DE813461C - Process for the production of polymers and copolymers - Google Patents

Description

Process for the production of polymers and copolymers The present invention relates to a process for the production of new thermoplastics and heat-curing polymers and copolymers that thereby It is indicated that oxystyrene polymers with free oxy groups in the nucleus to be aged. The plastics obtained in this way can be used for many purposes used, such as molding powder, paints or adhesives and the like.

Polymers can be used as starting products for the etherification mentioned or copolymers of o-, m- or lr-oxystyrenes or their low molecular weight Homologs are used, which werdin manufactured by methods known per se kiinnen.

If the simple polymer or a mixed polymer with sufficient Content of oxystyrenes with free nuclear oxy groups is to be etherified, so is the polymer or synthetic resin used as the starting product, in particular if the mixed monomer is polar in nature, preferably an alkaline polar one Medium, such as B. water, a lower aliphatic alcohol or a mixture both dissolved or dispersed. Otherwise a solution can be in a non-polar inert organic solvents or in a mixture of predominantly non-polar Solvents or a fine dispersion of the polymer or copolymer in a liquid medium such as that obtained in emulsion polymerization, be used. For example, a styrene copolymer that has more than about 20 Contains mole percent of oxystyrene with free core oxy groups, or a vinyl acetate copolymer having greater than about 5 mole percent oxystyrenes in any one as above specified dissolved or dispersed in an alkaline, polar medium while a styrene copolymer containing less than about 20 mole percent oxystyrenes contains, advantageously in a solution in benzene or a benzene-alcohol mixture is treated. If a non-polar agent is used, in the alkali or alkaline earth hydroxides are practically insoluble, a quaternary ammonium hydroxide is expediently used as Condensing agents are used because bases such as pyridine, although effective, tend to enter into conversions themselves with the etherifying agent, whereby they become ineffective. The alkali used as the condensing agent is preferred at least in an equimolecular amount, based on the phenol groups to be etherified, applied.

As an etherifying agent, for. B. a saturated or unsaturated one Aldehyde or an alkyl ester of an inorganic acid, e.g. B. an alkyl sulfate, chloride, -bromide or -iodide (but no -fluoride) or a mixture of these compounds is used such as dimethyl or diethyl sulfate and allyl chloride or ß-methallyl chloride, which provide unsaturated ethers. In many cases where an unsaturated product is obtained, the plastic obtained is curable by heat and can according to known Process to be vulcanized.

According to a modification of the invention, the polymeric material is with treated with an aldehyde and an etherifying agent, either at the same time or sequentially, thereby obtaining an improved thermosetting resin that with fillers, plasticizers and lubricants and the like for the purpose of production of molding powders or the like. Mixed or for the purpose of producing paints or adhesives can be dissolved or dispersed in a suitable agent. Becomes an aldehyde is also used, it is essential that the oxystyrenes are in the nucleus with free Oxy groups with respect to these oxy groups at least one, but preferably two have unsubstituted o- or p-positions. Furthermore, the polymer or The mixed polymer contains, if possible, no o-oxystyrene or only a small amount of it, because the material then reacts much more easily with aldehydes. This modified The reaction can be carried out under the same conditions as those used for the simple etherification have been given.

The effect of treating the oxystyrenes with free nuclei Oxy groups with the etherifying agent and the aldehyde consists in that certain Quantities converted into etherified products with little further reactivity and at the same time changed the properties of the plastic finally obtained and also a condensation between at least a part of the remaining Amount is effected with the aldehyde, whereby reactive centers are formed, which cross-link the polymer chains during later hardening. If more than one equivalent Amount of either reactant used, they will be in sales compete with each other with the oxystyrenes, but in general one becomes sufficient Part of reacting with the aldehyde, so that the convertibility of the product by heat is guaranteed. In this regard, it is advantageous that each is used Copolymer contains at least 2 mol percent of oxystyrenes necessary for the reaction with the aldehyde are available.

If necessary, the modified process can also be carried out in two stages be carried out, the oxystyrenes initially with less in the first stage as one equivalent of one reactant and then react with the other to be brought. The most suitable order depends on the solubility of the resin the effect of etherification usually in an increase in solubility in non-polar solvents and in a decrease in solubility in polar ones Solvents. If, therefore, a deposition of the intermediate product in the end or is to be avoided during the course of the first procedural stage, it is best the etherification carried out first when a solution in a non-polar solvent is used, and the aldehyde condensation is carried out first if a solution is used in a polar solvent. When a fine dispersion of the solid When plastic is used, the order of treatment is less important.

