EP1807471A1 - Procede de production de polymerisats modifies par silicone - Google Patents

Procede de production de polymerisats modifies par silicone

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Publication number
EP1807471A1
EP1807471A1 EP05806523A EP05806523A EP1807471A1 EP 1807471 A1 EP1807471 A1 EP 1807471A1 EP 05806523 A EP05806523 A EP 05806523A EP 05806523 A EP05806523 A EP 05806523A EP 1807471 A1 EP1807471 A1 EP 1807471A1
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EP
European Patent Office
Prior art keywords
silicone
ethylenically unsaturated
vinyl
water
prepolymer
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.)
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Application number
EP05806523A
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German (de)
English (en)
Inventor
Kurt Stark
Christian HÖGL
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Wacker Chemie AG
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Wacker Chemie AG
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Publication date
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Publication of EP1807471A1 publication Critical patent/EP1807471A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • 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
    • 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
    • C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • 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
    • 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 invention relates to a process for the preparation of silicone-modified polymers of ethylenically unsaturated monomers in the form of their aqueous polymer dispersions or water-redispersible polymer powders.
  • EP-A 771826 discloses a process for the preparation of a crosslinked silicone copolymer latex, in which initially water, monomer, emulsifier and water-soluble initiator are initially charged, the reaction is started, further monomer is slowly metered in, and finally the crosslinking agent Silicone, which is short-chain and polyunsaturated, is added together with the remaining monomer.
  • 6,609,949 describes the preparation of silicone-organopolymer graft polymers, in which a branched, short-chain silicone having a dendrimeric structure with ethylenically unsaturated radical, ethylenically unsaturated monomers and free-radically polymerizable emulsifier are reacted in the presence of an oil-soluble initiator.
  • the dendritic structure of the short-chain silicone macromer improves the copolymerization with organic monomers. It is shown in comparative examples that long-chain silicone macromers (without dendrimeric structure) have polymerized only up to a maximum of 75% with organic monomers and a large amount of unreacted silicone macromer remains.
  • EP-A 810243 are silicone macromers with organic monomers in Emulsion polymerized, being carried out exclusively with oil-soluble initiator.
  • a disadvantage of the methods under initiation with oil-soluble initiator is the insufficient stability of the resulting dispersions, which are very prone to phase separation.
  • JP-A 09-052923 describes a process for the preparation of silicone-containing graft polymers in which first a mixture of organopolysiloxane and ethylenically unsaturated silane is polymerized and then vinyl monomer is added in two stages for grafting.
  • the invention relates to a process for the preparation of silicone-modified polymers of ethylenically unsaturated monomers in the form of their aqueous polymer dispersions or water-redispersible polymer powder, characterized in that
  • a prepolymer is prepared and isolated by polymerization of one or more ethylenically unsaturated monomers and at least one silicone macromer having ethylenically unsaturated groups,
  • this solution is emulsified in water and free-radically polymerized, and optionally D) the aqueous dispersion of the polymers modified with silicone is dried.
  • one or more monomers are used as ethylenically unsaturated monomers from the group comprising vinyl esters of unbranched or branched alkylcarboxylic acids having 1 to 15 carbon atoms, methacrylic acid esters and acrylic esters of alcohols having 1 to 15 carbon atoms. Atoms, vinyl aromatics, olefins, dienes and vinyl halides. In general, from 1 to 99% by weight of the ethylenically unsaturated monomers are used, preferably from 40 to 95% by weight, based in each case on the total weight of silicone macromer and monomer.
  • 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-methylvinyl acetate, vinyl pivalate and vinyl esters of ⁇ -branched monocarboxylic acids having 5 to 13 C atoms, for example VeoVa9 R or VeoVal0 R ( Trading name of the company Resolution Performance Products). Particularly preferred is vinyl acetate.
  • Suitable monomers from the group of esters of acrylic acid or methacrylic acid are esters of unbranched or branched ver ⁇ branched alcohols having 1 to 15 carbon atoms.
