleic acid, benzoin and / or ascorbic acid and reducing saccharides such as sorbose, glucose, fructose and / or dihydroxyacetone.
  • polyvalent metals such as iron (II) sulfate, iron (II) Ammonium sulfate, iron (II) phosphate, endiols such as dihydroxymaleic acid, benzoin and / or ascorbic acid and reducing saccharides such as sorbose, glucose, fructose and / or dihydroxyace
  • the amount of the radical initiator used based on the total amount of monomers, 0.01 to 5 wt .-%, preferably 0.1 to 3 wt .-% and particularly preferably 0.2 to 1, 5 wt .-%.
  • the total amount of the radical initiator in the aqueous reaction medium before initiation of the polymerization reaction can be presented.
  • Initiation of the polymerization reaction is understood to mean the start of the polymerization reaction of the monomers present in the polymerization vessel after radical formation of the radical initiator.
  • the initiation of the polymerization reaction by adding radical initiator to the aqueous polymerization mixture in the polymerization vessel can be carried out under polymerization conditions.
  • a partial or total amount of the free radical initiator may be added to the aqueous polymerization mixture containing the monomers initially introduced in the polymerization vessel under conditions which are not suitable for initiating a polymerization reaction, for example at low temperature, and then polymerization conditions in the aqueous polymerization mixture be set.
  • Polymerization conditions are to be understood as meaning in general those temperatures and pressures under which the free-radically initiated aqueous emulsion polymerization proceeds at a sufficient rate of polymerization. They are dependent, in particular, on the radical initiator used.
  • the type and amount of the radical initiator, polymerization temperature and polymerization pressure are selected such that the free-radical initiator has a half life of ⁇ 3 hours, more preferably ⁇ 1 hour and most preferably ⁇ 30 minutes, and there are always enough starting radicals available to initiate the polymerization reaction or uphold.
  • the reaction temperature for the novel free-radical aqueous emulsion polymerization is the entire range from 0 to 170 ° C. In this case, temperatures of 50 to 120 0 C, often 60 to 1 10 0 C and often used 70 to 100 0 C in the rule.
  • the radical aqueous emulsion polymerization of the present invention can be carried out at a pressure less than or equal to 1 atm (atmospheric pressure). be carried out so that the polymerization temperature 100 0 C exceed and can be up to 170 0 C.
  • volatile monomers such as n-butene-1, n-butene-2, 2-methylpropene, 2-methylbutene-1, 3-methylbutene-1, 2-methylbutene-2, butadiene or vinyl chloride are polymerized under elevated pressure.
  • the pressure may be 1, 2, 1, 5, 2, 5, 10, 15 bar or even higher values. 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 according to the invention is advantageously carried out at 1 atm with exclusion of oxygen, for example under an inert gas atmosphere, for example under nitrogen or argon.
  • the aqueous reaction medium may in principle also in minor amounts ( ⁇ 5 wt .-%) include water-soluble organic solvents such as methanol, ethanol, isopropanol, butanols, pentanols, but also acetone, etc.
  • water-soluble organic solvents such as methanol, ethanol, isopropanol, butanols, pentanols, but also acetone, etc.
  • the process according to the invention is preferably carried out in the absence of such solvents.
  • free radical-transferring compounds in the process according to the invention in order to reduce or control the molecular weight of the polymers obtainable by the polymerization.
  • These are essentially aliphatic and / or araliphatic halogen compounds, such as n-butyl chloride, n-butyl bromide, n-butyl iodide, methylene chloride, ethylene dichloride, chloroform, bromoform, bromotrichloro methane, Dibromdichlormethan, carbon tetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide, organic Thio compounds, such as primary, secondary or tertiary aliphatic thiols, such as ethanethiol, n-propanethiol, 2-propanethiol, n-butanethiol, 2-butanethiol, 2-methyl
  • Methylbenzenethiol and all other in the Polymerhandbook 3 rd edtition, 1989, J. Brandrup and EH Immergut, John Weley & Sons, Section II, pages 133 to 141 described sulfur compounds, but also aliphatic and / or aromatic aldehydes, such as acetaldehyde, propionaldehyde and or benzaldehyde, unsaturated fatty acids, such as oleic acid, dienes with non-conjugated double bonds, such as divinylmethane or vinylcyclohexane or Hydrocarbons with easily abstractable hydrogen atoms, such as toluene, are used.
