EP1587849A2 - Polymerisats aux silicones - Google Patents

Polymerisats aux silicones

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Publication number
EP1587849A2
EP1587849A2 EP03795917A EP03795917A EP1587849A2 EP 1587849 A2 EP1587849 A2 EP 1587849A2 EP 03795917 A EP03795917 A EP 03795917A EP 03795917 A EP03795917 A EP 03795917A EP 1587849 A2 EP1587849 A2 EP 1587849A2
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EP
European Patent Office
Prior art keywords
silicone
containing polymers
radical
vinyl
branched
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03795917A
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German (de)
English (en)
Other versions
EP1587849A3 (fr
Inventor
Kurt Stark
Christian Herzig
Christian HÖGL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wacker Chemie AG
Original Assignee
Wacker Chemie AG
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Filing date
Publication date
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Publication of EP1587849A2 publication Critical patent/EP1587849A2/fr
Publication of EP1587849A3 publication Critical patent/EP1587849A3/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • 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
    • C08L51/08—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 otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—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 otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
    • 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
    • C09J151/08—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 otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C09J151/085—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 otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes

Definitions

  • the invention relates to silicone-containing polymers, processes for their preparation and their use.
  • Organosilicon compounds such as organosiloxane polymers are used for the hydrophobization of polymers of ethylenically unsaturated monomers.
  • Such hydrophobically modified polymers are used in many areas in the form of their polymer powder, in particular polymer powder redispersible in water, or as an aqueous polymer dispersion. They are used as binders in coating materials or adhesives, particularly in the construction and textile sectors, and as binders in cosmetics and hair care products.
  • EP-A 0352339 describes protective coatings for concrete structures which contain copolymers of divinyl-polydimethylsiloxane with acrylate or methacrylate esters and with vinyl or acrylic-functional alkoxysilanes as a solution in organic solvents.
  • EP-B 771826 describes aqueous binders for coatings and adhesives based on emulsion polymers of vinyl esters, acrylic or methacrylic acid esters or vinyl aromatics which, as crosslinking agents, contain polysiloxanes with unsaturated residues, for example vinyl, acryloxy or methacryloxy Groups.
  • EP-A 943634 describes aqueous latices for use as coating agents, which are prepared by copolymerization of ethylenically unsaturated monomers in the presence of a silicone resin containing silanol groups.
  • EP-A 1095953 describes silicone-grafted vinyl copolymers, a carbosiloxane dendrimer being grafted onto the vinyl polymer.
  • silicone-containing polymers can be obtained by polymerizing ethylenically unsaturated monomers in the presence of a linear polydialkylsiloxane with polyalkylene oxide side chains. Disadvantages are the tendency to form coagulate and the broad particle size distribution of the products.
  • US-A 5216070 describes a process for the inverse emulsion polymerization of carboxyl-functional monomers, linear polydialkylsiloxanes with polyalkylene oxide side chains being used as emulsifiers.
  • DE-A 4240108 describes a polymerization process for the preparation of binders containing polysiloxane, for use in dirt-repellent coatings, the monomers being polymerized in the presence of an OH-, COOH- or epoxy-functional polydialkylsiloxane, which may also contain polyether groups.
  • DE-A 10041163 discloses a production process for hair cosmetic formulations in which vinyl esters are polymerized in the presence of a polyether-containing compound, for example polyether-containing silicone compounds.
  • a disadvantage of the silicone-modified emulsion polymers described in the prior art is a strong tendency to hydrolysis and to uncontrolled crosslinking, which, in some applications, is desired and subsequently increased by adding silane and catalyst, but in the case of paint dispersions or when used as a coating agent undesirable gel bodies, "specks" and insoluble constituents.
  • the previously known silicone-containing emulsion polymers are often not alkali-resistant, since it is known that silicones are not stable in alkaline.
  • the object of the invention was to develop polymers which are hydrolysis-resistant and hydrophobic, thereby weather-resistant, water-repellent and not polluting, and moreover have good water vapor permeability and have a high resistance to wet abrasion. Another object was to provide a process by which hydrophobically modified polymers with a narrow particle size distribution and without coagulation are accessible.
  • the invention relates to silicone-containing polymers obtainable by radical polymerization of ethylenically unsaturated monomers in the presence of a polysiloxane, characterized in that a) 60 to 99.99% by weight of one or more monomers from the group comprising vinyl esters of unbranched or branched alkylcarboxylic acids with 1 to 15 C atoms, methacrylic acid esters and acrylic acid esters of alcohols with 1 to 15 C atoms, vinyl aromatics, olefins, dienes and vinyl halides, in the presence of b) 0.01 to 40% by weight of at least one branched polysiloxane are polymerized, whose lipophilic siloxane portion contains branched structures, and whose hydrophilic organopolymer part can be linear or branched, the data in% by weight relating to the total weight of a) and b).