  • Preferred methacrylic esters or acrylates are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, polypropyl acrylate, propyl methacrylate, n-, iso- and t-butyl acrylate, n-, iso- and t-butyl methacrylate, 2-ethylhexyl acrylate, norboyl acrylate , Particularly preferred are methyl acrylate, methyl methacrylate, n-, iso- and t-butyl acrylate, 2-ethylhexyl acrylate and norbornyl acrylate.
  • Suitable dienes are 1,3-butadiene and isoprene.
  • Examples of copolymerizable olefins are ethene and propene.
  • vinylaromatics styrene and vinyltoluene can be copolymerized. From the group of vinyl halides usually vinyl chloride, vinylidene chloride or vinyl fluoride, preferably vinyl chloride, are used.
  • auxiliary monomers can 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 nitrites, 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 salts thereof, preferably vinylsulfonic acid, 2-acrylamiclo-2-methylpropanesulfonic acid.
  • auxiliary monomers are cationic monomers such as diallyldimethylammonium chloride (DADMAC), 3-trimethylammoniumpropyl (meth) acrylamidechloroLd (MAPTAC) and 2-trimethylammoniumethyl (meth) acrylate chloride.
  • DMAC diallyldimethylammonium chloride
  • MATAC 3-trimethylammoniumpropyl (meth) acrylamidechloroLd
  • 2-trimethylammoniumethyl (meth) acrylate chloride are particularly suitable as auxiliary monomers.
  • vinyl ethers vinyl ketones, further vinylaromatic compounds which may also have heteroatoms.
  • Suitable auxiliary monomers are also polymerisable silanes or. Mercaptosilanes. Preference is gamma-acrylic or. gamma-meth acryloxypropyltri (alkoxy) silanes, ⁇ -methacryloxymethyltri (alkoxy) silanes, gamma-methacryloxypropylmethyldi (alkoxy) silanes, vinylalkyldi (alkoxy) silanes and vinyltri (alkoxy) silanes, alkoxy groups being, for example, methoxy, ethoxy, methoxyethylene , Ethoxyethylene, Methoxypropylenglykolether- or
  • Ethoxypropylenglykolether residues can be used.
  • these are vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltris (1-methoxy) isopropoxysilane, vinyltributoxysilane, vinyltriacetoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-imethacryloxypropylmethyldimethoxysilane, methacryloxymethyltrimethoxysilane, 3-methacryloxypropyltris (2-methoxyethoxy) silane, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyltris (2-methoxyethoxy) silane, trisacetoxyvinylsilane, 3- (triethoxysilyl) propylsuccinic anhydride silane. Also preferred are 3-
  • functionalized (meth) acrylates and functionalized alcohols and vinyl ethers in particular epoxy-functional compounds such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, vinyl glycidyl ether or hydroxyalkyl functionals such as hydroxyethyl (meth) acrylate, or substituted or unsubstituted aminoalkyl (meth) acrylates, or cyclic monomers, such as N-vinylpyrrolidone; or N-vinylformamide.
  • epoxy-functional compounds such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, vinyl glycidyl ether or hydroxyalkyl functionals such as hydroxyethyl (meth) acrylate, or substituted or unsubstituted aminoalkyl (meth) acrylates, or cyclic monomers, such as N-vinyl
  • auxiliary monomers are precursor comonomers, such as polyethylenically unsaturated comonomers, for example divinyl adipate, divinylbenzene, diallyl maleate, allyl methacrylate, butanediol diacrylate or triallyl cyanurate, or postcrosslinking comonomers, for example acrylamidoglycolic acid (AGA), methyl acrylamidoglycolate methyl ester (MAGME ), N-methylolacrylamide (NMA), N-methylolmethacrylamide, N-methylolallyl carbamate, alkyl ethers such as the isobmoxyether or esters of N-methylolacrylamide, N-methylolmethacrylamide and N-methylolallylcarbamate.
  • AGA acrylamidoglycolic acid
  • MAGME methyl acrylamidoglycolate methyl ester
  • NMA N-methylolacrylamide
  • NMA N-methylolme
  • Silicone macromers which are suitable for the preparation of the prepolymer are linear, branched, cyclic and three-dimensionally crosslinked polysiloxanes having at least 10 siloxane repeat units and having at least one free-radically polymerizable functional group.
