DE1123471B - Process for the production of partial amides or partial esters from anhydride polymers - Google Patents

Description

Process for the production of partial amides or partial esters from anhydride polymers The invention relates to a method for producing partial esters and partial amides of polymeric "unsaturated monocarboxylic acids, such as acrylic acids, in particular of Partial esters and part amides of polycarboxylic acids by treating polymeric anhydrides the c-unsaturated monocarboxylic acids with a primary or secondary alcohol, with ammonia or a primary or secondary amine. In the reaction products is no more than half of the carboxyl groups on the main polymer chain esterified or amidated. With partial esters or partial amides of the polycarboxylic acids are the ester and amide groups so distributed over the polymer chain that not more than two adjacent carboxyl groups have been converted into ester or amide bonds.

The polymeric anhydrides of o;, ß-unsaturated monocarboxylic acids or acrylic acids or substituted acrylic acids have a number of the following repeating units: which can be referred to as methyleneglutaric anhydride groups. In the above formula, R represents hydrogen, chlorine, fluorine, bromine, a nitrile group, an alkyl group having 1 to about 10 carbon atoms, an aryl group, an aralkyl group, or an alkaryl group. R means hydrogen, chlorine, bromine or fluorine. The polymer is thus a polymeric anhydride of acrylic acid or a substituted derivative thereof. If the anhydride polymer is reacted with a primary or secondary alcohol or a primary or secondary amine or with ammonia, the anhydride group is opened and the reaction is directed so that only one of the carboxyl groups is esterified or amidated and the other carboxyl group remains free in the event of esterification . In the case of amidation, the carboxyl group is converted into the ammonium or amine salt, except in the case of very weakly basic amines, e.g. B. Aniline, where an amide group is formed without amine salt formation.

The reaction between the polymeric anhydride and an alcohol or phenol, represented by XOH, proceeds according to one of the following formulas: with the formation of alternating ester and carboxyl groups or to form a structure in which adjacent carboxyl groups are esterified. It is very likely that both forms of reaction will take place. However, when the anhydride bonds are opened, only one of the carboxyl groups is esterified and the other is not converted. If all anhydride groups are converted, half of the carboxyl groups are free and the other half esterified, but neither more than two adjacent carboxyl groups are free nor are more than two adjacent ester bonds present.

A similar reaction takes place when the anhydride bonds with Amines or ammonia can be opened. One of the carboxyl groups is amidated, and the other forms a salt with the amine or NH3.

So far, this type of arrangement of ester and amide groups on one Acrylic acid polymer chain not possible. Mixed polymers of acrylic acids and substituted ones Acrylic acids with acrylamide or substituted acrylamides or with acrylic acid esters or esters of substituted acrylic acids are known. In these copolymers however, is the arrangement of the carboxyl ester or bonded to the main polymer chain Amide groups more or less randomly and not uniformly. The even distribution the ester or amide groups along the chain gives the polymers some fairly unusual properties.

According to a certain process, linear anhydride polymers are produced, by acrylic acid or substituted derivatives thereof in the presence of an inert Diluents, such as benzene, and an excess of a dehydrating agent, such as acetic anhydride, and in the presence of catalytic amounts of a free radical forming catalyst are polymerized at a temperature of about 50 to 70 ° C.

Crosslinked acrylic anhydride polymers in which the cross bonds are not destroyed by cleavage of the anhydride bonds, can be produced by a polyunsaturated monomer, e.g. B. polyallylsucrose with at least three allyl groups in the molecule, with an acrylic acid or a substituted derivative the same in an inert diluent in the presence of a free radical forming agent Catalyst and a dehydrating agent such as acetic anhydride, copolymerized will. A process for the preparation of these polymeric anhydrides is the subject of Patent 1,079,836.

For the preparation of the anhydride polymers, x,-unsaturated monocarboxylic acids of the structure are suitable in which R and R have the meanings given above. Special anhydride polymers are those derived from acrylic acid, methacrylic acid, a-ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl and decyl acrylic acid, o; - Chlorine, bromine and fluoroacrylic acid, cyanoacrylic acid, sc-benzyl acrylic acid, a-tolylacrylic acid and other a-substituted acrylic acids with hydrocarbon substituents of up to about 10 carbon atoms are produced. Anhydride polymers produced from acrylic, methacrylic, α-chloroacrylic and α-cyanoacrylic acid are preferred. Anhydride polymers made from acrylic and methacrylic acid and mixtures of these acids are most suitable. All of these anhydride polymers contain the unique repeating structure in which tu is an integer greater than 1 and R and R have the meanings given above. If the anhydride polymer is a homopolymer, each R group represents the same substituent and Ri also represents the same group. If the anhydride is prepared from a mixture of different acrylic acids or substituted acrylic acids, R and Ri can each be different and one or more of the above represent mentioned substituents.

The partial esters according to the invention can be prepared by the anhydride form of the polymers with primary or secondary alcohols or one Phenol, which are each free of primary or secondary amine groups, implemented will. The reaction is preferably carried out in an inert diluent, e.g. B. a liquid hydrocarbon or halogenated hydrocarbon in which the alcohol is soluble, in the presence of a trace of an alkaline tertiary amine such as pyridine, carried out at a slightly elevated temperature of about 50 to 100 ° C. The reaction runs even at room temperature, but the speed is for practical purposes too low. Is a tertiary amine substituent in the one in the esterification reaction contain alcohol or phenol used, the above-mentioned tertiary Amine not to be used as an esterification catalyst.