  • Suitable vinyl esters are vinyl esters of unbranched or branched carboxylic acids having 1 to 15 carbon atoms.
  • Preferred vinyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methyl vinyl acetate, vinyl pivalate and vinyl esters of ⁇ -branched monocarboxylic acids having 5 to 13 carbon atoms, for example VeoVa9 R or VeoVal0 R (trade name of Shell).
  • Vinyl acetate is particularly preferred, most preferred is a combination of vinyl acetate with ⁇ -branched monocarboxylic acids having 5 to 11 carbon atoms, such as VeoValO.
  • Suitable monomers from the group of the esters of acrylic acid or methacrylic acid are esters of unbranched or branched alcohols having 1 to 15 carbon atoms.
  • Preferred methacrylic acid esters or acrylic acid esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-, iso- and t-butyl acrylate, n-, iso- and t-butyl methacrylate, 2-ethylhexyl acrylate, norbornyl acrylate.
  • Methyl acrylate, methyl methacrylate, n-, iso- and t-butyl acrylate, 2-ethylhexyl acrylate and norbornyl acrylate are particularly preferred.
  • Suitable dienes are 1,3-butadiene and isoprene.
  • Examples of copolymerizable olefins are ethene and propene.
  • Styrene and vinyl toluene can be copolymerized as vinyl aromatics. From the group of vinyl halides, vinyl chloride, vinylidene chloride or vinyl fluoride, preferably vinyl chloride, are usually used.
  • auxiliary monomers can also be copolymerized.
  • auxiliary monomers are ethylenically unsaturated mono- and dicarboxylic acids or their salts, preferably crotonic acid, acrylic acid, methacrylic acid, fumaric acid and maleic acid; ethylenically unsaturated carboxylic acid amides and nitriles, preferably acrylamide and acrylonitrile; Mono- and diesters of fumaric acid and maleic acid such as the diethyl and diisopropyl esters and maleic anhydride, ethylenically unsaturated sulfonic acids or their salts, preferably vinylsulfonic acid, 2-acrylamido-2-methyl-propanesulfonic acid.
  • Cationic monomers such as diallyldimethylammonium chloride (DADMAC), 3-trimethylammonium propyl (meth) acrylamide chloride (MAPTAC) and 2-trimethylammoniumethyl (meth) acrylate chloride are also suitable as auxiliary monomers.
  • DMAC diallyldimethylammonium chloride
  • MATAC 3-trimethylammonium propyl (meth) acrylamide chloride
  • 2-trimethylammoniumethyl (meth) acrylate chloride are also suitable as auxiliary monomers.
  • Suitable auxiliary monomers are also polymerizable silanes or mercaptosilanes.
  • ⁇ -acrylic or ⁇ -methacryloxy are preferred propyltri (alkoxy) silanes, ⁇ -methacryloxymethyltri (alkoxy) silanes, ⁇ -methacryloxypropylmethyldi (alkoxy) silanes, vinylalkyldi (alkoxy) silanes and vinyltri (alkoxy) silanes, the alkoxy groups being, for example, methoxy, ethoxy, Methoxyethylene, ethoxyethylene, methoxypropylene glycol ether or ethoxypropylene glycol ether residues can be used.
  • Examples of these are vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltris- (1-methoxy) -isopropoxysilane, vinyltributoxysilane, vinyltriacetoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxoxiloxylmethyl, 3-methacryloxoxiloxylmethyl, 2-methoxyethoxy) silane, vinyltrichorsilane, vinylmethyldichlorosilane, vinyltris- (2-methoxyethoxy) silane, trisacetoxyvinylsilane, 3- (triethoxysilyl) propylberis-succinic anhydride silane. 3-Mercaptopropyltriethoxysilane, 3-Mercaptopropyltrimethoxysilane and 3-Mercapto-propylmethyldimethoxysilane are also preferred.
  • acrylates in particular epoxy-functional parts such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, vinyl glycidyl ether, or hydroxyalkyl-functional ones such as hydroxyethyl (meth) acrylate, or substituted or unsubstituted aminoalkyl (meth) acrylates, or cyclic monomers such as N-vinyl pyrrolidone.
  • epoxy-functional parts such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, vinyl glycidyl ether, or hydroxyalkyl-functional ones such as hydroxyethyl (meth) acrylate, or substituted or unsubstituted aminoalkyl (meth) acrylates, or cyclic monomers such as N-vinyl pyrrolidone.