  • the chain length is 10 to 10,000 siloxane repeating units.
  • Etlrylenisch unsaturated groups such as alkenyl groups are preferred as polymerizable functional groups.
  • R 1 a R3 a SiO (SiR 2 O) n SiR3- a R 1 a Bei ⁇ are games for R methyl, ethyl, n-propyl, iso-propyl, 1-n- Butyl, 2-n-butyl, iso-butyl, tert.
  • the radical R is preferably a monovalent hydrocarbon radical having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, A-methyl and hexyl Radical, the methyl radical being particularly preferred.
  • Preferred alkoxy radicals R are those having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy and n-butoxy radicals, which may optionally also be substituted by oxyalkylene radicals, such as oxyethylene or oxymethylene radicals. Particularly preferred are the methoxy and ethoxy.
  • the stated alkyl radicals and alkoxy radicals R may optionally also be sub- may be substituted, for example, with halogen, mercapto groups, epoxy-functional groups, carboxy groups, keto groups, enamine groups, amino groups, aminoethylamino groups, isocyanate groups, aryloxy groups, alkoxysilyl groups and hydroxyl groups.
  • Suitable polymerizable groups R 1 are alkenyl radicals having 2 to 8 C atoms.
  • Examples of such polymerizable groups are the vinyl, allyl, butenyl, and acryloxyalkyl and methacryloxyalkyl group, wherein the alkyl radicals contain 1 to 4 carbon atoms. Preference is given to the vinyl group, 3-methacryloxypropyl, acryloxymethyl and 3-acryloxypropyl group.
  • silicones which are only substituted by unsaturated groups
  • ⁇ -monovinyl-poly-dimethylsiloxanes ⁇ -mono- (3-acryloxypropyl) -polydimethylsiloxanes, ⁇ -mono- (acryloxymethyl) -polydimethylsiloxanes, ⁇ -mono- (3 - methacryloxypropyl) -Polydimethylsiloxane preferred.
  • an alkyl or alkoxy radical for example a methyl or butyl radical, is located at the other end of the chain.
  • the vinyl groups are at the end of the chain.
  • examples of such mixtures are silicones of the solvent-free Dehesive s -6 series (branched) or Dehesive ⁇ D -9 series (unbranched) of Wacker-Chemie GmbH.
  • the proportion of unfunctional polydialkylsiloxanes is at most up to 15% by weight, preferably up to 5% by weight; the proportion of monofunctional polydialkylsiloxanes up to 50% by weight; and the proportion of the difunctional Polydialkylsilo ⁇ xane at least 50 wt .-%, preferably at least 60 wt .-%, each based on the total weight of the Silikonmakromers.
  • the polymerizable Silikonmakroraere as described in EP-A 614924.
  • silicone macromers are ⁇ , ⁇ -divinyl-polydimethylsiloxanes, ⁇ -mono- (3-methacryloxypropyl) -polydimethylsiloxanes and ⁇ , ⁇ -di- (3-methacryloxypropyl) -polydimethylsiloxanes.
  • the preparation of the prepolymer in step A) takes place by means of radical polymerization by mass, solution, suspension or emulsion polymerization in an aqueous medium. Preference is given to the solution polymerization process and the suspension polymerization process.
  • Suitable solvents are esters such as methyl acetate and ethyl acetate, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, t-butanol, isopropanol, or mixtures thereof.
  • the polymerization is usually carried out in a, temperature-interval of 20 0 C to 100 0 C, in particular between 40 0 C and 80 0 C.
  • the silicone macromer with ethylenically ungesnostitig ⁇ th groups in an amount of 1 to 99 wt .-%, preferably used 5 to 60 wt .-%, in each case based on the total weight of silicone macromer and ethylenically unsaturated monomer.
  • Initiation takes place by means of free-radical initiators (initiators), which are preferably used in amounts of from 0.01 to 5.0% by weight, based on the total weight of silicone macromer and monomer. It is possible to work with water-soluble or oil-soluble initiator or mixtures thereof.
  • Suitable water-soluble initiators are those whose solubility in water under standard conditions is> 10% by weight.
