Title of Invention

PROCESS FOR THE PREPARATION OF THERMALLY STABLE VINYL CHLORIDE COPOLYMERS

Abstract

A process for the preparation of vinyl chloride copolymers obtainable by means of free radical suspension polymerization or emulsion polymerization of a mixture of vinyl chloride, epoxide-containing vinyl monomers and further comonomers copolymerizable therewith, characterized in that a) from 49.5 to 90% by weight of vinyl chloride, b) from 0.01 to 0.7% by weight of epoxide-containing vinyl monomers and c) from 9.5 to 50% by weight of further comonomers copolymerizable with a) and b) are polymerized, the data in % by weight summing to 100% by weight, and from 0.001 to 0.1% by weight of one or more carboxylic acids from the group consisting of aliphatic and alicyclic, saturated and unsaturated dicarboxylic acids having 1 to 10 carbon atoms and aliphatic and alicyclic, saturated and unsaturated hydroxymono-, hydroxydi- and hydroxy tricarboxylic acids having 3 to 10 carbon atoms and 1 to 4 hydroxyl groups is added during or after the polymerization.

Full Text

Thermally stable vinyl chloride copolymers The invention relates to thermally stable vinyl chloride copolymers, processes for the preparation thereof, and the use thereof in particular in coating resin compositions. A major problem with the use of vinyl chloride copolymers is the insufficient stability of solutions of these polymers in organic solvents, in particular in ketones. In warm regions having an ambient temperature of more than 30°C, a yellow or brown discoloration of the originally colorless solutions occurs after storage of such solutions for only a few days. Also problematic is the storage of pulverulent resins based on vinyl chloride copolymers at elevated temperatures. Here, discoloration of the powder may occur after a storage time of only a few months, subsequently leading to discoloration of solutions of these powders. The lack of thermal stability of these copolymers is said to be a reason for the tendency of solutions of vinyl chloride copolymers to become discolored. Other adverse phenomena are corrosion phenomena in the form of rusjt formation on metal parts of machines and storage containers which come into contact with solutions of vinyl chloride copolymers. EP-B 358067 proposes the use of vinyl chloride copolymers comprising from 1 to 20% by weight of glycidyl methacrylate and from 12 to 40% by weight of further comonomers for improving the resistance to yellowing. EP-B 219097 discloses that the thermal stability can be improved by copolymerizing vinyl chloride with OH-functional acrylates, epoxide-containing comonomers and acid-functional comonomers. For the epoxide-containing comonomers, such as glycidyl methacrylate, it is recommended to use these in an amount of from 1 to 12% by weight. Similar copolymers form the subject of EP-B 2 64 3r£6, in which a content of less . than 0.5% by weight of epoxide groups, corresponding to about 1.7% by weight of glycidyl methacrylate, is described as being insufficient for improving the thermal stability. Against this background, it was the object of the invention to provide thermally stable vinyl chloride copolymers. The invention relates to vinyl chloride copolymers obtainable by means of free radical polymerization of a mixture of vinyl chloride, epoxide-containing vinyl monomers and further comonomers copolymerizable therewith, characterized in that a) from 49.5 to 90% by weight of vinyl chloride, b) from 0.01 to 0.7% by, weight of epoxide-containing vinyl monomers and c) from 9.5 to 50% by weight of further comonomers copolymerizable with a) and b) are polymerized, data in % by weight summing to 100% by weight. Suitable epoxide-containing vinyl monomers b) are, for example, methyl glycidyl methacrylate, methyl glycidyl aerylate, allyl glycidyl ether, allylphenol glycidyl ether and glycidyl methacrylate. Glycidyl methacrylate (GMA) is preferred. Preferably from 0.01 to 0.5% by weight, particularly preferably from 0.1 to 0.4% by weight, of epoxide-containing vinyl monomers is copolymerized. Suitable copolymerizable comonomers c) are one or more ethylenically unsaturated monomers from the group consisting of vinyl esters of straight-chain or branched alkylcarboxylic acids having 1 to 18 carbon atoms, acrylates or methacrylates of branched or straight-chain alcohols or diols having 1 to 18 carbon atoms, ethylenically unsaturated mono- and dicarboxylic acids and anhydrides thereof. Preferred vinyl esters are those of carboxylic acids having 1 to 12 carbon atoms. Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethyhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate and vinyl esters of ct-branched monocarboxylic acids having 9 to 13 carbon atoms, for example VeoVa9R or VeoValOR (trade names of Shell) are preferred. Vinyl acetate is most preferred. Preferred monomers from the group consisting of acrylates or methacrylates are esters of straight-chain or branched alcohols having 1 to 15 carbon atoms. Particularly preferred methacrylates or acrylates are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate and 2-ethylhexyl acrylate. Methyl acrylate, methyl methacrylate, n-butyl acrylate, tert-butyl acrylate and 2-ethylhexyl acrylate are most preferred. Examples of suitable ethylenically unsaturated mono-and dicarboxylic acids and anhydrides, thereof are acrylic acid, methacrylic acid, fumaric acid, itaconic acid, crotonic acid, maleic acid and maleic anhydride. The free radical polymerization can be effected by means of solution polymerization, suspension polymerization and emulsion polymerization. Suspension polymerization and emulsion polymerization are preferred. The polymerization temperature is in general from 20°C to 75°C. The initiation of the polymerization can be effected with the customary water-soluble or monomer-soluble initiators or redox initiator combinations. Examples of water-soluble initiators are the sodium, potassium and ammonium salts of peroxodisulfuric acid. Examples of monomer-soluble initiators are diacetyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, dibenzoyl peroxide and tert-butyl peroxypivalate. Said initiators are used in general in an amount of from 0.01 to 1.0% by weight, preferably from 0.1 to 0.5% by weight, based in each case on the total weight of the monomers. In the case of solution polymerization, organic solvents, such as ethyl acetate, are used. In the case of the suspension and emulsion polymerization processes which are mentioned as being preferred, polymerization is effected in water in the presence of surface-active substances, such as protective colloids and/or emulsifiers. Suitable protective colloids are, for example, partly hydrolyzed polyvinyl alcohols. Suitable emulsifiers are anionic, cationic and nonionic emulsifiers, for example anionic surfactants, such as alkylsulfates having a chain length of from 8 to 18 carbon atoms, alkane- or alkylarylsulfonates having from 8 to 18 carbon atoms, esters and monoesters of sulfosuccinic acid with monohydric alcohols or alkylphenols, or nonionic surfactants, such as alkylpolyglycol ethers or alkylarylpolyglycol ethers having up to 60 ethylene oxide or propylene oxide units. For controlling the molecular weight, regulating substances can be used during the polymerization. If regulators are used, these are usually used in amounts of from 0.02 to 10.0% by weight, based on the monomers to be polymerized, and are metered separately or in a form premixed with reaction components. Examples of such substances are halogenated alkanes and halogenated alkenes, such as carbon tetrachloride, chloroform, methyl chloride and trichloroethylene, and aldehydes, such as acetaldehyde, propionaldehyde, butyraldehyde and isobutyraldehyde. Polymerization is preferably effected in the presence of propionaldehyde. Compared with other regulators, such as, for example, trichloroethylene, propionaldehyde has the advantage that a regulating effect is achieved even with smaller amounts. It is therefore preferably added in an amount of from 0.02 to 5% by weight, based on the monomer, depending on the desired molecular weight. A disadvantage of the use of propionaldehyde was that colored products are obtained therewith. Surprisingly, it was found that, in the procedure according to the invention, no discoloration occurs in the presence of epoxide-containing vinyl monomers and (iso)ascorbic acid. The monomers can be metered in together or can be initially introduced in portions and the remainder can be metered in after initiation of the polymerization. The meterings can be carried out separately (with respect to space and time) , or some or all of the components to be metered can be metered in preemulsified form. In a preferred embodiment, the epoxide-containing vinyl monomers are metered in together batchwise or particularly preferably together continuously. After the end of the polymerization, postpolymerization can be effected for removing residual monomers using known methods, for example by postpolymerization initiated by a redox catalyst. Volatile residual monomers can also be removed by means of distillation, preferably under reduced pressure, and optionally by passing through or passing over inert entraining gases, such as air, nitrogen or steam. In a preferred embodiment, from 0.001 to 0.1% by weight of one or more carboxylic acids from the group consisting of aliphatic and alicyclic, saturated and unsaturated dicarboxylic acids having 1 to 10 carbon atoms and aliphatic and alicyclic, saturated and unsaturated hydroxymono-, hydroxydi- and hydroxytricarboxylic acids having 3 to 10 carbon atoms and 1 to 4 hydroxy1 groups is added during or after the polymerization. The addition is preferably effected after the end of the monomer metering and before, during or after the removal of residual monomers. Examples of dicarboxylic acids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and maleic acid and fumaric acid. Said hydroxycarboxylic acids are particularly preferred, for example tartronic acid, malic acid, tartaric acid, citric acid, isocitric acid, ascorbic acid and