  • aldehydes such as acetaldehyde, propionaldehyde and or benzaldehyde
  • unsaturated fatty acids such as oleic acid
  • dienes with non-conjugated double bonds such as divinylmethane or vinylcyclohexane
  • the total amount of radical-chain-transferring compounds optionally used in the process according to the invention is generally ⁇ 5% by weight, often ⁇ 3% by weight and frequently ⁇ 1% by weight.
  • a partial or total amount of the radical chain transferring compound optionally used is fed to the reaction medium before the initiation of the free-radical polymerization.
  • a partial or total amount of the radical chain-transferring compound can advantageously also be fed to the aqueous reaction medium together with the monomers B to D during the polymerization.
  • the accessible by the novel process can in principle polymers glass transition temperatures ranging from -70 to +150 0 C, often -30 to +100 0 C, often -20 to +50 0 C.
  • the monomers A to D selected such that the polymer obtained has a glass transition temperature T 9 ⁇ +20 0 C.
  • the monomers A to D are chosen so that polymers having a T 9 value ⁇ + 10 0 C, ⁇ 0 0 C, ⁇ -10 0 C, ⁇ -20 0 C, ⁇ -30 0 C, ⁇ -40 0 C or ⁇ -50 0 C are formed.
  • glass transition temperature is meant here the midpoint temperature according to ASTM D 3418-82, determined by differential thermal analysis (DSC) [cf. also Ullmann 's Encyclopedia of Industrial Chemistry, page 169, Verlag Chemie, Weinheim, 1992 and Zosel in paint and varnish, 82, pages 125 to 134, 1976].
  • DSC differential thermal analysis
  • x 1 , x 2 , .... x n the mass fractions of the monomers 1, 2, .... n and T 9 1 , T 9 2 , .... T 9 "the glass transition temperatures of each of only one of Monomers 1, 2, .... n in polymers of degrees Kelvin.
  • the glass transition temperatures of these homopolymers of most ethylenically unsaturated monomers are known (or can be determined experimentally in a simple manner known per se) and, for example, in J. Brandrup, EH Immergut, Polymer Handbook 1 st Ed. J. Wiley, New York, 1966, 2 nd Ed. J. Wiley, New York, 1975 and 3 rd Ed. J. Wiley, New York, 1989, and in Ullmann 's Cncyclopedia of Industrial Chemistry, page 169, Verlag Chemie, Weinheim, 1992.
  • the free-radically initiated aqueous emulsion polymerization in the presence of a polymer seed for example in the presence of 0.01 to 3 wt .-%, often from 0.02 to 2 wt .-% and often from 0.04 to 1, 5 wt. % of a polymer seed, in each case based on the total amount of monomers.
  • a polymer seed is used in particular when the particle size of the polymer particles to be produced by means of a free-radically aqueous emulsion polymerization is to be specifically adjusted (see, for example, US Pat. No. 2,520,959 and US Pat. No. 3,397,165).
  • a polymer seed is used whose polymer seed particles have a narrow particle size distribution and weight-average diameters D w ⁇ 100 nm, frequently> 5 nm to ⁇ 50 nm and often> 15 nm to ⁇ 35 nm.
  • the determination of the weight-average particle diameter is known to the person skilled in the art and is carried out, for example, by the method of the analytical ultracentrifuge.
  • Weight-average particle diameter in this document is understood to mean the weight-average D W 5o value determined by the method of the analytical ultracentrifuge (see, in this regard, 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 Eight-Cell AUC Multiplexers: High Resolution Particle Size Distribution and Density Gradient Techniques, W. Gurchtle, pp. 147-175).