  • water-soluble, inorganic peroxides such as ammonium, sodium, potassium peroxodisulfate or hydrogen peroxide, either alone or in combination with reducing agents, such as sodium sulfite, sodium hydrogen sulfite, sodium formaldehyde sulfoxylate or ascorbic acid.
  • reducing agents such as sodium sulfite, sodium hydrogen sulfite, sodium formaldehyde sulfoxylate or ascorbic acid.
  • water-soluble organic peroxides for example t-butyl hydroperoxide (TBHP), cumene hydroperoxide, usually in combination with reducing agent, are used, or even wasserlös ⁇ Liche azo compounds.
  • Oil-soluble initiators are those whose solubility in water under standard conditions is ⁇ 1% by weight.
  • Representatives of the group of oil-soluble initiators are initiators such as t-butyl peroxy-2-ethylhexanoate (TBPEH), t-butyl peroxypivalate (PPV), t-butyl peroxyneodecanoate (TBPND), dibenzoyl peroxide, t-amyl peroxypivalate (TAPPI), di - (2-ethylhexyl) peroxy dicarbonate (EHPC), 1, 1-bis (t-butylperoxy) -3, 3, 5-trimethylcyclohexane and di (4-t-butylcyclohexyl) peroxydicarbonatissue ⁇ sets.
  • Suitable oil-soluble initiators are also azo initiators such as azobisisobutyronitrile (AIBN).
  • the usual regulators may be used to control the molecular weight, for example alcohols such as isopropanol, aldehydes such as acetaldehyde, chlorine-containing compounds, mercaptans such as n-dodecylmercaptan, t-dodecylmercaptan, mercaptopropionic acid (ester).
  • alcohols such as isopropanol
  • aldehydes such as acetaldehyde
  • chlorine-containing compounds such as n-dodecylmercaptan, t-dodecylmercaptan, mercaptopropionic acid (ester).
  • mercaptans such as n-dodecylmercaptan, t-dodecylmercaptan
  • mercaptopropionic acid ester
  • pH-regulating compounds such as sodium acetate or formic acid can be used in the preparation of the dispersion.
  • step C If polymerization is carried out in an aqueous phase, the emulsifiers and protective colloids mentioned in the description of step C) can also be used for stabilization.
  • the polymerization can be carried out independently of the polymerization process with the introduction of all or individual constituents of the reaction mixture, or with partial introduction and subsequent metering of the or individual constituents of the reaction mixture, or after the metering process without preparation.
  • the prepolymer Upon completion of the polymerization, the prepolymer becomes isolated.
  • Wei ⁇ se by means of filtration, precipitation or distilling off the Lö ⁇ sungsstoffs.
  • the prepolymers thus obtained are dissolved in one or more ethylenically unsaturated monomers in the next step.
  • the proportion of prepolymer in the solution is preferably from 5 to 60% by weight, based on the total weight of prepolymer and ethylenically unsaturated monomer.
  • Suitable ethylenically unsaturated monomers are the monomers already mentioned under step A) from the group comprising vinyl esters of branched or unbranched alkylcarboxylic acids having 1 to 15 carbon atoms, methacrylic acid esters and acrylic esters of alcohols having 1 to 15 carbon atoms, vinylaromatics, Olefins, dienes and vinyl halides, and optionally also additionally the aforementioned auxiliary monomers in the stated amounts.
  • vinyl acetate Preference is given to vinyl acetate; Mixtures of vinyl acetate and ethylene; Mixtures of vinyl acetate with further vinyl esters such as vinyl laurate, vinyl pivalate, vinyl 2-ethylhexanoic acid ester, vinyl ester of an alpha-branched carboxylic acid, in particular vinyl versatate (VeoVa9 R , VeoVal0 R ), and optionally ethylene; Mixtures of vinyl ester, ethylene and vinyl chloride, vinyl esters preferably 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 Versaticklarevinylester (VeoVa9 R , VeoVal0 R ), ent are keep; Vinyl ester-acrylic acid ester mixtures with vinyl acetate and / or vinyl laurate
  • the abovementioned mixtures may also contain the stated auxiliary monomers in the stated amounts.
  • the solution of prepolymer and ethylenically unsaturated monomer is emulsified in water and preferably free-radically polymerized by the emulsion polymerization process.