isoascorbic acid. Ascorbic acid and isoascorbic acid are most preferred, in particular combinations of ascorbic acid or isoascorbic acid with citric acid. The amount of (iso)ascorbic acid and citric acid is preferably in each case from 0.005 to 0.05% by weight, based in each case on the total weight of the comonomers. The vinyl chloride copolymer obtained by this process can be isolated by customary methods, by precipitation, filtration and subsequent drying. The vinyl chloride copolymers are suitable, for example, as binders for coatings, in particular in heat-seal coatings, for example for aluminum coating. The following examples serve for further explanation of the invention: Example 1: A copolymer comprising 83.8% by weight of vinyl chloride, 14.8% by weight of vinyl acetate, 1.0% by weight of fumaric acid and 0.4% by weight of glycidyl methacrylate was prepared by the suspension polymerization process, 0.05% by weight of ascorbic acid and 0.0075% by weight of citric acid, based in each case on the total weight of the comonomers and in each case as a 10% strength aqueous solution, being added to the batch at the end of the comonomer metering. Immediately after this addition, the batch was let down to atmospheric pressure. Thereafter, demoncmerization was effected, the batch was neutralized by adding 0.5% by weight of sodium hydroxide solution and the copolymer was filtered, washed and dried. For testing the thermal stability, a 20% strength by weight solution of the copolymer in methyl ethyl ketone was prepared and was stored at 60 °C, and the discoloration of the solution was monitored as a function of time. The solution remained completely colorless even after a storage time of one week. Example 2: Analogously to the procedure of example 1, a copolymer was prepared from 83.8% by weight of- vinyl chloride, 14.8% by weight of vinyl acetate, 1% by weight of fumaric acid and 0.4% by weight of glycidyl methacrylate. A 20% strength by weight solution of the copolymer in methyl ethyl ketone showed a slight discoloration after a storage time of six days at 60°C. Example 3: A copolymer of 83.8% by weight of vinyl chloride, 14.8% by weight of vinyl acetate, 1% by weight fumaric acid and 0.4% by weight of glycidyl methacrylate was prepared by the procedure in example 1, with the only difference that only 0.05% by weight of ascorbic acid (no citric acid) was added. A 20% strength by weight solution of the copolymer in methyl ethyl ketone showed only a very slight discoloration even after a storage time of one week at 60°C. Example 4: A copolymer was prepared from 84.8% by weight of vinyl chloride, 14.8% by weight of vinyl acetate and 0.4% by weight of glycidyl methacrylate by the emulsion polymerization process. At the end of the reaction, the mixture was let down to atmospheric pressure and 0.02% by weight of ascorbic acid and 0.0025% by weight of citric acid, based in each case on the total weight of the comonomers and in each case as a 10% strength aqueous solution, were added to the batch. Thereafter, demonomerization was effected and the copolymer was precipitated, filtered, washed and dried. A 20% strength by weight solution of the copolymer in methyl ethyl ketone remained completely colorless even after a storage time of one week at 60°C. Comparative example A: A copolymer was prepared from 85% by weight of vinyl chloride and 15% by weight of vinyl acetate by means of emulsion polymerization analogously to example 4. A 20% strength by weight solution of the copolymer in methyl ethyl ketone showed a slight discoloration even at room temperature. After storage for 1 day at 60°C, a substantial brown coloration was found. Example 5: The procedure was analogous to example 4, with the difference that polymerization was effected in the presence of 2% by weight of propionaldehyde, based on total monomer. A 20% strength by weight solution of the copolymer in methyl _ethyl ketone showed a lower solution viscosity than the product from example 4 and remained completely colorless even after a storage time of one week at 60°C. Example 6: The procedure was analogous to example 5, with the difference that polymerization was effected in the presence of 4% by weight of trichloroethylene, based on total monomer. A 20% strength by weight solution of the copolymer in methyl ethyl ketone showed a similar solution viscosity to the product from example 5 and remained completely colorless even after a storage time of one week at 60°C. Comparative example B: A copolymer was prepared from 85% by weight. of vinyl chloride and 15% by weight of vinyl acetate in the presence of 2% by weight of propionaldehyde, based on total monomer, by means of emulsion polymerization analogously to comparative example A. A 20% strength by weight solution of the copolymer in methyl ethyl ketone showed a lower solution viscosity than a solution of the product from comparative example' A, and a slight discoloration even at room temperature. The comparison of example 3 with example 2 shows that a thermally stable product is obtained