  • a narrow particle size distribution should be understood within the scope of this document if the ratio of the weight-average particle diameter D w determined by the method of the analytical ultracentrifuge and number-average particle diameter DN 50 [D W 5O / DN 50] ⁇ 2.0, preferably ⁇ 1.5 preferably ⁇ 1, 2 or ⁇ 1, 1 is.
  • the polymer seed is used in the form of an aqueous polymer dispersion.
  • the aforementioned amounts are based on the polymer solids content of the aqueous Polymersaatdispersion; they are therefore given as parts by weight of polymer seed solids, based on the total amount of monomers.
  • a polymer produced by free-radically initiated aqueous emulsion polymerization is understood to mean a polymer seed which has been prepared in a separate reaction step and whose monomeric composition is different from that produced by the free-radically initiated aqueous emulsion polymerization, which, however, means that Production of Fremdpolymersaat and for the preparation of the aqueous polymer dispersion different monomers or monomer mixtures are used with different compositions.
  • the preparation of a foreign polymer seed is familiar to the person skilled in the art and is usually carried out by initially charging a relatively small amount of monomers and a relatively large amount of emulsifiers in a reaction vessel and adding a sufficient amount of polymerization initiator at reaction temperature.
  • a polymer seed having a glass transition temperature> 50 0 C, often> 60 0 C or> 70 0 C and used often> 80 0 C or> 90 0 C.
  • Particularly preferred is a polystyrene or polymethyl methacrylate polymer seed.
  • the total amount of foreign polymer seed can be presented in the polymerization vessel. But it is also possible to submit only a subset of Fremdpolymerse seed in the polymerization and add the remaining amount during the polymerization together with the monomers A to D. If necessary, however, it is also possible to add the total amount of polymer seed in the course of the polymerization. Preferably, the total amount of Fremdpolymersaat is submitted before initiation of the polymerization in the polymerization.
  • the aqueous polymer dispersions obtainable in accordance with the invention usually have a polymer solids content of 10 10 and ⁇ 70% by weight, frequently 20 20 and ⁇ 65% by weight and often 25 25 and ⁇ 60% by weight, based in each case on the aqueous Polymerisate, on.
  • the number-average particle diameter (cumulant z-average) determined by quasi-elastic light scattering (ISO standard 13 321) is generally between 10 and 2000 nm, frequently between 20 and 1000 nm and often between 100 and 700 nm and 100 to 400 nm.
  • aqueous polymer dispersions obtainable by the process according to the invention have a significantly higher monomer conversion with the same polymerization time or a higher polymer solids content after the polymerization reaction has ended.
  • aqueous polymer dispersions obtainable by the process according to the invention can be used in particular for the production of adhesives, sealants, plastic plasters, paper coating slips, fiber webs, paints and coating compositions for organic substrates, such as leather or textile materials, and for the modification of mineral binders.
  • the aqueous polymer dispersions obtainable by the process according to the invention are preferably a tackifier, i. H. a tackifying resin is added.
  • Tackifiers are for example from Adäsive Age, July 1987, pages 19 to 23 or Polym. Mater. Be. Closely. 61 (1989), pages 588 to 592 known.
  • Tackifiers are z.
  • natural resins such as rosin resins and their by disproportionation or isomerization, polymerization, dimerization or hydrogenation deriving derivatives. These can be in their salt form (with eg mono- or polyvalent
  • Alcohols used for esterification may be monovalent or polyvalent. Examples are methanol, ethanediol, diethylene glycol, triethylene glycol, 1, 2,3-propanetriol (glycerol) or pentaerythritol.
  • hydrocarbon resins eg. As coumarone-indene resins, polyterpene resins, hydrocarbon resins based on unsaturated CH compounds such as butadiene, pentene, methylbutene, isoprene, piperylene, divinylmethane, pentadiene, cyclopentene, cyclopentadiene, cyclohexadiene, styrene, ⁇ -methylstyrene or vinyltoluenes use.
  • unsaturated CH compounds such as butadiene, pentene, methylbutene, isoprene, piperylene, divinylmethane, pentadiene, cyclopentene, cyclopentadiene, cyclohexadiene, styrene, ⁇ -methylstyrene or vinyltoluenes use.