  • polymerizable silicone macromers with at least one unsaturated group such as linear or branched polydialkylsiloxanes with C 1 -C 6 -alkyl radical, and with a chain length of 10 to 1000, preferably 50 to 500 SiO (C n H n + ⁇ ) units , These can contain one or two terminal, or one or more chain-linked, polymerizable groups (functional groups).
  • pre-crosslinking comonomers such as polyethylenically unsaturated comonomers, for example divinyl adipate, divinylbenzene, diallyl maleate, allyl methacrylate, butanediol diacrylate or triallyl cyanurate, or post-crosslinking comonomers, for example acrylamidoglycolic acid (AGA), methyl ME-acrylacrylamido-methylol (MAGA-acrylacrylamido-methylol) ), N-methylol methacrylamide, N-methyl olallyl carbamate, alkyl ethers such as isobutoxy ether or esters of N-methylol acrylamide, N-methylol methacrylamide and N-methylolallyl carbamate.
  • AGA acrylamidoglycolic acid
  • MAGA-acrylacrylamido-methylol methyl ME-acrylacrylamido-methylol
  • alkyl ethers such as is
  • Components a) are preferably selected so that aqueous copolymer dispersions and aqueous redispersions of the copolymer powders result which, without the addition of film-forming aids, have a minimum film-forming temperature MFT of ⁇ 10 ° C., preferably ⁇ 5 ° C., in particular from 0 ° C. to 2 ° C.
  • MFT minimum film-forming temperature
  • Tg glass transition temperature
  • the glass transition temperature Tg of the polymers can be determined in a known manner by means of differential scanning calorimetry (DSC).
  • the Tg can also be roughly predicted using the Fox equation. According to Fox TG, Bull. Am. Physics Soc.
  • Vinyl ester copolymers of vinyl acetate with other vinyl esters such as vinyl laurate, vinyl pivalate, vinyl 2-ethylhexanoic acid ester, vinyl ester of an alpha-branched carboxylic acid, in particular vinyl versatic acid (VeoVa9 R , VeoVal0 R );
  • Vinyl ester-ethylene copolymers such as vinyl acetate-ethylene copolymers, which may also contain other vinyl esters, such as vinyl laurate, vinyl pivalate, vinyl 2-ethylhexanoic acid ester, vinyl ester of an alpha-branched carboxylic acid, in particular vinyl versatic acid (VeoVa9 R , VeoVal0 R ), or fumaric acid or Contain maleic acid diesters;
  • Vinyl ester-ethylene copolymers such as vinyl acetate-ethylene copolymers, which optionally also contain other vinyl esters, such as vinyl laurate, vinyl pivalate, vinyl 2-ethylhexanoic acid ester, vinyl ester of an alpha-branched carboxylic acid, in particular vinyl versatic acid (VeoVa9 R , VeoVal0 R ) and a polymerizable Silicone macromer included;
  • Vinyl ester-ethylene-vinyl chloride copolymers vinyl acetate and / or vinyl propionate and / or one or more copolymerizable vinyl esters such as vinyl laurate, vinyl pivalate, vinyl-2-ethylhexanoic acid ester, vinyl ester of an alpha-branched carboxylic acid, in particular vinyl vinyl versatate (VeoVa0 R , R ) are included; Vinyl ester / acrylic acid ester copolymers with vinyl acetate and / or vinyl laurate and / or vinyl acetate / versatic acid and acrylic acid ester, in particular butyl acrylate or 2-ethylhexyl acrylate, which may also contain ethylene; Acrylic ester copolymers, preferably with n-butyl acrylate and / or 2-ethylhexyl acrylate;
  • Methyl methacrylate copolymers preferably with butyl acrylate and / or 2-ethylhexyl acrylate, and / or 1, 3-butadiene; Styrene-1, 3-butadiene copolymers and styrene (meth) acrylic acid ester copolymers such as styrene-butyl acrylate, styrene-methyl methacrylate-butyl acrylate or styrene-2-ethylhexyl acrylate, n-, iso-, tert-burylacrylate being used as the butyl acrylate can be.
  • vinyl ester-ethylene copolymers such as vinyl acetate-ethylene copolymers, and copolymers of vinyl acetate and ethylene and vinyl esters of an ⁇ -branched carboxylic acid with 9 or 10 C atoms (VeoVa9 R , VeoValO R ), and in particular copolymers of vinyl acetate, Ethylene, vinyl ester of an ⁇ -branched carboxylic acid with 9 or 10 carbon atoms (VeoVa9 R , VeoVal0 R ) with copolymerizable silicone macromers; with an ethylene content of preferably 2 to 30 wt .-%, which may optionally contain additional auxiliary monomer in the amounts specified.