  • the polyvinyl lymerisation is usually carried out in a temperature range from 20 0 C to 100 0 C. Initiation takes place by means of free-radical initiators (initiators), which are preferably used in quantities of from 0.01 to 5.0% by weight, based on the total weight of silicone organocopolymer and monomer. It can be worked with water-soluble or oil-soluble initiator or a mixture of such initiators. Suitable water-soluble and oil-soluble initiators are those already mentioned above.
  • Nonionic and nonionic emulsifiers and protective colloids are preferably used, more preferably a mixture of nonionic and anionic emulsifiers.
  • the nonionic emulsifiers used are preferably condensation products of ethylene oxide or propylene oxide with linear or branched alcohols having 8 to 18 carbon atoms, alkylphenols or linear or branched carboxylic acids having 8 to 18 carbon atoms, and also block copolymers of ethylene oxide and propylene oxide.
  • 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 3 to 60 EO units, alkylphenols, and mono- or diesters of sulfosuccinic acid.
  • the amount of emulsifier is 0.1 to 30
  • protective colloids can still be used.
  • suitable protective colloids are polyvinyl alcohols having 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.
  • polyglycol ethers such as polyethylene glycol, polypropylene glycol or mixed polyalkylene oxides having ethylene oxide and propylene oxide groups. Particularly preferred is the use of said polyvinyl alcohols. Preference is also given to the use of polyalkylene oxides which have at least one but at most two polymerizable groups, for example the vinyl or the allyl group.
  • the protective colloids are generally in an amount of from 0.1 to 30% by weight, based on the total weight of the monomer and prepolymer used.
  • the usual regulators may be used to control the molecular weight, for example alcohols such as isopropanol, aldehydes such as acetaldehyde, chlorine-containing compounds, mercaptans such as n-dodecylmercaptan, t-dodecylmercaptan, mercaptopropionic acid (ester).
  • alcohols such as isopropanol
  • aldehydes such as acetaldehyde
  • chlorine-containing compounds such as n-dodecylmercaptan, t-dodecylmercaptan, mercaptopropionic acid (ester).
  • mercaptans such as n-dodecylmercaptan, t-dodecylmercaptan
  • 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 latexes, all or individual constituents of the reaction mixture being prepared, or with partial introduction and subsequent addition of the or individual constituents of the reaction mixture, or after the metered addition process without preparation.
  • the prepolymer is always introduced dissolved in the monomer.
  • the emulsifiers and protective colloids can be initially charged for the preparation of the dispersion or metered in, or a portion is initially charged and the remainder is metered.
  • the desired amount is introduced by setting a bestimm ⁇ th pressure.
  • the pressure with which the gaseous monomer is introduced can initially be set to a specific value and degrade during the polymerization, or the pressure is kept constant during the entire polymerization. The latter embodiment is preferred.
  • Volatile residual monomers and other volatile, non-aqueous constituents of the dispersion can also be removed by means of distillation, preferably under reduced pressure, and, if appropriate, by passing or passing inert inert gases, such as air, nitrogen or steam.
  • the aqueous dispersions obtainable by the process according to the invention have a solids content of from 20 to 70% by weight, preferably from 25 to 65% by weight.
  • the setting of the Festge ⁇ haltes can also suc ⁇ by subsequent addition of water gene after the emulsion has been completed.
  • the aqueous dispersions are dried, if appropriate after addition of protective colloids as atomization aid, for example by means of fluidized bed drying, freeze drying or spray drying.
  • the dispersions are spray-dried.
  • the spray drying is carried out in conventional spray drying systems, wherein the atomization can be done by means of one-, two- or multi-fluid nozzles or with a rotating disk.
  • the outlet temperature is generally in the range of 45 ° C to 120 0 C, preferably 60 0 C to 90 0 C, depending on the system, Tg of the resin and the desired degree of drying selected.
  • the atomization aid is used in a total amount of from 3 to 30% by weight, based on the polymeric constituents of the dispersion. Suitable atomization aids are the already mentioned protective colloids. During atomization, a content of up to 1.5% by weight of antifoam, based on the base polymer, has proven to be favorable.