  • tackifiers are increasingly also polyacrylates, which have a low molecular weight used.
  • these polyacrylates have a weight average molecular weight below 30,000 g / mol.
  • the polyacrylates are preferably at least 60, in particular at least 80 wt .-% of Ci-Cs- alkyl acrylates or methacrylates.
  • Preferred tackifiers are natural or chemically modified rosin resins. Rosin resins consist predominantly of abietic acid or abietic acid derivatives.
  • the tackifiers can be added in a simple manner to the aqueous polymer dispersions obtainable according to the invention.
  • the tackifiers are preferably themselves in the form of an aqueous dispersion.
  • the amount of tackifier is preferably 5 to 100 wt .-%, particularly 10 to 50 wt .-%, each based on the total amount of the polymer (solid / solid).
  • tackifiers it is of course also possible to use other customary additives, for example thickeners, defoamers, plasticizers, pigments, wetting agents or fillers in the formulation of pressure-sensitive adhesives.
  • the aqueous polymer dispersions may be applied to substrates such as paper or polymer tapes and films, preferably consisting of polyethylene, polypropylene, which may be biaxially or monoaxially stretched, polyethylene terephthalate, polyvinyl chloride, by conventional methods, for example by rolling, knife coating, brushing, etc. Polystyrene, polyamide or metal surfaces are applied.
  • the water can be easily removed by drying at 50 to 150 0 C.
  • the pressure-sensitive adhesive-coated side of the substrates for example the labels or tapes, can be covered with a release paper, for example with a siliconized paper.
  • aqueous polymer dispersions obtainable by the process according to the invention are advantageously suitable as components in adhesives, in particular pressure-sensitive adhesives.
  • these adhesives according to the invention advantageously have improved adhesion to plastic surfaces, in particular polyethylene surfaces.
  • Leverkusen (mixture of primary and secondary sodium alkylsulfonates with an average chain length of 15 carbon atoms), 10.5 g of a 20 wt .-% aqueous solution of Lutensol ® tO (ethoxylated C13-oxo alcohol, average degree of ethoxylation: 20) 20 BASF Aktiengesellschaft and 10.5 g of a 7 wt .-% aqueous solution of sodium persulfate and heated with stirring to 90 0 C.
  • Lutensol ® tO ethoxylated C13-oxo alcohol, average degree of ethoxylation: 20
  • the monomer feed consisting of 370 g deionized water, 1, 8 g of a 40 wt .-% aqueous solution of emulsifier K30 ®, 10.5 g a 20 wt .-% aqueous solution of Lutensol ® TO 20, 4.5 g of a 25 wt .-% aqueous solution of sodium hydroxide, 581 g of n-butyl acrylate and 14.0 g of acrylic acid and the initiator feed consisting of 59.5 g of a 7 wt .-% aqueous solution of sodium persulfate, started simultaneously, wherein the monomer feed within 3 hours and the initiator feed was added continuously within 3.5 hours.
  • aqueous polymer dispersion obtained at 90 0 C for 2 hour Hess then to react for the aqueous polymer dispersion obtained at 90 0 C for 2 hour. Thereafter, the aqueous polymer dispersion was cooled to room temperature and added with 35.0 g of a 10 wt .-% aqueous solution of sodium hydroxide. After filtration of the aqueous polymerizate dispersion over a 400 ⁇ m sieve, no coagulum was obtained. The aqueous polymer dispersion obtained had a solids content of 39.6% by weight, based on the total weight of the aqueous polymer dispersion. The glass transition temperature of the polymer was -46 0 C. The average particle size was 164 nm.
  • the solids content was determined by drying a defined amount of the aqueous polymer dispersion (about 5 g) at 140 ° C. in a drying oven to constant weight. Two separate measurements were made. The value given in the example represents the mean value of the two measurement results.
  • the determination of the glass transition temperature was carried out according to DIN 53765 by means of a DSC 820 device, TA 8000 series from Mettler-Toledo.