Suitable alcohols are methanol, ethanol, n-propanols and secondary ones Propanols, n-butanols and secondary butanols, n-pentanols and secondary pentanols, n-hexanols and secondary hexanols, n-heptanol and secondary heptanol, n-octanol and secondary octanol, n-nonanol and secondary nonanol, n-decanol and secondary Decanol and n-dodecanol and secondary octadecanol, n-eicosanol and secondary eicosanol. Suitable aromatic hydroxyl compounds are phenol, cresol, resorcinol, phloroglucinol, Hydroquinone, oc-us IB-naphthols and the like.

Suitable polyols are ethylene glycol, polyethylene glycols, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, glycerine, erythritol, Pentaerythritol, mannitol, sorbitol, glucose, levulose, sucrose, starch, cellulose, Polyvinyl alcohol and other polyhydric alcohols.

Other alcohols that do not react with the anhydride bonds Containing substituents, such as acidic or tertiary amino groups, are dimethylaminoethanol, Diethylaminoethanol, dipropylaminoethanol, dibutylaminoethanol, 2-chloroethanol, 2-bromoethanol, B-hydroxypropionic acid, monoalkyl ethers of ethylene glycol, 3-nitropropanol and other alcohols that have neither a thiol nor a primary or secondary amino group contain.

The partial amide derivatives according to the invention can be prepared by the anhydride polymer with a primary amine, a secondary amine, or ammonia gas in an inert diluent, e.g. B. a liquid hydrocarbon or a liquid halogenated hydrocarbon. The amines can be saturated or unsaturated, aliphatic, alicyclic or aromatic. A catalyst is usually not required. The reaction goes well at room temperature, however, elevated temperatures can be used to shorten the reaction time. An excess of the amines or ammonia reacts under these mild conditions with one of the two anhydride bonds to an amide group, and the other carboxyl group is converted into the ammonium or amine salt, but remains very weakly basic Amines have not reacted the carboxyl group. Becomes 1 mole of ammonia per anhydride group or amine reacted, the hemiamide is formed and the carboxyl group does not remain implemented.

Less than 1 mole of ammonia or amine per anhydride group results in one Polymers with amide groups, free carboxyl groups and unreacted anhydride groups.

The following amines are particularly suitable for amide formation: methylamine, Dimethylamine, ethylamine, diethylamine, propyl and dipropylamine, amyl, hexyl, heptyl, Octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, octadecyl and eicosylamine, Aniline, toluidines, xylidines, mesitylene, cumidine, phenylenediamines, toluylenediamines, mixed aromatic-aliphatic secondary amines, e.g. B. N-methylaniline, N-ethylaniline and other N-alkyl substituted aromatic amines.

The reaction of primary and secondary amines with the anhydride polymer leads to the formation of the following structural units: Here, R and R have the same meaning as before, X means hydrogen and / or hydrocarbon radical with 1 to 20 carbon atoms, and X represents hydrogen and a hydrocarbon radical with 1 to 20 carbon atoms. As already mentioned, these different structures can be regulated by regulating the Amine or ammonia reacted with the anhydride are formed.

It can be achieved that on the same polymer chain ester, Amide, free carboxyl groups, anhydride and amine salt groups are present by the Polymers with less than stoichiometric amounts of the primary or secondary alcohol or primary or secondary amine or ammonia to form a polymer, in which between 0 to 5 and 80% of the anhydride groups are not converted, converted will. The anhydride will first convert some of the anhydride groups to it Ester groups reacted with an alcohol, so the remaining anhydride groups are then reacted with an amine, some or all of the anhydride groups are converted into amide and free carboxylic acid groups. Reversed the anhydride polymer first reacted with less than the stoichiometric amount of an amine, so can the remaining anhydride groups or part of them with an alcohol to form ester bonds and free carboxylic acid groups are reacted on the polymer. That way you can End products with various properties are produced.

In the following examples, all parts are by weight understand unless otherwise stated.

Example 1 In a mixture of about 10% acrylic acid and 90% benzene 1 mole of acetic anhydride was added per mole of acrylic acid. Benzoyl peroxide was added in such an amount that its concentration is 2% based on acrylic acid, fraud. The air was expelled from the polymerization flask with nitrogen, the flask closed and the temperature adjusted to 50 ° C. After about 16 hours the reaction was over. The linear polyacrylic anhydride turned out to be a white, flaky powder suspended in benzene was formed. The polymer was filtered, washed with benzene and then dried in a vacuum oven at 50 ° C.

The partial methyl ester of polyacrylic anhydride was produced by slurrying the polymer in benzene with 1 mole of methanol per anhydride group in Presence of a trace of pyridine as an esterification catalyst treated became. The esterification was carried out at 50 ° C. for 16 hours. The partial methyl ester formed was soluble in water and ethanol.

It formed rather viscous solutions in water and after drying the Solutions a clear, colorless, flexible film. This polymer is suitable as Thickener and emulsifier for mixtures of 70 parts of water and 30 parts Hexane.