  • the powder obtained can be equipped with an antiblocking agent (anticaking agent), preferably up to 30% by weight, based on the total weight of polymeric constituents. Examples of antiblocking agents are Ca or Mg carbonate, talc, gypsum, silicic acid, kaolins, silicates.
  • the procedure according to the invention makes it possible to obtain silicone-containing copolymers which are distinguished by complete attachment of the silicone fraction to the organic fraction, which is ensured by the separate preparation of the prepolymer.
  • the dispersions thus obtained have a number of advantages: Advantageous Sectionchengrö ⁇ .verotti, storage stability, no phase separation, no sweating of the silicone, no specks and an ex ⁇ zellente film formation. Non-lubricating films with high cohesion and favorable mechanical behavior are obtained.
  • the silicone can unfold its effect in the form of the previously formed silicone organocopolymer; B. lead to release behavior and hydrophobic behavior.
  • the effect of the silicone organocopolymer can also be caused by thermal activation.
  • copolymers in the form of their aqueous dispersions and water-redispersible powders are suitable for use in adhesives, coating compositions, as well as a protective coating z. B. for metals, foils, wood or release coating or for paper treatment, eg. B. in the tissue sector, as a binder for the consolidation of fibers or other particles ticular materials.
  • dispersions can be used as release agents They are also suitable as binders in the construction sector for paints, adhesives and coating compositions, for example in tile adhesives and non-thermal protection adhesives, and especially for use in low-emissivity They can also be used as an additive, for example in paints or in cosmetic formulations, such as hairsprays, creams, lotions or shampoos.
  • copolymers in the form of their aqueous dispersions and water-redispersible powders are furthermore suitable as binders for toners for producing silicone-modified toner particles.
  • Composition 33 wt .-% polydimethylsiloxane and. 67% by weight
  • the initiator feed (4.03 kg of ethyl acetate and 199.3 g PPV) at a rate of 819.0 g / h.
  • Ten minutes after the start of the initiator feed was the Monomerdosie tion (7.88 kg Wacker silicone macromer VIPO 300 ® and 15.99 kg of vinyl acetate) at a rate of 5.97 kg / h retracted.
  • the iodine dosing extended over a period of 310 min, the monomer dosing ended 60 min earlier. After the end of both dosages further 120 min at 7O 0 C was nachpolymerisie rt.
  • Prepolymer prepared by suspension polymerization composition 30.0% by weight polydimethylsiloxane (silicone), 70.0% by weight styrene
  • composition 30.0% by weight polydimethylsiloxane (silicone) 70.0% by weight styrene
  • a 500 l stirred tank with stirrer, reflux condenser, metering device, heater (with temperature control) and nitrogen inlet 237.35 kg of deionized Water, 771.94 g of copper acetate (1% aqueous solution) and 10.29 kg of polyvinylpyrrolidone (5% aqueous solution) submitted.
  • the solution was stirred at 100 rpm.
  • the monomer mixture with the initiators was stirred for a short time at room temperature and then added slowly to the aqueous receiver in the stirred tank.
  • the kettle contents were mixed by stirring at 100 rpm, whereupon the monomers were suspended in water. Subsequently, the temperature was raised to 55 0 C and held for 4 hours.
  • the temperature was raised at a ramp of 0.1 ° C / min to 60 0 C and held for 4 h. Then it was heated to 65 ° C. with a temperature ramp of 0.1 ° C./min. This temperature was held for 4 hours. Then it was heated to 7O 0 C with a temperature ramp of 0.1 ° C / min. This temperature was held for 4 hours. The temperature was then increased at a ramp of 0.1 ° C / min to 75 0 C and held for 4 h. To polymerize seine span-, the temperature was raised to 80 0 C and held for 2 hours. The batch was subjected to steam treatment to drive off volatile compounds and finally cooled to room temperature. The resulting beads were separated by a filtration step from the suspending medium, ie from the water. The beads were washed several times with water and then dried. Highly transparent, hard beads were obtained.
  • Mersolat K30 Na alkyl sulfonate with 12 to 14 C atoms in the alkyl radical.