  • vinyl ester-ethylene copolymers such as vinyl acetate-ethylene copolymers, and copolymers of vinyl acetate and ethylene and vinyl esters of an ⁇ -branched carboxylic acid with 9 or 10 C atoms (VeoVa9 R , VeoValO R ),
  • the branched polysiloxanes b) contain structural elements of the formula Y [-C n H 2n - (R 2 SiO) m -A p -R 2 Si-G] x (I), where
  • Y is a tri- to tetravalent, preferably tri- to tetravalent, hydrocarbon radical which can contain one or more heteroatoms selected from the group of oxygen, nitrogen and silicon atoms,
  • R can be the same or different and represents a monovalent optionally halogenated hydrocarbon radical having 1 to 18 carbon atoms per radical,
  • A is a radical of the formula -R 2 Si-R 1 - (R 2 SiO) m -, where R 1 is a divalent hydrocarbon radical having 2 to 30 carbon atoms, which is separated from one another by one or more oxygen atoms, preferably 1 to 4 separate oxygen atoms can be interrupted, G means a monovalent radical of the formula -C n H 2n _ Z or -C n H 2n _ 2k -Z, or a divalent radical -C n H 2n -, the second bond to a further radical Y , Z means a monovalent hydrophilic radical, x is an integer from 3 to 10, preferably 3 or 4, k is 0 or 1, n is an integer from 1 to 12, preferably 2, an integer of at least 1, preferably an integer from 1 to 1000 and p is 0 or an integer positive number, preferably 0 or an integer from 1 to 20, with the proviso that the branched polysiloxanes contain on average at least one group Z and the group Z
  • the polysiloxanes with a branched structure generally contain chain-like siloxane blocks, the ends of which are each connected to the structural elements Y and Z via a C n H 2n bridge.
  • the polysiloxanes are constructed in such a way that siloxane blocks and organic blocks alternate with one another, the branching structures and the ends consisting of organic blocks. There are only stable Si-O-Si bonds or Si-C bonds in the molecule.
  • the ratio of end groups Z to branch groups Y (Z / Y ratio) is preferably 1.0 to 2.0, preferably 1.1 to 1.5.
  • the polysiloxanes b) preferably have a viscosity of 50 to 50,000,000 mPa's at 25 ° C, preferably 500 to 5,000,000 mPa's at 25 ° C and particularly preferably 1,000 to 1,000,000 mPa's at 25 ° C.
  • radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. -Butyl-, n-pentyl-, iso-pentyl-, neo-pentyl-, tert.
  • Pentyl hexyl such as the n-hexyl, heptyl such as the n-heptyl, octyl such as the n-octyl and iso-octyl such as the 2, 2, 4-trimethylpentyl, nonyl such as the n-nonyl , Decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-decadyl radical, and octadecyl radicals, such as the n-octadecyl radical; Cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals; Aryl radicals such as the phenyl, naphthyl, anthryl and phenanthryl radical; Alkaryl groups such as o-, m-, p-tolyl groups,
  • halogenated radicals R are haloalkyl radicals, such as the 3, 3, 3-trifluoro-n-propyl radical, the 2, 2, 2, 2 ', 2', 2 '-hexafluoro-isopropyl radical, the heptafluoroisopropyl radical and halogenaryl radicals, such as the o-, m- and p-chlorophenyl radical.
  • the radical R is preferably a monovalent hydrocarbon radical having 1 to 6 carbon atoms, the methyl radical being particularly preferred.
  • radicals R 1 are those of the formula ⁇ (CH 2 ) 2 -, - (CH 2 ) 4 -, - (CH 2 ) 6 -, - (CH 2 ) 8 -, - (CH 2 ) ⁇ o-, - C 6 H 4 -, -C 2 H 4 C 6 HC 2 H 4 -, -CH 2 CH (CH 3 ) CH 6 H 4 CH (CH 3 ) CH- and -C 2 H 4 -norbornanediyl-.
  • radical Y examples of the radical Y are those of the formula
  • Preferred Z radicals are derived from hydrophilic building blocks, which may be in monomeric, oligomeric or polymeric form, the solubility of which in water under normal conditions (DIN 50014, 23/50) is> 1 g / 1.
  • the molecular weight of the Z radicals is generally 30 to 10,000.
  • polymeric residues are polyols, polyethers such as polyalkylene oxides, preferably with methylene oxide, ethylene oxide
  • EO ethylene glycol
  • PO propylene oxide
  • Further examples are polyacids and their salts, preferably poly (meth) acrylic acid.
  • Suitable polymeric residues are also polyester, polyurea and polycarbonate residues. Copolymers of are also suitable
  • (Meth) acrylic acid ester monomers which still contain comonomer units ten with functional groups such as carboxyl, amide, sulfonate, dialkylammonium and trialkylammonium radicals.
  • Preferred (meth) acrylic acid ester monomers are those already mentioned above.
