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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/42—Introducing metal atoms or metal-containing groups
• • 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
  • C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
  • C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
  • C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol

Definitions

• the invention relates to silane-modified polyvinyl alcohols, a novel process for the preparation of silane-modified polyvinyl alcohols, and their use.
• Polyvinyl alcohol and polyvinyl alcohol copolymers find various applications as binders, as protective colloid in emulsion and suspension polymerization, as co-binder in paper coatings, and as oxygen barrier in the packaging industry.
• the modification of polyvinyl alcohol with silane groups gives higher strengths and better binding to minerals such as pigments, fillers and glass.
• Silane-modified polyvinyl alcohols have been by means of co-polymerization of vinyl acetate and ethylenically unsaturated silane and subsequent hydrolysis produced, or by subsequent silylation of the vinyl alcohol units of polyvinyl alcohol with a silylating agent having at least two hydrolyzable groups 0.
• EP 0076490 A1 describes a paper coating composition based on silanized polyvinyl alcohols, which are accessible by means of the two mentioned process variants.
• EP 1127706 A1 relates to inkjet recording materials which have a coating with silicone-functional polyvinyl alcohol, the silanized polyvinyl alcohols used there also being obtainable with these two aforementioned process variants.
• silanized polyvinyl alcohols from EP 1380599 A1 and EP 1380600 are obtained by copolymerization of vinyl ester and ethylenically unsaturated silanes and subsequent hydrolysis of the silanized polyvinyl esters, where appropriate if necessary, can be polymerized in the presence of mercapto compounds.
• EP 1080940 A2 describes three alternatives for the preparation of silanized polyvinyl alcohols: Vinyl ester is copolymerized with olefinically unsaturated monomers with silyl group and then hydrolyzed.
• Vinyl ester is copolymerized with epoxy-functional comonomers, the copolymer thus obtained is reacted with a compound containing both mercapto and silyl groups, and then hydrolyzed. Vinyl ester is copolymerized in the presence of a compound 0 with mercapto and silyl groups and then hydrolyzed.
• WO 2004/013190 A1 describes the preparation of silane-modified polyvinyl alcohols, wherein vinyl esters are polymerized in the presence of silane-containing aldehydes, and the vinyl ester polymer thus obtained
• the invention provides silane-modified polyvinyl alcohols obtainable by treating vinyl alcohol polymers with one or more ethylenically unsaturated, silane-containing monomers at elevated temperature.
• Suitable vinyl alcohol polymers are partially or fully hydrolyzed vinyl ester polymers having a degree of hydrolysis of preferably 50 mol% to 99.99 mol%, more preferably from 70 mol% to 99 mol%, most preferably from> 96 mol%. %. Fully hydrolyzed is understood as meaning those polymers whose degree of hydrolysis is> 96 mol%. As partially hydrolyzed vinyl ester lymerisate are those with a degree of hydrolysis> 50 mol% and ⁇ 96 mol%.
• the viscosity of the vinyl alcohol polymer (DIN 53015, Höppler method, 4% solution in water) is 1 to 60 mPas, preferably 1 to 10 mPas, and 5 serves as a measure of the molecular weight and the degree of polymerization of the partial or fully saponified polyvinyl alcohols.
• Suitable vinyl alcohol polymers are commercially available polyvinyl alcohols or can be prepared by polymerization of vinyl ester followed by hydrolysis.
• Suitable vinyl esters for preparing the vinyl alcohol polymers are vinyl esters of unbranched or branched carboxylic acids having 1 to 18 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 C-C-branched monocarboxylic acids having 5 to 13 carbon atoms, for example VeoVa9 R or VeoVal0 R (trade names of
• one or more monomers from the group comprising methacrylic acid esters and acrylic esters of alcohols having 1 to 15 C atoms, olefins, dienes, vinylaromatics and vinyl halides may optionally also be polymerized.
• 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 C atoms.
• Preferred methacrylic esters or acrylic 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.
• 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 polymerizable olefins are ethene and propene.
• vinylaromatics styrene and vinyltoluene can be copolymerized.
• From the group of vinyl halides are usually vinyl chloride, vinylidene chloride or Vinyl fluoride, preferably vinyl chloride used. The proportion of these comonomers is such that the proportion of vinyl ester monomer is> 50 mol% in the vinyl ester polymer. 5
• further comonomers may be present in a proportion of preferably 0.02 to 20 wt .-%, based on the total weight of the vinyl ester polymer.
• ethylenically unsaturated mono- and dicarboxylic acids preferably acrylic acid, methacrylic acid, fumaric acid and maleic acid
• carboxylic acid amides and nitrites preferably N-vinylformamide, acrylamide and acrylonitrile
• Mono- and diesters of fumaric acid and maleic acid such as diethyl and diisopropyl esters and maleic anhydride
• ethylenically unsaturated sulfonic acids or salts thereof preferably vinylsulfonic acid, 2-acrylamido-2-methyl-propane sulfonic acid.