The modified method can also be used as an etherifying agent a substance such as dimethyl sulfate can be used, whereby saturated ethers are obtained or a compound such as allyl chloride; thereby obtaining unsaturated ethers by which the property of faster hardening by heat is obtained.

The production of the new plastics by the process according to the invention is illustrated by the following examples. The parts given are parts by weight.

Example i 50 parts of a colorless, practically pure m-oxystyrene polymer, which was obtained by the fact that m-oxystyrene for a week at 18 ° in a closed vessels in the absence of any polymerization catalyst left to a soft rubber-like mass, were consecutively twice kneaded with 50 parts of benzene each, then broken into coarse lumps, in a Werner-Pfleiderer chipper, through which benzene was constantly being sent, chipped and then dried, whereby 2o parts of a high molecular weight poly-m-oxystyrene oil in the form of a white, free-flowing coarse powder were obtained.

This powder was then dissolved in 40 parts of a 300% aqueous sodium hydroxide solution dissolved, and 19 parts of allyl chloride were added to the solution. That the mix The vessel containing it was then closed and the whole was left to stand at 18 ° for 24 hours. After this time the mass formed an opaque, rubber-like gel. The product became then crushed, freed from salts by washing with dilute sulfuric acid, washed neutral with water and dried. It became a heat curable one Obtain plastic that can be used as a molding powder.

Examples A mixture of 75 parts of m-oxystyrene and 25 parts of styrene was held at 10 ° in a nitrogen atmosphere for 16 hours, producing a soft rubber-like mixed polymer was obtained (read soluble in ethyl alcohol and was practically insoluble in benzene. 10 parts of this product were divided into 20 parts dissolved in hot 3oo / o aqueous sodium hydroxide solution and then cooled to 20 °. () The 1.östing was then done with stirring and cooling, tim the temperature below 5o ° to keep, treated dropwise with i i parts of methyl sulfate.

1) The purification was continued until the methyl ether was found to be one rubber-like: let goodbye, washed with water and dissolving in io parts Benzene and precipitating by pouring it into a relatively large quantity of ethyl alcohol has been cleaned.

By repeating this cleaning process several times, a Obtain non-sticky plastic that is easily crushed to a fibrous powder that could be used for the preparation of thermoplastic I # ormptilvern and t1ierzugmittel can be used. Compared to the original, polymerizate that was etherified material not only against water, but also against aqueous sodium hydroxide solution stable and was soluble in benzene, while the original, lischpolynierisat was insoluble in it.

EXAMPLE 3 10 parts of a Polish m-oxystyrene obtained by voluntary polymerization of pure m-oxystyrene at 110 ° for one week and subsequent extraction of the lower molecular weight material using benzene were dissolved in 40 parts of a 100% sodium hydroxide solution, and this 6t / 2 parts of a 37.5% formaldehyde solution were added to the solution with stirring. The mixture was heated to 50 ° for 30 minutes, and then 5.3 parts of ethyl stilfate were added with vigorous stirring, and stirring was continued until the etherified product separated. The mass was then neutralized with 2N sulfuric acid, the product filtered, washed salt-free with water and then dried in vacuo at a temperature below 40 °. The product was heat curable and useful in the manufacture of molding powders, paints and adhesives.

Example 4 A mixture of 10 parts of m-oxystyrene and cgo parts of steel was kept at 100 'for 16 hours in a nitrogen atmosphere, producing a hard, Brittle copolymer was obtained, which is soluble in benzene, but in ethyl alcohol and was practically insoluble in boiling aqueous sodium hydroxide solution. 10 parts of this product were dissolved in 50 parts of benzene and 1 part of methylpyridinium hydroxide was dissolved, and then 2 parts of dimethyl sulfate were added with stirring and the mixture was kept at 50 ° for 2 hours. After the reaction was over, it was etherified Copolymer precipitated by the mixture in a relatively large Excess of ethyl alcohol was poured.