Polymethacrylic anhydride is made in the same way however, methacrylic acid is used instead of acrylic acid.

Example 2 Another polyacrylic anhydride was based on that in Example 1 described manner produced. The polymer was isolated by filtration and freed from acetic anhydride by washing with benzene.

It was then dried in a vacuum oven at 50 to 60 ° C.

Half esters were prepared as follows: 100 μg solutions were obtained of the anhydride polymer in several different liquid alcohols and a halohydrin prepares. The solutions were heated to 50 ° C. and stirred for 24 hours. The part esters were then precipitated with hexane, filtered and dried. When alcohols were in this production method the half esters ethanol, n-butanol, n-pentanol, n-hexanol and allyl alcohol used; Ethylenechloride served as halohydrin. All part esters were soluble in acetone, methanol and benzene and formed clear, colorless films out of solution. The water sensitivity of the films increased with increasing molecular weight of the alcohol used in the esterification. The part ester is a good suspension or suspension Thickener in alkaline aqueous solution. The partial butyl ester is an excellent one Glue for bonding glass to glass or aluminum foils to glass. The partial allylester can be in adhesive or film form due to a small amount of a free radical forming agent Catalyst, e.g. B. Benzoyl peroxide, are cured.

The ammonium salt of the n-pentyl partial ester, produced by neutralization of the carboxyl groups of the partial ester with ammonium hydroxide is a very good stiffness for cotton and cellulose triacetate. It affects the tensile strength or tear strength or the abrasion resistance of the fiber is not significant. A 1% solution of the ammonium salt of the n-pentyl partial ester was prepared by adding 1 part of the partial ester partial acid polymer 100 parts of 1% ammonium hydroxide was added. A cotton print fabric and a cellulose triacetate cloth was dipped in the solution and air dried.

The amount adhered to the fabric was 1550/0 on a dry basis. The test results are shown below. Cotton cellulose triacetate Untreated Treated Untreated Treated Sample sample comparison sample sample Clark stiffness, cm ...... 6, 2 11, 2 50 539 Bending and abrasion test according to Stols 530 69 039 39 (0, 5 lb. on head, (1 lb. on head, 2 lb. on yoke) 2 lb. on yoke) Elmendorf strength, g .......... 385, 6 399, 2 259, 6 235, 9 Tensile strength, kg / cm2 3, 29 3, 43 2, 24 2, 24 Articulation angle ................... 82 65 82 77 No visible discoloration was found on the cotton after 40 hours in a fadeometer.

Analysis of that formed by reaction with ethylene chlorohydrin Partial ester showed that about 90% of the anhydride bonds to an ester group and a carboxyl group were reacted.

Partial esters of the anhydride copolymers of firstly acrylic acid and methacrylic acid, secondly acrylic acid and α-bromoacrylic acid and thirdly methacrylic acid and α-bromoacrylic acid and the aforementioned alcohols were prepared in the manner described above manufactured. The partial esters were all in acetone, methanol, benzene, γ-butyrolactone and dimethylformamide and all made excellent adhesives.

The properties of these partial esters are different from those of Copolymers of acrylic acid with acrylic acid esters. For comparison purposes, a Range of copolymers of acrylic acid and substituted acrylic acid with esters of acrylic acid and substituted acrylic acid prepared as follows: There were 10% Solutions of the monomers in Benzene prepares. The flasks were closed and the Temperature set to 50 ° C. The polymerization conditions were essential the same as in the preparation of the anhydride polymers except for the dehydrating agent was not present and an ester of an acrylic acid or substituted acrylic acid was added to the monomer mixture.

In this way, mixed polymers of 45, 60 /, acrylic acid and 54.4% methyl acrylate, 41.8% acrylic acid and 58.2% ethyl acrylate, 20, 24, 28, 32, 36, 40 and 52% acrylic acid with 80, 76, 72, 68, 64, 60 and 48% butyl acrylate, respectively and 46.2% methacrylic acid with 53.8% methyl methacrylate. None this copolymer was in acetone, methanol, γ-butyrolactone or dimethylformamide soluble.

Example 3 A mixture of 20 g of linear acrylic anhydride and 200 g of lauryl alcohol was used for several days in the absence of an esterification catalyst held at 50 ° C. After adding excess hexane to the mixture, the Part esters as fine, flaky, white powder precipitated. The polymer was filtered, washed with more hexane and dried. The partial ester gained weighed 26 g. It was soluble in ethanol and methyl ethyl ketone, but insoluble in water. The polymer was an excellent emulsifier for a mixture of 70 parts of heptane and 30 parts of water. Films of the partial ester were not sensitive to water.

Partial esters of lauryl alcohol were also made by dissolving of the alcohol in benzene, addition of 19 g of the linear polyacrylic anhydride and 6 drops of pyridine followed by heating to 50 ° C for 24 hours. A part ester was made from a solution of 26 g of lauryl alcohol in benzene and another with 13, 5 g of the alcohol made in benzene. The partial esters produced in this way were soluble in acetone and sparingly soluble in water.

Example 4 A series of partial esters were prepared by dispersing of 10 g of linear polyacrylic anhydride in benzene and the addition of one of the following named alcohols. All esterifications were made at a temperature of about 50 ° C or executed above.