• precrosslinking comonomers such as polyethylenically unsaturated comonomers, for example divinyl adipate, diallyl maleate, allyl methacrylate, butanedioldiacrylate or triallyl cyanurate, or post-crosslinking comonomers, for example acrylamidoglycolic acid (AGA), methyl acrylamide-glycolate (MAGME), N-methylolacrylamide (NMA), N Methylolmethacrylamide, N-methylolallylcarbamate, alkyl ethers such as the isobutoxy ether or esters of N-methylol-1-acrylamide, N-methylolmethacrylamide and N-methylol-allylcarbamate.
• the vinyl ester polymers can be prepared in a known manner by means of polymerization; preferably by sub-stamping polymerization, suspension polymerization or by polymerization in organic solvents, more preferably in alcoholic solution. Suitable solvents and regulators are, for example, methanol, ethanol, propanol, isopropanol.
• the polymerization is carried out under reflux at a temperature of 5 50 0 C to 100 0 C and initiated by free radicals by adding common initiators.
• common initiators are percarbonates, such as cyclohexyl peroxidicar- carbonate or perester such as t-butylperneodecanoate or t-butylperpivalate.
• the adjustment of the molecular weight can be carried out in a known manner 5 by the solvent content, by varying the initiator concentration, by varying the temperature, and by adding regulators.
• the monomers can be initially charged in total, metered in in total, or be introduced in portions, and the remainder added after initiation of the polymerization.
• the dosages can be carried out separately (spatially and temporally) or the components to be metered can be metered in all or in part pre-emulsified.
• the saponification of the vinyl ester polymers to give polyvinyl alcohols can be carried out in a manner known per se, for example by the belt or kneader process, in the alkaline or acidic state with the addition of acid or base.
• the solid polyvinyl ester resin is taken up in alcohol, for example methanol, to give a solids content of 15 to 70% by weight.
• the hydrolysis is preferably carried out in the basic, for example by adding NaOH, KOH or NaOCH 3 .
• the base is generally used in an amount of 1 to 5 mol% per mole of ester units.
• the hydrolysis is ⁇ performed at temperatures from 30 0 C to 70 0 C.
• the solvent is distilled off and the polyvinyl alcohol is obtained as a powder.
• the polyvinyl alcohol can also be obtained as an aqueous solution 0 by a successive addition of water, while the solvent is distilled off.
• Preferred ethylenically unsaturated, silane-containing monomers are ⁇ -acrylic or ⁇ -methacryloxypropyltri (alkoxy) silanes, OC-methacryloxymethyltri (alkoxy) silanes, ⁇ -methacryloxypropylmethyldi (alkoxy) silanes; Vinylsilanes such as Vinylalkyldi (alkoxy) - silanes silane and vinyltri (alkoxy) silanes, where as alkoxy groups, for example, methoxy, ethoxy, methoxyethylene, Ethoxyethy- len, Methoxypropylenglykolether- or Ethoxypropylenglykol- ether radicals can be used.
• Examples of preferred silane-containing monomers are 3-methacryloxypropyltrimethoxy
• (2-methoxyethoxy) silane trisacetoxyvinylsilane, allylvinyltrimethoxysilane, allyltriacetoxysilane, vinyldimethylmethoxysilane,
• vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinyltris (1-methoxy) isopropoxysilane, methacryloxypropyltris (2-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane are most preferable and methacryloxymethyltrimethoxysilane and mixtures thereof.
• Atoms, R 9 is an alkoxy group having 1 to 40 carbon atoms, which may be substituted with other heterocycles. In monomers where 2 or more R 5 or R 9 groups are present, these may be identical or different.
• the ethylenically unsaturated, silane-containing monomers are preferably used in an amount of 0.01 to 40 wt .-%, particularly preferably 1.0 to 25 wt .-%, each based on the weight 5 of the vinyl alcohol polymer.
• the vinyl alcohol polymer is initially introduced in solution.
• the vinyl alcohol polymer is dissolved in water or a water / alcohol mixture.
• Suitable alcohols are, for example, methanol, ethanol, propanol, isopropanol.
• the ethylenically unsaturated, silane-containing monomers can be initially introduced in total, be metered in in total, or be introduced in portions, and the remainder added after the initiation of the modification.
• silane-containing monomers preferably up to 20 wt .-% silane-containing monomers, based on 0, the vinyl alcohol polymer, the total amount of silane-containing monomer initially charged and the intitiator added, or the initiator and presented the total amount of silane-containing monomer added.
• concentration of the silane-containing monomers preferably up to 20 wt .-% silane-containing monomers, based on 0, the vinyl alcohol polymer, the total amount of silane-containing monomer initially charged and the intitiator added, or the initiator and presented the total amount of silane-containing monomer added.
• monomer concentrations preferably greater than 20% by weight of silane-containing monomers based on vinyl alcohol.
• the silane-containing monomers and the initiator are partly introduced and the remainder added in each case.