  • Genapol X050 C 13 oxo alcohol ethoxylate with 5 EO Texapon K12: Na dodecyl sulfate
  • Genapol PF80 EO-PO block polymer with 80% EO.
  • Brüggolith sodium formaldehyde sulfoxylate (reducing agent)
  • Polyvinyl alcohol W25 / 140 polyvinyl alcohol with a Viskosi ⁇ ty of about 25 mPas (20 0 C, 4% solution, measured according to Höppler), and a saponification value of 140 (mg KOH / g polymer) ( Degree of hydrolysis 88 mol%).
  • the kettle was heated to 60 0 C.
  • the temperature of 60 0 C was maintained for 2 hours while stirring at 300 rpm.
  • the dispersion was treated with steam for stripping the residual monomer ("stripped") and then preserved with Hydorol W.
  • the dispersion was diluted with 185 g of water before filling.A homogeneous and stable dispersion was obtained.
  • Example 2 In a 2 liter stirred apparatus with anchor stirrer were
  • Example 3 116.74 g of W 25/140 (polyvinyl alcohol, 10% strength aqueous solution), 29.18 g of Genapol PF 80 (20% strength aqueous solution), 2.22 g of Mersolat K30 (30% strength aqueous solution) were mixed in a 2 liter stirring apparatus with anchor stirrer ) submitted.
  • W 25/140 polyvinyl alcohol, 10% strength aqueous solution
  • 29.18 g of Genapol PF 80 (20% strength aqueous solution)
  • 2.22 g of Mersolat K30 (30% strength aqueous solution) were mixed in a 2 liter stirring apparatus with anchor stirrer ) submitted.
  • a previously prepared solution of 23.35 g of a silicone organocopolymer having a composition of 70.0% by weight of styrene and 30.0% by weight of silicone (prepared in Example b)) in 93.4 g of vinyl acetate was added. This original was stirred at 300 rpm. With 10% formic
  • the reaction was stirred at 200 rpm.
  • the total dosing time for the pre-emulsion dosing was 3 hours.
  • the TBHP and Brüggolitdostechnik continued for 1 hour.
  • the dispersion was then treated with water vapor ("stripped") for residual monomer minimization and preserved with Hydorol W. Before dispersion, the dispersion was diluted with 200 g of water to give a homogeneous and stable dispersion.
  • a mixture in the form of a pre-emulsion of 210.56 g of water, 366.19 g W 25/140 (polyvinyl alcohol, 10% aqueous solution), 91.55 g of Genapol PF 80 (20% aqueous Lö solution), 6.96 g of Mersolat K30 (30% strength aqueous solution) and a previously prepared solution of 73.24 g of a silicone organocopolymer having the composition 67.0% by weight of vinyl acetate and 33.0% by weight of silicone (prepared in Example a)) in 292.95 g of methyl methacrylate at a rate of 346.7 g per hour to meter (pre-emulsion dosage).
  • EXAMPLE 6 91.55 g of water, 91.55 g of W 25/140 (polyvinyl alcohol, 10% strength aqueous solution), 22.89 g of Genapol PF 80 (20% strength aqueous solution), 1.74 g of Mersolat K30 were used in a 2 liter stirring apparatus with anchor stirrer (30% aqueous solution) submitted. To this was added a previously prepared solution of 18.31 g of a SiIi konorganocopolymeren the composition 70.0 wt .-% of styrene and 30 wt .-% silicone (prepared in Example b)) in 36.62 g of methyl methacrylate and 36.62 g of butyl acrylate.
  • Solids content 37.54%; pH: 4.9; Brookfield viscosity 20 (spindle 4): 12300 mPas; Glass transition temperature Tg:
  • the emulsifier dosage contained 385.32 g of water, 406.18 g of Genapol X 050, and 462.62 g of Texapon K12 (10% aqueous solution).
  • the total dosing time for the monomer metering and the emulsifier doses amounted to 2 hours.
  • the APS dosage was increased to 126 g per hour, the Na sulfite dosage to 262 g per hour.