Example s 20 parts of a copolymer obtained by emulsion polymerization of equal amounts by weight of styrene and m-oxystyrene were dissolved in 150 parts of a mixture of equal volumes of benzene and ethyl alcohol. 40 parts of a 25% aqueous solution of tetramethylammonium hydroxide and then 30 parts of dimethyl sulfate were then carefully dispersed in the solution with vigorous stirring. The mass was then left to stand for 1½ hours at 40 °. Alcohol was then added until the etherified product separated which was then filtered off, washed with alcohol, redissolved in benzene and reprecipitated by pouring into alcohol to give a fibrous precipitate which, after separation and drying, had improved pliability and water resistance. Example 6 25 parts of a poly-m-oxystyrene, as used in Example i, were dissolved in 100 parts of a 100% aqueous sodium hydroxide solution, followed by a mixture of 24 parts of diethyl sulfate (3/4 mol) and 6.25 parts Allyl bromide (1/4 mol) was added and this was thoroughly dispersed by shaking. The temperature rose to 45 ° and after 30 minutes the mixed ether had separated from the solution. A 50% sulfuric acid solution was then added in order to neutralize the sodium hydroxide, whereupon the product was filtered off and washed free of salt with water. After further washing with alcohol, the product was air dried.

This material was then treated as follows: i. A stake became heated under pressure to 130 ° for 1 hour, after which the product became a hard mass was hardened.

2. To 10 parts of the product, which were dissolved in 50 parts of benzene, o, i part of tertiary butyl hydroperoxide was added.

Films were made from the mass and heated to 130 ° for 15 minutes. making them insoluble in benzene.

Example ? 2o parts of a copolymer obtained by emulsion polymerization of 75 parts of methyl acrylate and 25 parts of m-oxystyrene were prepared in i5o parts of a mixture of equal amounts of technical denatured alcohol and benzene dissolved. Thereupon 40 parts of a 25% water Solution of Tetramethy laminoniumhydroxyd and then i g ß-Methallylchlorid added. To make the mixture homogeneous, a further 60 parts were then denatured Spirit added. The mixture was then left to stand for 18 hours at room temperature, neutralized by the addition of II-sulfuric acid up to pH = 7 and divided into iooo parts poured a 5% aqueous saline solution. The rubbery one that separates out Precipitate was filtered off, washed with water and dried at room temperature. The product was then further purified by adding it to 100 parts of an alcohol-benzene mixture dissolved and by adding a large amount of a mixture of 25% benzene and 75% Petroleum ether precipitated, the precipitate filtered off, washed with petroleum ether and finally was dried by standing at room temperature. After one hour of heating this etherified copolymer at 130 ° under pressure was crosslinked the product so that it was insoluble in an alcohol-benzene mixture.

Example 8 54 parts of a copolymer obtained by polymerization a mixture of 74.5% styrene and 24.5% o-oxystyrene in the presence of i% tertiary Butyl hydroperoxide was dissolved in benzene so that a weight percent Solution was obtained. There were then 19 parts of methylpyridinnium hydroxide and then 16 parts of diethyl sulfate were added. The mixture was then stirred for 2 hours kept at 40 °, then filtered and the etherified copolymer by pouring precipitated in technical alcohol denatured by methyl alcohol, filtered off, washed with denatured alcohol and finally in an oven at 70 ° for 3 hours dried.

Copolymers according to the present invention with or without crosslinking can be etherified, consist, for example, of oxystyrenes and the mixed monomers, such as butadiene hydrocarbons, chloroprene, styrene compounds, vinyl naphthalenes, Acenaphthylene, N-vinyl compounds such as vinyl pyridine, cyclopentadiene, and vinyl Vinylidene halides, vinyl esters, acrylic acid esters, unsaturated aldehydes, such as Acrolein and allyl compounds. These copolymers can be used in any desired amounts on oxystyrenes, e.g. B. from 0.1% to 99.9%. Suitable aldehydes are, for. B. acetaldehyde, butyraldehyde, furfural, benzaldehyde and formaldehyde, the latter being is preferred.

Claims (5)

PATENT CLAIMS: i. Process for the production of polymers and copolymers, characterized in that oxystyrene polymers with free core oxy groups are etherified. 2. The method according to claim i, characterized characterized in that the etherification in the presence of alkaline condensing agents which are relatively inert to the etherification agent, and the condensing agent at least in an equimolecular amount calculated on the free nuclear oxy groups, is used. 3. The method according to claim i and 2, characterized in that the etherification is in solution, suspension or emulsion he follows. 4. The method according to claim i to 3, characterized in that oxystyrene polymers are used which, with respect to the free nuclear oxy groups, have one or have two unsubstituted o- or p-positions, and the polymer before, during or, after the etherification, is also reacted with an aldehyde. 5. The method according to claim 4, characterized in that such polymers are used contain at least 2 mol percent of oxystyrenes with free oxy groups in the nucleus contain.