Table 1 lot Alcohol solubility G Methallyl alcohol ..... 25 γ-butyrolactone Pentanol-3 ........... 20 dimethylformamide 2-nitro-1-pentanol .... 25 γ-butyrolactone Butanol-2 20 γ-butyrolactone Isobutanol ........... 24 Dimethylformamide 2,4-Dimethyl-1-pentanol 25 y-butyrolactone n-nonanol ........... 50 γ-butyrolactone Geraniol 50 5% NaOH Myristyl alcohol ...... 50 acetone n-Undecanol ......... 80 In dimethyl form- amide swollen n-Heptadecanol ...... 70 In dimethyl form- amide swollen Cetyl alcohol ......... 50 acetone n-octadecanol 18, 5 dimethylformamide Ceryl alcohol ......... 50 In dimethyl form- amide swollen )> Keryl <(alcohol * .... 30 5% NaOH 3-chloro-1-propanol ... 5% NaOH * This means an alcohol that was produced from an alkylated benzene and whose alkyl group usually contains 10 to 12 carbon atoms. -The exact position of the OH group in the side chain is unknown.-Production of sodium decylbenzoisulphonate.

Films could be precipitated from solutions from each of the partial esters. Those made from the partial ester of methallyl alcohol and the partial ester of geraniol Films can be produced by heating in the presence of a free radical forming catalyst, z. B.

Benzoyl peroxide, can be further polymerized, with hard, tough films are formed. The partial esters of the higher alcohols, such as undecanol or ceryl alcohol, are Soluble with some difficulty, but they are excellent emulsifiers in sodium, potassium or ammonium hydroxide solutions. The solutions of all part esters This example in organic solvents are excellent adhesives for Bonding glass to glass or metal to glass.

Example 5 A series of partial esters were made using glycol monoethers produced as alcohols.

To this end, about 10 g of linear polyacrylic anhydride were used in excess slurried by usually about 200 cc of benzene. After adding the alcohol with some Drops of a tertiary amine, the mixture was kept at 50 ° C for about 24 hours. The glycol monoethers used in the production of the partial esters, their quantities and the solubility properties of the derivative are shown in Table 2.

Table 2 Glycol Monoether I Amount I Solubility I g I Diethylene glycol monoethyl ether 38 5% NaOH- solution Diethylene glycol monobenzyl ether 60 in dimethyl form amide swollen Ethylene glycol monoethyl ether 20 in dimethyl form amide swollen 50 in methanol Ethylene glycol swollen monobutyl ether .... 40 In 5% NaOH Solution soluble Ethylene glycol monobenzyl ether ... 50 Insoluble Polyethylene glycol monomethyl ether (Molecular weight about 350) ......... 55 γ-butyrolactone The solubility behavior of these partial esters is somewhat different from that of the esters of the aliphatic alcohols mentioned in Table 1, as only some of the derivatives are themselves soluble in very effective solvents. Dry films of the diethylene glycol monoethyl ether derivative were very tough and rubbery. All part esters were good glue.

Example 6 Alcohols with a cycloaliphatic ring also react with linear polyacrylic anhydride to form partial esters. There were 10 g of polyacrylic anhydride Slurried in about 200 cm3 of benzene and then the alcohol and about 6 drops of one tertiary amine, e.g. B. pyridine added. The mixture was at about 24 hours Maintained about 50 ° C to prevent the reaction with the anhydride groups without esterification To bring carboxyl groups to essentially completion.

Listed below are some cycloaliphatic alcohols that were used for the production of partial stars.

Table 3 lot Alcohol solubility G Cyclohexanol .. .... 16 dimethylformamide Furfuryl alcohol ...... 20 Tetrahydrofurfuryl # In dimethyl form alcohol ..... .. 30 amide swollen Fenchyl alcohol ... .... 25 Each of these partial esters could be produced in the form of a film and is a very good adhesive for bonding metals or glass to one another.

Example 7 A number of phenols were made with linear polyacrylic anhydride reacted by adding a phenol to a slurry of the anhydride in benzene.

In each case 10 g of the anhydride were placed in 200 cm3 of benzene, the phenol with a few drops of pyridine added and the mixture at for 24 hours held about 50 ° C. The following table lists the phenols used, theirs Quantities and solubility of the derivatives are given.

Table 4 lot Phenol solubility G o-bromophenol ....... 28 γ-butyrolactone p-bromophenol ....... 27,5 γ-butyrolactone 2-bromo-4-tert. butyl phenol 40 dimethylformamide 2,4-dichlorophenol .... 26 γ-butyrolactone o-cresol ..... 20 dimethylformamide m-cresol .... 20 dimethylformamide p-cresol .......... 20 dimethylformamide p-Benzylphenol ....... 27 Dimethylformamide p-tert-butylphenol. 25 γ-butyrolactone 4-tert-butyl-7-chloro phenol 30 γ-butyrolactone o-Cyclohexylphenol ... 24,5 y-butyrolactone Diisobutylphenol ..... 33 γ-butyrolactone 2-chloro-4-phenylphenol 58 dimethylformamide 2, 4-dinitro-4-chloro phenol ..... 40 5 "/ igue NaOH- solution 2,4-Dinitrophenol .... 30 5% Na O H- solution Eugenol ............. 27 5 /. ige NaOH solution Carvacrol ......... 25 Dimethylformamide Hydroquinone mono- methyl ether 40 In dimethyl form amide swollen o-Hydroxyacetanilide ... 25 In dimethyl form- amide swollen p-Hydroxyacetanilide ... 25 γ-Butyrolactone mN-diethylamino- phenol ........ .. 28 γ-butyrolactone Acetoxy-o-methyl- aminophenol ...... 25 γ-butyrolactone Acetoxy-p-methyl- aminophenol ....... 25 dimethylformamide 3, 5-Dimethylphenol ... 19 Dimethylformamide The phenol derivatives listed above have a unique property in that they can be further reacted with aldehydes including formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde to form infusible and insoluble films. The solutions of the phenol derivatives are excellent adhesives.