  • Preferred functional comonomers are those mentioned for the auxiliary monomers a). Most preferred are homo- and cocondensates of ethylene oxide and propylene oxide.
  • Examples of monomeric and oligomeric radicals Z are those with hydroxyl groups, carboxyl groups and their salts, sulfonic acid groups and their salts, sulfate groups, ammonium groups, keto groups, ether groups, ester groups, amide groups. Residues Z with an anionic and cationic charge and with a zwitterionic structure are preferred. Further examples of this are:
  • the silicone-containing polymers are produced by means of radical polymerization in an aqueous medium, preferably emulsion polymerization.
  • the polymerization is usually carried out in a temperature range from 20 ° C. to 100 ° C., in particular between 45 ° C. and 80 ° C.
  • the initiation is carried out by means of the customary radical formers, which are preferably used in amounts of 0.01 to 3.0% by weight, based on the total weight of the monomers.
  • Inorganic peroxides such as ammonium, sodium, potassium peroxodisulfate or hydrogen peroxide are preferably used as initiators either alone or in combination with reducing agents such as sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxylate or ascorbic acid used. It is also possible to use water-soluble organic peroxides, for example t-butyl hydroperoxide, cumol hydroperoxide, usually in combination with a reducing agent, or else water-soluble azo compounds.
  • the copolymerization with gaseous monomers such as ethylene and vinyl chloride is carried out under pressure, generally between 1 and 100 bar abs.
  • anionic and nonionic emulsifiers and protective colloids can also be used to stabilize the dispersion.
  • Nonionic or anionic emulsifiers are preferably used, preferably a mixture of nonionic and anionic emulsifiers.
  • Nonionic emulsifiers are preferably condensation products of ethylene oxide or propylene oxide with linear or branched alcohols with 8 to 18 carbon atoms, alkylphenols or linear or branched carboxylic acids of 8 to 18 carbon atoms, and block copolymers of ethylene oxide and propylene oxide are used.
  • Suitable anionic emulsifiers are, for example, alkyl sulfates, alkyl sulfonates, alkylaryl sulfates, and sulfates or phosphates of condensation products of ethylene oxide with linear or branched alkyl alcohols and with 5 to 25 EO units, alkylphenols, and mono- or diesters of sulfosuccinic acid.
  • the amount of emulsifier is 0.01 to 40% by weight, based on the total weight of the monomers a) used.
  • protective colloids can also be used.
  • suitable protective colloids are polyvinyl alcohols with a content of 75 to 95 mol%, preferably 84 to 92 mol%, vinyl alcohol units; Poly-N-vinylamides such as polyvinylpyrrolidones; Polysaccharides such as starches and celluloses and their carboxymethyl, methyl, hydroxyethyl, hydroxypropyl derivatives; synthetic polymers such as poly (meth) acrylic acid, poly (meth) acrylamide. The use of the polyvinyl alcohols mentioned is particularly preferred.
  • the protective colloids are generally used in an amount of 0.05 to 10% by weight, based on the total weight of the monomers a) used.
  • the usual regulators can be used to control the molecular weight, for example alcohols such as isopropanol, aldehydes such as acetaldehyde, chlorine-containing compounds, mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, mercaptopropionic acid (ester).
  • alcohols such as isopropanol
  • aldehydes such as acetaldehyde
  • chlorine-containing compounds such as n-dodecyl mercaptan, t-dodecyl mercaptan, mercaptopropionic acid (ester).
  • mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, mercaptopropionic acid (ester).
  • pH-regulating compounds such as sodium acetate or formic acid can be used in the preparation of the dispersion.
  • the polymerization can be carried out independently of the polymerization process with or without the use of seed latices, with presentation of all or individual constituents of the reaction mixture, or with partial presentation and replenishment of the or individual constituents of the reaction mixture, or according to the metering process without presentation.
  • the comonomers a) and, if appropriate, the auxiliary monomers can all be introduced to prepare the dispersion (batch process), or some of the monomers are introduced and the rest are metered in (semibatch process).
  • Component b) can be initially charged or metered in to prepare the dispersion, or a portion is initially charged and the rest is metered in.
  • the surface-active substances can be metered in alone or as a pre-emulsion with the comonomers.
  • the desired amount is introduced by setting a certain pressure.
  • the pressure at which the gaseous monomer is introduced can initially be set to a certain value and decrease during the polymerization, or the pressure is left constant throughout the polymerization. The latter embodiment is preferred.
  • postpolymerization can be carried out using known methods to remove residual monomers. For example, by post-polymerization initiated with a redox catalyst. Volatile residual monomers and other volatile, non-aqueous constituents of the dispersion can also be removed by distillation, preferably under reduced pressure, and if appropriate by passing or passing through inert entraining gases such as air, nitrogen or water vapor.