with substantially smaller amounts of GMA than in the prior art on stopping the reaction with ascorbic acid, owing to the synergistic interaction of GMA and ascorbic acid. Example 1 shows that this synergistic effect can be even further increased with citric acid. The comparison of examples 5 and 6 and comparative example B shows the advantageous regulating effect of propionaldehyde without discoloration of the product occurring. Patent claims: 1. A vinyl chloride copolymer obtainable by means of free radical polymerization of a mixture of vinyl chloride, epoxide-containing vinyl monomers and further comonomers copolymerizable therewith, characterized in that a) from 4 9.5 to 90% by weight of vinyl chloride, b) from 0.01 to 0.7% by weight of epoxide-containing vinyl monomers and c) from 9.5 to 50% by weight of further comonomers copolymer izable with a) and b) are polymerized, the data in % by weight summing to 100% by weight, and optionally from 0.001 to 0.1% by weight of one or more carboxylic acids from the group consisting of aliphatic and alicyclic, saturated and unsaturated dicarboxylic acids having 1 to 10 carbon atoms and aliphatic and alicyclic, saturated and unsaturated hydroxymono-, hydroxydi-and hydroxytricarboxylic acids having 3 to 10 carbon atoms and 1 to 4 hydroxyl groups are added during or after the polymerization. 2. The vinyl chloride copolymer obtainable by means of free radical polymerization as claimed in claim 1, characterized in that from 0.001 to 0.1% by weight of ascorbic acid and/or isoascorbic acid, based on the total weight of the monomers, is added. 3. The vinyl chloride copolymer obtainable by means of free radical polymerization as claimed in claim 1 or 2, characterized in that citric acid in an amount of from 0.001 to 0.1% by weight, based on the total weight of the comonomers, is also added in addition to the ascorbic acid and/or isoascorbic acid. 4. The vinyl chloride copolymer obtainable by means of free radical polymerization as claimed in any of claims 1 to 3, characterized in that one or more vinyl esters from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl-2-ethylhexanoate, vinyl laurate, 1-methyl vinyl acetate, vinyl pivalate and vinyl esters of a-branched monocarboxylic acids having 9 to 13 carbon atoms, optionally in combination with one or more comonomers from the group consisting of acrylic acid, methacrylic acid, fumaric acid, itaconic acid, crotonic acid, maleic acid and maleic anhydride, are copolymerized as comonomers c) . 5. The vinyl chloride copolymer obtainable by means of free radical polymerization as claimed in any of claims 1 to 4, characterized in that one or more epoxide-containing vinyl monomers from the group consisting of methyl glycidyl methacrylate, methyl glycidyl aerylate, allyl glycidyl ether, allylphenol glycidyl ether and glycidyl methacrylate are copolymerized as comonomers b). 6- A process for the preparation of * the vinyl chloride copolymers as claimed in claim 1 by means of free radical polymerization of a mixture of vinyl chloride, epoxide-containing vinyl monomers and further comonomers copolymerizable therewith, characterized in that a) from 49.5 to 90% by weight of vinyl chloride, b) from 0.01 to 1.0% by weight of epoxide-containing vinyl monomers and c) from 9.5 to 50% by weight of further comonomers copolymerizable with a) and b) are polymerized, the data in % by weight summing to 100% by weight, and optionally from 0.001 to 0.1% by weight of one or more carboxylic acids from the group consisting of aliphatic and alicyclic, saturated and unsaturated dicarboxylic acids having 1 to 10 carbon atoms and aliphatic and alicyclic saturated and unsaturated hydroxymono-, hydroxydi- and hydroxytricarboxylic acids having 3 to 10 carbon atoms and 1 to 4 hydroxy 1 groups is added during or after the polymerization. 7. The process for the preparation of the vinyl chloride copolymers as claimed in claim 6, characterized in that from 0.001 to 0.1% by weight of ascorbic acid and/or isoascorbic acid, and optionally additionally citric acid in an amount of from 0.001 to 0.1% by weight, based in each case on the total weight of the comonomers, are added during or after the polymerization. 8. The process for the preparation of the vinyl chloride copolymers as claimed in claim 6 or 7, characterized in that polymerization is effected in the presence of from 0.02 to 10% by weight, based on the monomers to be polymerized, of regulating substances, in particular propionaldehyde. 9. The use of the vinyl chloride copolymers as claimed in any of claims 1 to 4 as binders for coatings. 10. The use as claimed in claim 9 in heat-seal coatings. Dated this 5 day of September 2005

Documents:

2154-chenp-2005-abstract.pdf

2154-chenp-2005-claims.pdf

2154-chenp-2005-correspondnece-others.pdf

2154-chenp-2005-correspondnece-po.pdf

2154-chenp-2005-description(complete).pdf

2154-chenp-2005-form 1.pdf

2154-chenp-2005-form 18.pdf

2154-chenp-2005-form 26.pdf

2154-chenp-2005-form 3.pdf

2154-chenp-2005-form 5.pdf

2154-chenp-2005-pct.pdf