Example 8 Other hydroxyl-containing compounds can be used with linear Polyacrylic anhydride are converted into partial esters that are in certain solvents are soluble and make excellent adhesives. The method of manufacture of the derivatives is the same as described in Example 5.

Table 5 Alcohol amount of solubility Glycolic acid ... 25 5% NaOH- solution Glyconitrile ....... 25 dimethylformamide p-hydroxypropionitrile 25 50 / ge Na O H- solution y-hydroxypropionitrile Aldol ... 30 5% NaOH- solution Diacetin ........... 50 dimethylformamide Ethyl acetoacetate 22 5% NaOH- solution Kojic acid 40 5% NaOH- solution All derivatives form tough, flexible films. The film formed with diacetin was rubbery. Solutions to the products are all very good adhesives.

The ethyl acetoacetate also forms a keto form Enol, with whose hydroxyl groups the anhydride groups react.

Example 9 A partial ester of linear polyacrylic anhydride and Methyl acetate was prepared in the manner described in Example 5. The product was also a good glue.

Example 10 A group of phenyl substituted aliphatic alcohols was reacted with polyacrylic anhydride in the manner described in Example 5. The alcohols can contain other functional groups that are compatible with the anhydride or the carboxyl groups do not react.

Table 6 lot Alcohol solubility G Benzyl alcohol ....... 35 dimethylformamide Benzoin ............. 33 Dimethylformamide Cinnamon alcohol ......... 38 In dimethyl form- amide swollen 2-phenylethanol 40 dimethylformamide 3-Phenylpropanol ..... 40 In dimethylform- amide swollen p-tert-amylphenoxy- Dimethylformamide These derivatives also form water-insensitive films and can be used as an adhesive in solution. There were also 2.5 g of polyacrylic anhydride in dry acetone with an excess of p-chlorophenoxyethanol and another sample with 2,4-dichlorophenoxyethanol in excess. The former reacted with about 76% of the anhydride groups and the latter with about 87% of the anhydride groups. Tri-, tetra- and pentachlorophenoxyethanols were also reacted with polyacrylic anhydride. These derivatives form very viscous slimes in dilute aqueous NaOH solutions. A derivative of was prepared by reacting 0.1 mole with 0.1 mole of polyacrylic anhydride. Each derivative was soluble in dimethylformamide, acetone and 5% NaOH solution. In this way, polymers which act as weed killers are obtained.

The products are also good adhesives.

Example 11 Linear polyacrylic anhydride reacts with acetals to form unique derivatives in which one carboxyl group is esterified to an alkyl ester group and the other carboxyl group forms an alkyl ether ester group. For example, methylal forms a derivative with the following structure: It is therefore possible to convert essentially all anhydride bonds on the polymer chain with equimolecular or higher amounts of an acetal based on the anhydride groups to form a mixed ester-ether ester derivative with essentially the same number of ester and ether ester groups on the polymer chain. It is also possible to convert less than all anhydride bonds to ester-ether ester derivatives and to leave the remaining anhydride bonds unreacted so that the unreacted anhydride groups can be converted to partial esters of the same or a different alcohol, partial amides or salts.

Acetals of propionaldehyde, butyraldehyde, the acetals made from acrolein or crotonaldehyde with low molecular weight monohydric alcohols can be used.

The process of making the derivatives of acetals is essential the same as that used to make the partial esters. A slurry of 10 g of linear polyacrylic anhydride in 200 cm3 of benzene was prepared, with 20 g of methylal and a few drops of pyridine added and the mixture was kept at 50 ° C. for about 24 hours. The polymer was in Benzene insoluble.

It was filtered, washed with additional benzene and then dried. The methyl methoxymethyl ester derivative was swollen in dimethylformamide.

The derivatives formed by other acetals differ from that specifically described only in the groups attached to the side chain of the polymer. Acetal thus forms the unit and butyral the unit If 1/2 mole of the acetal is used per mole of anhydride in the polymer, only about half of the anhydride groups are converted into ester, ester-ether bonds, and the remaining anhydride groups are available for salt formation, partial ester formation or partial amide formation.

Example 12 Also primary or secondary alcohols, the tertiary amino bonds can be reacted with the linear polyacrylic anhydride to form partial esters.

It was worked in the same way as in Example 5, however no catalyst was added and a reaction time of only about 1/2 hour applied.