  • Solids content 50.5%, pH value: 5.3; Brookfield viscosity 20 (spindle 4): 1040 mPas; MFT: 0 C; Glass transition temperature
  • Comparative Example 7 shows that with conventional emulsion polymerization-in this case vinyl acetate with silicone macromer-an insufficient attachment of the silicone macromer to the organic monomer takes place, which is also described in the literature. During the extraction, 38.8% of the constituents could be washed out of a dried dispersion film. 1H NMR spectroscopy showed that most of the extractable components were free silicone macromers.

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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)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Silicon Polymers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Cosmetics (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne un procédé permettant de produire des polymérisats de monomères insaturés par voie éthylénique, modifiés par silicone, se présentant sous forme de leurs dispersions polymères aqueuses ou de poudres polymères redispersibles dans l'eau. Ledit procédé se caractérise en ce que: A) un prépolymère est produit par polymérisation d'un ou de plusieurs monomères insaturés par voie éthylénique et d'au moins un macromère de silicone avec des groupes insaturés par voie éthylénique, puis est isolé; B) le prépolymère ainsi obtenu est dissous dans un ou plusieurs monomères insaturés par voie éthylénique; C) cette solution est émulsionnée dans de l'eau et polymérisée par voie radicalaire, et éventuellement D) la dispersion aqueuse ainsi obtenue des polymérisats modifiés par silicone est séchée.
EP05806523A 2004-11-04 2005-10-20 Procede de production de polymerisats modifies par silicone Withdrawn EP1807471A1 (fr)

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DE102004053314A DE102004053314A1 (de) 2004-11-04 2004-11-04 Verfahren zur Herstellung von mit Silikon modifizierten Polymerisaten
PCT/EP2005/011301 WO2006048133A1 (fr) 2004-11-04 2005-10-20 Procede de production de polymerisats modifies par silicone

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AU2007291337B2 (en) * 2006-08-28 2011-11-03 Allnex Belgium S.A. Polymer compositions
US20100145001A1 (en) * 2006-12-12 2010-06-10 Unilever Plc branched organic-inorganic polymers
DE102007058713A1 (de) 2007-12-06 2009-06-10 Evonik Goldschmidt Gmbh Silicon(meth-)acrylat-Partikel, Verfahren zu deren Herstellung sowie deren Verwendung
DE102010001528A1 (de) 2010-02-03 2011-08-04 Evonik Goldschmidt GmbH, 45127 Neue Partikel und Kompositpartikel, deren Verwendungen und ein neues Verfahren zu deren Herstellung aus Alkoxysilylgruppen tragenden Alkoxylierungsprodukten
JP5855101B2 (ja) * 2010-08-03 2016-02-09 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ マルチビニルシロキサンオリゴマーベースのポリマー分散液およびその製造方法およびその使用
TWI530509B (zh) * 2011-03-31 2016-04-21 Shinetsu Chemical Co Cationic (meth) acrylic acid polysiloxane graft copolymer and cosmetics containing the same
JP6403379B2 (ja) * 2012-12-18 2018-10-10 日本合成化学工業株式会社 整髪剤用アクリル系樹脂エマルジョン、およびそれを含有する整髪剤、並びに整髪方法
DE102013217221A1 (de) * 2013-08-28 2015-03-05 Wacker Chemie Ag Vernetzbare Massen auf der Basis von Organosiliciumverbindungen und daraus hergestellte Formkörper
DE102013226568A1 (de) 2013-12-19 2015-06-25 Evonik Industries Ag Silicon(meth-)acrylat-Partikel, Verfahren zu deren Herstellung sowie deren Verwendung
CN105153346A (zh) * 2015-09-29 2015-12-16 南通瑞普埃尔生物工程有限公司 多元共聚锈转化底漆专用水性防腐乳液及其制备方法
CN115073649B (zh) * 2022-07-20 2023-10-27 智仑超纯环氧树脂(西安)有限公司 一种除氯剂及其制备方法和应用

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JP2008519114A (ja) 2008-06-05
KR20070084629A (ko) 2007-08-24
US20090104238A1 (en) 2009-04-23
TW200635966A (en) 2006-10-16
BRPI0517779A (pt) 2008-10-21
CN101056931A (zh) 2007-10-17
DE102004053314A1 (de) 2006-05-11

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