  • the aqueous dispersions obtainable by the process according to the invention have a solids content of 30 to 70% by weight, preferably 45 to 65% by weight.
  • the aqueous dispersions are dried, if appropriate after the addition of protective colloids as a spraying aid, for example by means of fluidized-bed drying, freeze drying or spray drying.
  • the dispersions are preferably spray dried. Spray drying is carried out in conventional spray drying systems, and atomization can be carried out using one-, two- or multi-component nozzles or with a rotating disc.
  • the outlet temperature is generally selected in the range from 45 ° C. to 120 ° C., preferably 60 ° C. to 90 ° C., depending on the system, the Tg of the resin and the desired degree of drying.
  • the atomization aid is used in a total amount of 3 to 30% by weight, based on the polymeric constituents of the dispersion.
  • Suitable colloidal aids are the protective colloids already mentioned.
  • a content of up to 1.5% by weight of antifoam, based on the base polymer has often proven to be advantageous.
  • the powder obtained can be equipped with an antiblocking agent (antibacking agent), preferably up to 30% by weight, based on the total weight of polymeric constituents.
  • antiblocking agents are calcium carbonate or magnesium carbonate, talc, gypsum, silica, kaolins, silicates.
  • Emulsion polymers are obtained which are hydrophobic, weather-resistant, water-repellent, very resistant, and not polluting and moreover have good water vapor permeability.
  • the silicone-containing polymers in the form of their aqueous dispersions and in the form of their polymer powders, in particular polymer powders redispersible in water are suitable for use in adhesives and coating compositions, for solidifying fibers or other particulate materials, for example for the textile sector. They are also suitable as modifiers and as water repellents. They can also be used in the Polish sector and in cosmetics, e.g. in the hair care sector. They are also suitable as binders in adhesives and coating agents, also as protective coatings e.g. for metals, foils, wood or release coating e.g. for paper treatment.
  • binders for paints, adhesives and coatings in the construction sector, for example in tile adhesives and full heat protection adhesives, and in particular for use in low-emission plastic emulsion paints and plastic dispersion plasters, both for indoor and outdoor use.
  • the recipes for emulsion paints and dispersion plasters are known to the person skilled in the art and generally contain 5 to 50% by weight of the silicone-containing polymers, 5 to 35% by weight of water, 5 to 80% by weight of filler, 5 to 30% by weight. % Of pigments and 0.1 to 10% by weight of further additives, the details in% by weight in the recipe adding up to 100% by weight.
  • fillers examples include carbonates such as calcium carbonate in the form of dolomite, calcite and chalk. Further examples are silicates, such as magnesium silicate in the form of talc, or aluminum silicates, such as clay and clays; Quartz flour, quartz sand, finely divided silica, feldspar, heavy spar and light spar. Fiber fillers are also suitable. In practice, mixtures of different fillers are often used. For example, mixtures of different fillers Particle size or mixtures of carbonate and silicate fillers. In the latter case, a proportion of more than 50% by weight, in particular more than 75% by weight, of carbonate or silicate in the total filler fraction is referred to as formulations rich in carbonate or silicate.
  • Plastic plasters generally contain coarser-grained fillers than emulsion paints. The grain size is often between 0.2 and 5.0 mm. Otherwise, plastic plasters can contain the same additives as emulsion paints.
  • Suitable pigments are, for example, titanium dioxide, zinc oxide, iron oxides, carbon black as inorganic pigments, and the customary organic pigments.
  • examples of other additives are wetting agents in proportions of generally 0.1 to 0.5% by weight, based on the total weight of the formulation. Examples include sodium and potassium polyphosphates, polyacrylic acids and their salts.
  • Additives also include thickeners, which are generally used in an amount of 0.01 to 2.0% by weight, based on the total weight of the formulation. Common thickeners are cellulose ether, starches or bentonite as an example of an inorganic thickener. Other additives are preservatives, defoamers, antifreezes.
  • the polymer dispersion or the polymer powder is mixed and homogenized with the other formulation constituents, filler and other additives, in suitable mixers.
  • the polymer powder can optionally also be added in the form of an aqueous redispersion at the construction site. In many cases a dry mix is made and the water required for processing is added immediately before processing. In the production of pasty masses, the water content is often initially introduced, the dispersion is added and the solids are then stirred in.
  • the silicone-containing polymers are particularly advantageous as binders in coating composition formulations for emission- poor interior paints, especially those with high PVC (highly filled colors), or suitable as a hydrophobizing binder for plasters.