Table 7 Alcohol amount of solubility | g | Di- (ethylhexyl) -ethanol- amine .............. 90 In dimethyl form- amide swollen Monomethyl-N, N'-di- methylhydantoin ... 25 γ-butyrolactone The monomethyl-N, N'-dimethylhydantoin forms an enol, which reacts with the anhydride groups to form an ester.

In the case of the amino alcohols, the anhydride ring is formed with a Open esters; the carboxyl groups react with additional amino compounds to an amine salt. In the polymer there are both esters and salts of the carboxylic acids and amines bound to the amine polymer chain.

The esterification process can also be carried out so that the linear anhydride polymers in a solvent, e.g. B. dimethylformamide, a dimethyl sulfoxide or dissolved in other solvents that do not react with the anhydride, the Alcohol added and the mixture depending on the type of alcohol or its concentration is held at about 50 ° C for about 1 to 24 hours.

The reaction takes place even in the absence of a diluent instead of when the alcohol is liquid at room temperature.

Ammonia, primary amines and secondary amines react with the anhydride bonds in the absence of water to form the following units: which are part of the main polymer chain. In the formula, R, RI, X and Y each represent the groups mentioned above. Amides and free carboxyl groups or amides, free carboxyl groups and unreacted anhydrides can also form.

Salt formation takes place with all but very weak amines, such as Aniline, instead. In the latter case the amide is formed, but the carboxyl group remains free and not implemented.

The partial amides can be made by mixing the anhydride and the amine in an inert solvent in which the amine is soluble, preferably in a liquid aromatic hydrocarbon, and heating the mixture up about 50 ° C. A catalyst is not required. The reaction is very quick and is usually completed in about 1 hour. It can also be worked that the linear anhydride polymer in a solvent such as dimethylformamide or Dimethyl sulfoxide or other solvents that do not react with the anhydride, dissolved, the amine was added and the mixture was kept at about 50 ° C. for about 1 hour will.

The heating is only done to speed up the reaction, because the same derivative can also be used at room temperature or even lower temperature, but can be obtained in a longer period of time.

The reaction takes place even in the absence of a diluent instead of when the amine is liquid at the reaction temperature.

The partial amides are unique in that they are good emulsifiers and are good suspending agents over a very wide pH range.

Example 13 A mixture of 22 g of linear polyacrylic anhydride and 17.8 g of 3-N, N-dimethylaminopropylamine was prepared and kept overnight at Kept room temperature. The amount of the amine was about 2 moles per mole of anhydride groups.

The derivative formed was not converted by the small amount Separated amine, washed with benzene and dried. The polymeric derivative contained 10.85 zozo nitrogen, from which it could be seen that about 71% of the anhydride groups were converted into amide-amine salts.

A series of 10% aqueous solutions of the derivative were prepared. At this concentration, the solution had a pH of 5.85 and a viscosity of 240 as determined on a Brookfield Viscometer using a spindle No. 4 at 20 rpm.

The pH of the remaining 10% solutions was adjusted to various levels by adding NaOH or HCl and the viscosity at the various pH values was determined. These values are given in the following table: Table 8 PH value } 5, 6 1 5, 0 1 4, 6 1 4, 0 1 2, 4 1 7, 8 rf Viscosity ... 84 72 44 40 j 48 40 PH value 7, 4 1 8, 0 1 9, 1 1 9, 7 10, 010. 4 Viscosity ... 180 192 188 168 168 204 The viscosity behavior over such a wide pH range is unique and typical of the partial amides.

Example 14 A series of linear polyacrylic anhydrides were made produced by polymerizing 20 g of acrylic acid in the presence of 34 g of acetic anhydride, 200 cm3 of benzene and 0.4 g of diisoazobutyronitrile. In each case the polymer was washed carefully with benzene and then resuspended in 200 cc of fresh benzene.

The following amines were used to produce the partial amides: amount, g diethyliminodiacetate 30 n-butylamine ....................... 11, 6 piperidine ................. ......... 13, 5 diisobutylamine .................... 20, 4 p-aminoacetophenone ............... 21, 3 1-aminoanthraquinone .............. 35, 3 4-aminobiphenyl ................... 26, 9 aminosilane ........................ 15 benzylamine 16, 9 m-bromoaniline .............. ........ 27, 2 In the preparation of the partial amides, the amine of the slurry of the polyacrylic anhydride added in benzene. The bottles were sealed and rotated at 50 ° C for 24 hours. All partial amides were in dimethylformamide and with the exception of 4-aminodiphenyl derivative also soluble in 5% NaOH solution.

Example 15 Another series of partial amides was prepared by treating a slurry of 44 grams of linear polyacrylic anhydride in benzene with varying amounts of the following amines: Amine amount of barcol hardness G Di-2-ethylhexylamine .......... 84 Aniline 32, 3 42 2-naphthylamine .............. 49, 7 30 n-Hexylamine ................. 35, 1 Dicyclohexylamine 63 33 Dimethylamine 35, 5 Propylamine 30 Cyclohexylamine 34, 4 25 The determination of the Barcol hardness was made after molding into tablets. All of the aforementioned polymers are excellent adhesives.

Example 16 A derivative of polyacrylic anhydride which is both ester and also containing amide groups was prepared as follows: The anhydride polymer was in the manner described in Example 13 and with the amounts of the specified there Components manufactured.

