DE1092202B - Process for the production of internally plasticized polymers - Google Patents

Description

GERMAN

It is known that polymerization plastics such as polyvinyl chloride or polyvinyl acetate are required for the majority the application areas a more or less large amount of plasticizer added. These additions allow that adjust the desired plastic or other mechanical properties of these plastics. However, since they are not chemically built into the macromolecule, they have the disadvantage that they are in the Over time - especially in the case of thermal stress or a large surface - of the polymer, be released again through exudation or evaporation, which leads to unfavorable changes, z. B. to embrittlement, leads.

To remedy this problem, it has already been proposed to use copolymerization with vinyl stearate, which is chemically incorporated into the main valence chain of the polymer molecule, an "internal" softening to achieve. However, a disadvantage of vinyl stearate is the poor compatibility of the long paraffinic Chain this connection with various polymers.

Copolymers of vinyl compounds, for example vinyl chloride and vinyl esters, are also shorter-chain Carboxylic acids, e.g. B. vinyl stearate or vinyl propionate, known. With these internally softened Copolymers, however, the ester bonds are relatively easy to saponify.

It has now been found that one can advantageously produce plasticized polymers if one polymerizable double bonds containing monomers with vinyl esters of α-methyl and / or α, α-dimethyl carboxylic acids, which contain at least 5 carbon atoms in the acid residue, under otherwise usual conditions copolymerized.

For the present process, all plastics come into question, which by polymerization or copolymerization obtained from monomers containing polymerizable double bonds, such as vinyl chloride, Vinyl acetate, vinylidene chloride, vinylidene acetate, acrylic acid esters, methacrylic acid esters, styrene. The quantities the polymerized vinyl esters of α-methyl and / or α, α'-dimethylcarboxylic acids, the at least 5 carbon atoms are contained in the acid residue, depending on the monomers used and the desired ones plastic or other properties different. They also depend on the structure, especially the The degree of branching of the aliphatic radical and the chain length of the carboxylic acid are from about 2% - based on the monomer to be polymerized - up to proportions of 40 to 50%, for example during production of vinyl chloride films. Copolymers according to the present invention are also compatible with the non-toxic, cheap plasticizers based on fatty acids, so that it is advantageous for some areas of application, Method of manufacture

from internally softened

Polymers

Applicant:

Aniline & Soda Factory in Baden

Corporation,

Ludwigshafen / Rhine

Dr. Henry Poltz, Wolfenbüttel,
has been named as the inventor

not to work with so high vinyl ester additions that a material with the desired degree of plasticity directly but you can create a polymer "plasticized" with vinyl esters by adding Bring the usual plasticizers to the desired consistency. This way of working will be reflected in some Recommend cases for the manufacture of such fabrics that are to be used for foil purposes. Lies on the other hand, the area of application of the polymers in the emulsion or dispersion paint sector, the Textile industry, adhesives or the like, so one chooses such a high vinyl ester addition from the start of the type described that the plasticization is fully sufficient.

The vinyl esters of these methyl carboxylic acids are recently known to be very easy by the synthesis of Reppe has become accessible through the addition of acetylene to the corresponding carboxylic acids. the α-methyl or α, α'-dimethylcarboxylic acids are in turn z. B. by the syntheses of Koch or Reppe can be produced from the corresponding olefins by the addition of carbon monoxide and water. Particularly suitable Vinyl esters of methyl or dimethyl carboxylic acids for the present process are those that by Addition of carbon monoxide and water to such olefins are produced by polymerization or Copolymerization of low molecular weight olefins, such as ethylene, propylene, butylene, have arisen. In addition, however, methyl or dimethyl carboxylic acids are also suitable, which by other methods and were produced starting from other olefins, for example from primary olefins of the Fischer-Tropsch synthesis or fission olefins.