  • the total amount of the SiH-functional highly branched siloxane polymer is mixed with 3200 g of a mono-allyl-terminated polyether from equal molar amounts of ethyleneoxy and propyleneoxy groups and an average molecular weight (Mn) of 1880 Da, with 5 g of a solution of hexachloroplatin - Acid activated in isopropanol (0.5% Pt content) and heated to 100 ° C. After the batch has been clarified, the mixture is left to react for 1 h, after which a conversion of> 98% is achieved.
  • the highly branched polyether siloxane copolymer has a viscosity of 6800 m 2 / s and a polyether content of approx. 62% by weight. It can be homogeneously dispersed in water without the use of other auxiliary substances.
  • the total metering time for the monomer metering was 5.3 h and for the emulsifier metering 5.0 h.
  • the APS dosage was reduced to 636 g per hour and the Na sulfite dosage to 1226 g per hour.
  • the "GMA metering” was run in 30 minutes after the end of the emulsifier metering. Composition of the "GMA metering”: 4.94 kg of vinyl acetate and 1.48 kg of glycidyl methacrylate. The dosing time was 30 minutes (rate: 12.84 kg per hour). After the “GMA metering” had ended, the APS and Na sulfite metering was continued for a further hour. After the pressure had been released, the dispersion was treated with “steam” (“stripped”) in order to minimize residual monomers and then preserved with Hydorol W. Dispersion analyzes: see Table 1
  • an emulsifier metering was run in with a metering rate of 12.89 kg per hour.
  • the emulsifier dosage contained 45.69 kg water and 25.20 kg Genapol X 150 (40% aqueous solution).
  • the total metering time for the monomer metering was 5.8 h and 5.5 h for the emulsifier metering.
  • the APS dosage was reduced to 636 g per hour and the Na sulfite dosage to 1226 g per hour.
  • the “GMA metering” was run in 30 minutes after the end of the emulsifier metering.
  • Composition of the “GMA metering” 4.80 kg of vinyl acetate, 720.01 g of Veova 10 and 2.88 kg of glycidyl methacrylate.
  • the dosing time was 30 minutes (rate: 16.8 kg per hour).
  • the APS and Na sulfite metering was continued for a further hour. After the pressure had been released, the dispersion was treated with “steam” (“stripped”) to minimize residual monomers and then preserved with Hydorol W. Dispersion analyzes: see Table 1
  • an emulsifier metering was run in with a metering output of 12.31 kg per hour.
  • the emulsifier dosage contained 12.18 kg water and 54.74 kg Genapol PF 80 (19.2% aqueous solution).
  • the total metering time for the monomer metering was 5.8 h and 5.5 h for the emulsifier metering.
  • the APS dosage was reduced to 636 g per hour and the Na sulfite dosage to 1226 g per hour.
  • the “GMA metering” was run in 30 minutes after the end of the emulsifier metering.
  • Composition of the “GMA metering” 5.01 kg of vinyl acetate, 750.78 g of Veova 10 and 3.00 kg of glycidyl methacrylate.
  • the dosing time was 30 minutes (rate: 17.52 kg per hour).
  • the APS and Na sulfite metering was continued for a further hour. After the pressure had been released, the dispersion was treated with “steam” (“stripped”) to minimize residual monomers and then preserved with Hydorol W. Dispersion analyzes: see Table 1
  • Example 4 (copolymer analogous to Example 2 with component b)
  • the emulsifier dosage contained 2.04 kg water and 340.61 g component b).
  • the total metering time for the monomer metering was 5.8 h and 5.5 h for the emulsifier metering.
  • the APS dosage was reduced to 42.2 g per hour and the Na sulfite dosage to 52.7 g per hour.
  • the "GMA metering” was run in 30 minutes after the end of the emulsifier metering.
  • Composition of the "GMA metering” 170.31 g of vinyl acetate, 25.55 g of Veova 10 and 51.09 g of glycidyl methacrylate.
  • the dosing time was 30 minutes (rate: 494 g per hour).
  • the APS and Na sulfite metering was continued for a further hour.
  • the dispersion was treated with “steam” (“stripped”) to minimize residual monomers and then preserved with Hydorol W. Dispersion analyzes: see Table 1
  • Example 5 (Analogous to Example 4 without Mersolat)
  • an emulsifier metering was run in at a rate of 431 g per hour.
  • the emulsifier dosage contained 2.03 kg water and 338.38 g component b).
  • the total metering time for the monomer metering was 5.8 h and 5.5 h for the emulsifier metering.
  • the APS dosage was reduced to 42.2 g per hour and the Na sulfite dosage to 52.7 g per hour.
  • the “GMA metering” was run in 30 minutes after the end of the emulsifier metering.
  • Composition of the “GMA metering” 169.19 g of vinyl acetate, 25.38 g of Veova 10 and 50.76 g of glycidyl methacrylate.