After washing and resuspending in benzene, the slurry First 7.3 g of ethanol were added, the bottle was moved at 50 ° C. for 24 hours, then 5.8 g of n-butylamine were added and the bottle was agitated at 50 ° C. for a further 24 hours. The product was soluble in 5% NaOH solution, methanol and dimethylformamide partially soluble in γ-butyrolactone.

Example 17 A crosslinked polyacrylic anhydride was prepared by adding 25 g of a copolymer of 99% acrylic acid and 1% allyl sucrose with 5, 6 allyl groups in the sucrose molecule 4 hours with 500 cm3 acetic anhydride treated under a reflux condenser. The copolymer treated in this way it was washed with benzene to remove the mixture of acetic anhydride and acetic acid was, and then the crosslinked copolymer of polyacrylic anhydride and allyl sucrose suspended in 500 cc of fresh benzene. After adding 56 g Ethylene chlorohydrin to the slurry in benzene was refluxed for 2 hours heated. The partial ester contained 13.5% chlorine, i. H. 87 to 88 ° / o of the theoretical Anhydride groups on the polymer had reacted with the alcohol to form a partial ester.

Partial esters of ethanol and n-butanol were made by a molar equivalent of an alcohol and the crosslinked copolymer described above of polyacrylic anhydride was implemented. The partial esters were then washed with aqueous Sodium hydroxide treated to neutralize about 75% of the free carboxyl groups. At a concentration Tration of 1n5% in water had that from a partial ethyl ester and partial sodium salt consisting product has a viscosity of 24, determined with a Brookfield Helipath viscometer, and that containing n-butyl as a partial ester component Derivative has a viscosity of 48 at the concentration given above. More part esters were made with methanol, 8-hydroxyquinoline, n-octanol and isopropanol.

Partial amide derivatives of crosslinked polyacrylic anhydride were produced by the anhydride with ammonia, ß-dimethylaminopropylamine, dipyridylamine and N- (2-Aminoethyl) morpholine was implemented. All of the partial amide derivatives were exceptional Suspending agent at low pH in aqueous media.

Example 18 A copolymer of 90% acrylic acid and 10% Allyl sucrose with five to six allyl groups in the sucrose molecule was obtained by heating converted to its anhydride form under reflux with acetic anhydride. The washed crosslinked polyacrylic anhydride was with 1 equivalent of diethylaminoethanol in one Excess benzene implemented at 50 ° C. The partial ester derivative had a nitrogen content of 2.52%. This polymer is a good ion exchange resin with both anionic as well as cationic exchange capacity.

Another derivative was made using 1 equivalent of ß-diethylaminopropylamine made in the same way. This partial amide derivative had a nitrogen content from 7, 35 ° / 0. Any of these nitrogen-containing polymers were good ion exchange resins.

Example 19 Methallylamine was in excess of 10 percent by weight Solution of linear polyacrylic anhydride in dimethyl sulfoxide added. The mixture was kept at 38 ° C for 24 hours. The derivative was precipitated with hexane, filtered and dried. It was soluble in aqueous ammonium hydroxide. One from the aqueous Solution cast film that was dried in an oven at 121 ° C for 1/2 hour, was only slightly sensitive to water.

The polymeric anhydride reacts with natural compound polyamides or polyols. Woolen yarn, which at 50 ° C in a 10% solution of polyacrylic anhydride is immersed, experiences a weight gain of about 33% and swells upon treatment with soapy water.

Casein also reacts to form a very viscous thick one Gels in water. Washed milk casein becomes after reaction with polyacrylic anhydride insoluble in water.

Gelatin forms in a solution of polyacrylic anhydride in dimethylformamide a very thick gel.

The gel swells in water, but does not dissolve, and so does the heat reversibility no longer appears.

Example 20 A sample of I26 g of polyacrylic anhydride in 1500 cm3 dry benzene was mixed with 17g of anhydrous ammonia in a mechanical stirrer and Treated device provided with dry ice-acetone condenser. The reaction between the anhydride polymer and ammonia were exothermic. After the mixture 16 hours had reacted with stirring, it was heated to 45 to 50 ° C. for 1.5 hours. One Yield of 140 g of dry polymer (98% of theory) with the following analysis was obtained: Calculated .......................... N 9.79 ° / 0COOH 6.99 (milliequivalents / g) ; Found .......................... N 9X29 ° / oC O O H 6.74 (milliequivalents / g).

This half-amide of polyacrylic anhydride was in water, dimethylformamide, Pyridine, acetone, acetonitrile, ethyl acetate and tetrahydrofuran are soluble, was used in the procedure described uses more than one equivalent of ammonia the partial ammonium salt of the hemiamide of polyacrylic anhydride. The hemiamide like its ammonium salt, is an excellent glue.

A collodion solution was a 10% solution of polyacrylic anhydride added in dimethylformamide and kept at 50 ° C. for 24 hours. It formed a precipitate that was insoluble in acetone.

"Cellophane" (registered trademark) began under the same Conditions to swell and then formed a gel. 5, 6 g cotton yarn learned under under the above conditions a weight gain of 4.4 g. The cotton was badly swollen. After drying and washing with soapy water, the cotton fibers swelled again.