The particular advantage of the process described here for the internal plasticization of polymerization

009 630/442

plastics versus the use of vinyl stearate There is also the fact that the stabilizing effect of the methyl groups in the α position is essential increased stability of the ester bond towards saponifying agents is achieved. In addition, the here preferably proposed methyl carboxylic acid vinyl ester from branched-chain aliphatic radicals the particular advantage of a much better tolerance and also better effectiveness than with the Use of vinyl stearate. The better tolerance is expressed in the fact that higher percentages are incorporated can be, which is particularly important for the production of flexible films that require a higher addition of internal plasticizers. The better effectiveness is especially then given when branched-chain vinyl esters of methyl carboxylic acids are used as they are when the methyl or dimethyl carboxylic acids are formed from olefins produced by polymerization or copolymerization of low molecular weight olefins will. This better effectiveness is expressed in the fact that for the same degree of plasticization a lower degree of plasticization Percentage of these substances can be used for copolymerization than with vinyl stearate. Aside from that economic advantage in this - the vinyl esters are generally more expensive than simple monomers, which are used for polymerization - there is also a procedural advantage, since the individual Monomers, e.g. B. vinyl chloride and a vinyl ester, what have different polymerization rates becomes noticeable all the more unpleasant, the higher the percentage of the vinyl ester to be incorporated.

Finally, the softening effect of the proposed compounds is particularly also in the case of deeper ones Temperatures significantly higher than those of vinyl stearate, which creates some additional new areas of application be developed, e.g. B. the incorporation in a small percentage in polystyrene, whereby the notched impact strength this polymer is increased significantly.

Because the proposed vinyl ester is inevitably perfect due to the way in which the carboxylic acids are produced Have saturated hydrocarbon radicals in the carboxylic acid chain, there is no delay in the reaction Appearance as it always occurs with the use of vinyl stearate because of the stearic acid available on the market olefinic double bonds that are still present in small amounts in copolymerization in particular makes unpleasant noticeable.

The incorporation of the vinyl esters according to the invention can, as in the case of vinyl stearate, in the block, solution, Emulsion or dispersion polymerization take place, so that all areas of application for the copolymers are open.

Two of the many possible applications of the claimed method are shown below Embodiments given.

example 1

500 ecm of distilled water, 1 g of sodium oleate, 3 ecm of a 30% hydrogen peroxide solution, 2 g of polyvinyl alcohol and 0.2 g of disodium phosphate are placed in an enamelled autoclave with a capacity of 1.21. To this solution are added 25 g of the vinyl ester of a methyl carboxylic acid, which was prepared by the synthesis of Koch from tetramerpropylene, and 100 g of vinyl acetate. The sealed autoclave is then heated under vigorous stirring to 8O ⁰ C. When the reaction is complete, a copolymer is obtained in the form of a stable emulsion, which is brought to a solids content of 60% by centrifugation. This emulsion is ideally suited for the production of paints in which the plastic properties of the film formed are of particular importance. In addition, however, it is also extremely useful for many other purposes, e.g. B. in the textile and adhesive industry.

Example 2

In a thick-walled glass tube, which is in a cold bath, 15 g of vinyl chloride and 5 g Vinyl ester of an α-methyl carboxylic acid, which is produced from propylene trimer according to the synthesis of Koch was frozen. After adding 0.3 g of benzoyl peroxide, the glass tube, which is with its lower End still in the cold bath, melted shut. The cold bath is then removed and the glass tube is brought in into an electrically heated shaker. The polymerization is then carried out at 85.degree. After the polymerization has taken place, the copolymer, which is a white mass, is after the taken from cooled glass tube. A wide variety of objects can be used at temperatures as low as 90 to 95 ° C are processed.

Is worked in the manner indicated above, but with changed proportions, namely 13 g of vinyl chloride and 7 g of vinyl ester, the material obtained is suitable for film production.

Claims (2)

Patent claims: 1. A process for the production of internally plasticized polymers, characterized in that that polymerizable double bonds containing monomers with vinyl esters of a-methyl and / or α, α-dimethylcarboxylic acids which contain at least 5 carbon atoms in the acid radical, under Copolymerized under normal conditions. 2. The method according to claim 1, characterized in that the vinyl esters of α-methyl and / or α, α-Dimethylcarboxylic acids containing at least 5 carbon atoms in the acid residue, in amounts of 2 to 50 percent by weight, based on the amount of monomers to be polymerized, copolymerized will. Considered publications:
German Patent Nos. 679 897, 593 399;
British Patent Nos. 498,329, 498,464;
French patent specification No. 835 357.