  • the dosing time was 30 minutes (rate: 491 g per hour).
  • the APS and Na sulfite metering was continued for a further hour.
  • the dispersion was treated with “steam” (“stripped”) to minimize residual monomers and then preserved with Hydorol W. Dispersion analyzes: see Table 1
  • Example 7 (Analogously to Example 5 with less polyvinyl alcohol) 2.23 kg of water, 425.65 g of W25 / 140 (polyvinyl alcohol; 10% solution), 567.54 g of component b) (15% aqueous solution), 157.86 g of mersolate (30% aqueous solution) were placed in a 19 liter pressure autoclave. , 68.10 g of sodium vinyl sulfonate (25%), 851.31 g of vinyl acetate, 170.26 g of PDMS mixture and 851.31 g of VeoVa 10. The pH was adjusted to 5 with 10% formic acid.
  • the APS dosage was reduced to 42.2 g per hour and the Na sulfite dosage to 52.7 g per hour.
  • the “GMA metering” was run in 30 minutes after the end of the emulsifier metering.
  • Composition of the “GMA metering” 170.26 g of vinyl acetate, 25.54 g of Veova 10 and 51.08 g of glycidyl methacrylate.
  • the dosing time was 30 minutes (rate: 494 g per hour).
  • the APS and Na sulfite metering was continued for a further hour.
  • the dispersion was treated with “steam” (“stripped”) to minimize residual monomers and then preserved with Hydorol W.
  • Example 8 (copolymer without silicone macromer)
  • the emulsifier dosage contained 1000.0 g W 25/140 (polyvinyl alcohol; 10% solution) and 2.36 kg component b) (15% aqueous solution).
  • the total metering time for the monomer metering was 5.8 h and 5.5 h for the emulsifier metering.
  • the APS dosage was reduced to 42.2 g per hour and the Na sulfite dosage to 52.7 g per hour.
  • the “GMA metering” was run in 30 minutes after the end of the emulsifier metering. Composition of the “GMA metering”: 177.20 g of vinyl acetate and 53.16 g of glycidyl methacrylate. The dosing time was 30 minutes (rate: 462 g per hour). After the “GMA metering” had ended, the APS and Na sulfite metering was continued for 1 hour.
  • Dispersion analyzes see Table 1 Table 1: Dispersion analyzes
  • Dn average particle size (number average, Coulter Counter),
  • Table 5 shows the application data.
  • Example 8 shows that the use of the silicone-containing polymer can significantly increase the hydrophobicity in all formulations.
  • Example 8 copolymer without silicone macromer
  • Examples 4, 5, 6 and 7 shows, the hydrophobicity can be markedly improved once again if a polymerizable silicone macromer is also polymerized into the silicone-containing polymer.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Silicon Polymers (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Cosmetics (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des polymérisats aux silicones obtenus par polymérisation radicalaire de monomères éthyléniquement insaturés en présence d'un polysiloxane. Les polymérisats selon l'invention sont caractérisés en ce que a) 60 à 99,99 % en poids d'un ou de plusieurs monomères, provenant du groupe comprenant des vinylesters d'acides alkylcarboxyliques linéaires ou ramifiés ayant 1 à 15 atomes de C, des méthacrylates et des acrylates d'alcools ayant 1 à 15 atomes de C, des composés aromatiques vinyliques, des oléfines, des diènes et des halogénures vinyliques, sont polymérisés en présence de b) 0,01 à 40 % en poids d'au moins un polysiloxane ramifié dont la part siloxane lipophile contient des structures ramifiées et dont la part polymère organique hydrophile peut être linéaire ou ramifiée, les indications de pourcentage en poids se rapportant au poids total de a) et b).
EP03795917A 2003-01-20 2003-12-18 Polymerisats aux silicones Withdrawn EP1587849A3 (fr)

Applications Claiming Priority (3)

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DE10301976 2003-01-20
DE10301976A DE10301976A1 (de) 2003-01-20 2003-01-20 Silikonhaltige Polymerisate
PCT/EP2003/014490 WO2004065441A2 (fr) 2003-01-20 2003-12-18 Polymerisats aux silicones

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EP1587849A2 true EP1587849A2 (fr) 2005-10-26
EP1587849A3 EP1587849A3 (fr) 2005-11-02

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WO2004065441A2 (fr) 2004-08-05
CN1829752A (zh) 2006-09-06
JP2006513296A (ja) 2006-04-20
EP1587849A3 (fr) 2005-11-02
AU2003298202A1 (en) 2004-08-13
WO2004065441A3 (fr) 2005-09-09
AU2003298202A8 (en) 2004-08-13
US20060116495A1 (en) 2006-06-01

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