Corn starch swells quickly in this treatment in dilute water Alkali to form a clear, thick gel. Soluble starch becomes insoluble but swells in dilute aqueous alkali. Tragacanth gum loses after treatment with the polyacrylic anhydride its swellability in water.

A uniform mixture of 10 g dry polyacrylic anhydride, 6, 24 g Na2COs and 10 g sucrose were produced. Will be such a lot of this Mixture given in water so that its concentration is 1, 5%, forms a very viscous slime with a viscosity of 56 poise as determined with the Brookfield viscometer. A cross-linked polyacrylic anhydride, produced by reacting 99n5% acrylic acid and 1/2% allyl sucrose with five to six allyl groups in the sucrose molecule in the presence of acetic anhydride, was mixed with sucrose. The unmixed Polymers had a viscosity of 97 in dilute aqueous NaOH solution while the mixture at a concentration of 1.5% had a viscosity of 216.

The crosslinked anhydride copolymers can instead of the linear Polyacrylic anhydrides for the production of partial esters and partial amide derivatives according to the procedure described for linear polyacrylic anhydrides can be used.

Partial esters and part amides of linear or crosslinked polymethacrylic anhydride can be prepared by the methods described above.

Example 21 A series of partial esters were prepared by adding an alcohol to a slurry of 50 g of polymethacrylic anhydride in an excess of benzene and agitating the mixture at 50 ° C for 24 hours. Softening Ge-temperature Barcol- Alcohol weight of the garden Derivative g ° C Methyl alcohol ....... 30 192 55 Ethyl alcohol ........ 13.4 113.5 43 n-propyl alcohol ..... 17, 5 119 37 Isopropyl alcohol .. 17, 5 121, 5 37 n-butyl alcohol ....... 21, 5 117, 5 42 n-amyl alcohol .. 25, 6 103 34 Isoamyl alcohol ....... 25, 6 108 35 n-Hexyl alcohol ...... 29, 6 110 34 n-octyl alcohol ....... 37, 8 109 23 2-ethylhexyl alcohol. 37, 8 104 27 The abovementioned polymers were isolated by suction and subsequent drying in air at 50.degree. The hardness was determined with a melted tablet of each polymer. In each case, the melted tablet was clear and essentially colorless.

From these values it can be seen that the derivatives are unusual have high softening temperatures and completely unexpected hardness values. the Polymer derivatives are all excellent adhesives, truly thermoplastic and can be processed into foils or molded parts.

Example 22 Another group of partial esters was prepared by adding the alcohols listed below to a slurry of 10 g of linear polymethacrylic anhydride in 200 cc of benzene and agitating the mixture at 50 ° C. for 24 hours. Ge Solvent for the Alcohol weight derivative G Isobutyl alcohol ...... 18 γ-butyrolactone Sec. Butyl alcohol ..... 20 5% NaOH- solution Pentanol-3 30 γ-butyrolactone 2,4-Dimethylpentanol-3 20 γ-butyrolactone Sec. Butyl carbinol .... 23 γ-butyrolactone Nonyl alcohol ........ 25 5% NaOH- solution n-Undecyl alcohol ..... 50 5% Na O H- solution Lauryl alcohol ........ Myristyl alcohol ...... 50 γ-butyrolactone Heptadecyl alcohol .... 70 γ-butyrolactone n-octadecyl alcohol ... 50 y-butyrolactone continuation Ge Solvent for the Alcohol weight derivative ..... Cetyl alcohol ......... 80 dimethylformamide Ceryl alcohol ......... 20 Keryl alcohol ......... 50 Dimethylformamide Methallyl alcohol ..... 25 γ-butyrolactone Geraniol 50 5% NaOH- solution Furfuryl alcohol ...... 30 γ-butyrolactone Tetrahydrofurfuryl ... 30 dimethylformamide Diethyl carbinol 30 γ-butyrolactone These polymeric partial esters were worked up in the manner described in Example 15. All of the polymers in this example have a softening point above 100 ° C. and can be melted into molded parts.

Claims (2)

PATENT CLAIMS: 1. Process for the production of partial amides or partial esters from anhydride polymers, the amide or ester groups in the partial amides or partial esters being distributed in such a way that no more than one amide or ester group is present on each anhydride group of the polymeric chain and at least 20 mol percent of the Anhydride groups of the polymeric chain are converted into partial amides or esters, characterized in that an anhydride polymer with the recurring groups of the following structure in which R is hydrogen, chlorine, fluorine, bromine, cyano, an alkyl group with 1 to 10 carbon atoms, an aryl group, an alkaryl group or an aralkyl group and Ri is hydrogen, chlorine, bromine or fluorine, with a compound of the general formula in which X denotes hydrogen or a hydrocarbon radical with 1 to 20 carbon atoms and Y denotes hydrogen or a hydrocarbon group with 1 to 20 carbon atoms, or with a compound of the general formula XO H in which X denotes a hydrocarbon group with I to 20 carbon atoms Means atoms, and optionally a tertiary amine with 4 to 20 carbon atoms at a temperature of about 75 ° C. 2. The method according to claim 1, characterized in that the implementation in an inert organic solvent, in particular benzene or dimethylformamide, is carried out. Documents considered: British Patent No. 528,438; U.S. Patent No. 2,321,738.