• the modification takes place at elevated temperature, i.e. at temperatures of ⁇ 30 0 C, and is preferably initiated by adding common initiators radical.
• the modification is carried out at a temperature of 50 ° C. to
• the proportion of initiator is preferably from 0.1 to 10.0% by weight, based on the amount of the silane-containing monomers used in total.
• Examples of common initiators are peroxodisulfates, such as potassium peroxodisulfate and Amoniumperoxo- fifth
• silane-modified polyvinyl alcohols thus obtained can be used in solution.
• the silane-modified polyvinyl alcohols can also be isolated in a known manner by means of precipitation, distillation or drying, for example spray-drying, and used as a solid. It is particularly advantageous that the silane-modified polyvinyl alcohols according to the invention show high storage stability even at relatively high silane content.
• silane-modified polyvinyl alcohols which are obtained by copolymerization of ethylenically unsaturated silane with vinyl ester and subsequent hydrolysis, already at a content of silane-functional comonomer units of 2 % By weight tend to gel, the silane-modified polyvinyl alcohols according to the invention are storage-stable even when modified with up to 40 wt .-% of silane-containing monomers.
• the silane-modified polyvinyl alcohols are accessible by the process according to the invention in colorless form.
• the occurrence of discoloration or yellowing in the course of the modification of polyvinyl alcohol polymers with ethylenically unsaturated silane monomers can thus be prevented.
• This is achieved by the selection of the reaction conditions according to the invention, in particular by use of the reaction temperatures according to the invention and optionally by use of inventive amounts of initiators.
• the silane-modified polyvinyl alcohols are suitable for use in the typical applications for polyvinyl alcohols.
• the silane-modified polyvinyl alcohols are useful as binders or co-binders for coatings and adhesives.
• the silane-modified polyvinyl alcohols are particularly suitable as binders in paper coatings, in particular for Inkj et papers.
• the silane-modified polyvinyl alcohols are also suitable as protective colloids, for example for aqueous dispersions and during the reaction in an aqueous medium, and in the preparation of water-redispersible dispersion powders.
• Further fields of application are the treatment of pigments and fillers and the use as binders in the ceramics industry.
• Other applications are those in cosmetics, especially hair cosmetics, and as a binder in food packaging and textile industry.
• Example 2 0 in a thermostatically controlled laboratory apparatus with 2.5 liter filling volume under nitrogen, 1000 g of a 20% aqueous polyvinyl alcohol solution (Mowiol 8-88, Kuraray Properties Europe) submitted and heated to 90 0 C with stirring. At this temperature was stirred for 2 h and then the
• the temperature was maintained at 80 0 C for 4 h and then the temperature was reduced to 40 0 C and the pH adjusted to 9 with ammonia and stirred for 2 hours. After cooling, the pH was adjusted to 5 with hydrochloric acid.
• a clear polymer solution having a solids content of 20% by weight and 7.0% by weight, based on the total weight of the silane-modified polyvinyl alcohols, of silane content was obtained.
• the template was heated under nitrogen and stirring (95 rpm) and polymerized under reflux (57 ° C - 60 0 C). 0.64 g of tert-butyl peroxy pivalate were added each 60 minutes and 120 minutes after reflux. 180 min after reflux, 400 g of methanol were added to the reactor and stirred for a further 4 hours at reflux and then cooled, the polymer solution.
• the resulting resin solutions were saponified according to the following recipe for polyvinyl alcohol:
• Comparative Example 6 The procedure was analogous to Example 1 with the difference that 126 g of the 3% strength aqueous potassium peroxodisulfate solution were used.
• Raw paper sized paper approx. 80 g / m 2 ; Coating application approx. 15 g / m 2 Testing:
• a 4.5 cm wide and 19 cm long paper strip coated with the coating composition was processed in a scouring tester from the company Prufbau (Dr. Durner system) with a black drawing paper with 50 strokes applied to a stamp (500 g). The resulting black paper was then visually assessed, with grade 1 being the optimum.
• the whiteness was determined by reflectance measurement with a filter (R 457) and assessed visually, the grade 1 representing the optimum.
• the storage stability was tested by storing in each case an 18% aqueous solution of the silane-modified polyvinyl alcohol at a pH of 5 up to 14 days, and the Hoppler viscosity (according to DIN 53015 as 4% by weight). aqueous solution).
• the primer (solution of the corresponding silane-modified polyvinyl alcohol) was applied to a base paper by means of a laboratory size press and dried accordingly (coat weight 1.5 g / m 2 to 3 g / m 2 ).
• a release layer of 100 parts by weight of a vinyl-terminated polysiloxane (Dehesive 920), 2.4 parts by weight of an H-containing siloxane (crosslinker V90) and 1 part by weight of Pt catalyst (catalyst OL) was applied and the coated paper annealed at 150 0 C for 7 seconds.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• General Chemical & Material Sciences (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Paper (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Paints Or Removers (AREA)
• Graft Or Block Polymers (AREA)

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