  • the average particle diameter of the copolymer particles were generally determined by dynamic light scattering on a 0.005 to 0.01 percent by weight aqueous copolymer dispersion at 23 0 C using an Autosizer IIC from. Malvern Instruments, England.
  • the mean diameter of the cumulant evaluation (cumulant z-average) of the measured autocorrelation function (ISO standard 13321) is given.
  • the determination of the coagulum content was carried out in such a way that the entire amount of the respectively obtained aqueous polymer dispersion was filtered through a 400 ⁇ m sieve. Subsequently, the remaining coagulum residue on the screen was washed with about 200 ml of deionized water and dried in a vacuum oven at a pressure of about 30 mbar (absolute) at room temperature to constant weight.
  • Comparative Example 1 The implementation of Comparative Example 1 was carried out analogously to the example, but with the difference that no macromolecular host compound was used. There was no aqueous polymer dispersion, but only a liquid two-phase mixture of an aqueous and an organic (octadecene) phase was obtained. Comparative Example 2
  • Comparative Example 2 The procedure of Comparative Example 2 was carried out analogously to the example, but with the difference that the macromolecular host compound was not presented, but was added as a homogeneous component of the monomer emulsion. After filtration through a 400 ⁇ m sieve, an aqueous polymer dispersion having a solids content of 37.1% by weight was obtained. The coagulum amount was about 100 g.
  • Comparative Example 3 The procedure of Comparative Example 3 was carried out analogously to the example, but with the difference that the octadecene-1 was not initially charged, but was metered in as a homogeneous constituent of the monomer emulsion. After filtration through a 400 ⁇ m sieve, an aqueous polymer dispersion having a solids content of 39.0% by weight was obtained. The coagulum amount was about 8 g.
  • Comparative Example 4 The procedure of Comparative Example 4 was carried out analogously to the example, but with the difference that neither the octadecene-1 nor the macromolecular host compound were presented, but were metered in as homogeneous constituents of the monomer emulsion. There was no stable polymer dispersion, since the approach coagulated after the monomer emulsion was fed.

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

Abstract

L'invention concerne un procédé de fabrication d'une dispersion polymère aqueuse par utilisation d'un alcène ayant de 4 à 40 atomes de carbone.
EP07803379A 2006-09-14 2007-09-10 Procédé de fabrication d'une dispersion polymère aqueuse Withdrawn EP2066701A1 (fr)

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EP06120685A EP1900756A1 (fr) 2006-09-14 2006-09-14 Procédé de préparation d'une dispersion aqueuse de polymère
PCT/EP2007/059462 WO2008031790A1 (fr) 2006-09-14 2007-09-10 Procédé de fabrication d'une dispersion polymère aqueuse
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DE502008002695D1 (de) * 2007-10-09 2011-04-07 Basf Se Wässriges bindemittel für faserförmige oder körnige substrate
US20090275699A1 (en) * 2008-05-05 2009-11-05 Mingfu Zhang Starch containing formaldehyde-free thermoset binders for fiber products
WO2009135812A1 (fr) * 2008-05-08 2009-11-12 Basf Se Procédé de production d'une dispersion aqueuse de polymères
WO2017007765A1 (fr) 2015-07-06 2017-01-12 University Of North Carolina At Greensboro Procédés et compositions pour induire un comportement hygiénique chez l'abeille mellifère
CN109536060B (zh) * 2018-12-17 2021-08-10 江苏苏博生物医学科技有限公司 一种脱落细胞粘取胶及其制备方法
WO2020210559A1 (fr) 2019-04-09 2020-10-15 University Of North Carolina At Greensboro Mélange synergique pour induire un comportement hygiénique chez les abeilles mellifères, et compositions et procédés associés
CN113209943B (zh) * 2021-04-16 2022-02-01 武汉大学 一种环糊精微孔有机网材料及其制备方法和应用

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GB1104536A (en) * 1966-06-10 1968-02-28 Bp Chem Int Ltd A process for the production of film forming aqueous dispersions of copolymers of vinyl esters of organic acids
DE9014162U1 (fr) * 1990-10-11 1990-12-20 Siemens Ag, 8000 Muenchen, De
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