DE1645682A1 - Process for the production of organotin polymers and copolymers - Google Patents

Description

Process for the production of organotin polymers and copolymers The invention relates to a process for the production of organotin polymers and copolymers.

The method is characterized in that a salt is an acidic Compound that contains at least two identical or different acidic functions, dissolved in water, with an organotin compound of the general formula RlR2SnX1X2 is implemented. Carboxyl, sulfydryl, sulfonic acid, Amide primary or secondary sulfonamide groups or heterocyclic radicals with acidic Hydrogen atoms. In the general formula, R1 and R2 can be identical or different be and substituted or unsubstituted alkyl, aryl, aralcyl or heterocyclic bees Grpppen mean. X1 and X2 are halogen atoms or anions of acids with a pK of 4.8 or less. The Organoa tin compound can be mixed with water Immiscible organic solvents are dissolved.

Various organotin polymers are known, for example a Polymer of p-vinyltrialkyltin benzoate produced, which has a fungicidal effect (C.A. 61, 8340 (1964).

Polytrialkyltin acrylates are also known (M.F0Shostakovakii, Vysokomol. Soedin., 3,1128 (1960); D.A. Kochkin et al., O.A. 54, 5150 g (1960) Vysokomol. Soedin I, 482 (1959).

Polyorganostannates of the formula were made by reacting dialkyltin dichlorides with sodium. (SMZhivokhin, ED, Dudikova and AMKotow, Zh.Obsch.Khim.33,3274 (1963). In a further known process, polymers are obtained from dialkyl- or diaryl-tin ehydrides and diacetylene (Holläbd, patent specification 253 290).

The organotin polymer obtained according to the invention contains the tin atoms in the main chain and has the following general formula Here, A1 and A2 can be the same or different. they mean the radical defined above with at least two acidic functions. R1 and R2 have the same meaning as above.

The implementation of some dicarboxylic acids with dibutyltin diacetate and dibutyltin oxide has already been investigated (T.M.Andrews, F.A.Bower, B.R.Laliberte and J.O.Montermoso, J.Am.Chem.Soc.80. 4102 (1958). When heating adipic acid with dibutyltin diacetate in xylene at 1300 C a cyclic trimer of dibutyltin adipate is formed Melts at 136 - 137 ° C and has a molecular weight of 1205. With the same implementation with succinic anhydride and dibutyltin oxide, a cyclic tetramer is obtained with the melting point 18700 and the molecular weight 1430.

According to the invention, higher polymers are obtained, e.g. with adipic acid a polymer with a melting point above 200 ° C and with succinic acid a polymer, whose melting point is above 2300 C. These polyorganotin esters are in organic Solvent insoluble. This and its higher melting point shows that it is different are of the nature of the above-mentioned polymers produced by Andrewe et al.

According to the invention the salt of the compound with several acidic Groups dissolved in water. Then the organic compound as a solution in one Water-immiscible organic solvents are added and the reaction mixture is stirred. In general, the polymer forms immediately and, if so, precipitates it is unislich in the reaction mixture. The production is therefore very one subject and / there generally good yields.

The compound with several acidic groups is called the metal ammonium or amine salt applied.

The reaction between R2SnX2 and the salt of the compound with several Acid groups can act as an exchange between the X anion groups and the acid anions be understood. If z. B. X is chlorine and the acid anion is a carboxylate anion, the chlorine is the anion of a stronger acid (HC1) than the carboxylic acid Exchanging carboxyl groups, just as sulfuric acid can develop HC1 from NaCl. So it is required that the X in R2SnX2 be the remainder of a stronger acid than that of the anion taking its place. Accordingly, z. B. between dibutyltin dichloride and naphthol-2,6-disodium sulfonate no reaction leading to polymer formation take place because the sulfonic acid is stronger than the hydrochloric acid. On the other hand, can one from the implementation of R2Sn (ClO4) 2 with the disulfonate salt Expect polymer as the perchloric acid is stronger than the sulfonic acid.

In the implementation, the volume ratio is between aqueous and non-aqueous phase not critical. Ratios from 1 to 10 are applicable.

Organic solvents, such as aliphatic solvents, can be used for the non-aqueous phase or aromatic hydrocarbons, chlorinated hydrocarbons or ethers are used will. By exchanging the solvent you can polymers with different Make chain length.

The concentration of the reacting substances is neither in the aqueous one critical even in the non-aqueous phase. For example, it can be 1 molar to 1/10 molar @@in.

The reaction temperature is also not critical and can be at temperatures from -10 ° to around 500 a.

The polymers which can be produced according to the invention include, for. B. polyorganotin esters. The polycarbonic acids to be used have 2-4 carboxyl groups and correspond of the general formula R (COOH) N, in which n is a number from 2 to 4 and R is a Uflaubstitute or substituted alkyl, Aryl, aralkyl, or heterocyclic ones Group data.

Examples are adipic acid, sebacic acid, terephthalic acid, nitroterephthalic acid, Fumaric acid, itaconic acid, citric acid, tartaric acid, N-acetylglutamic acid, acetyldicarboxylic acid - and ethylenediaminetetraacetic acid.

Furthermore, according to the invention, polyorganotin thioether can be produced, by using polythiols of the general formula R (SH) n, in which n and R have the same meaning as above have implemented.

Organotin polymers from the conversion of thio acids, such as p-thiolbenzoic acid, also belong to the process products.

In addition, polymers are obtained by reacting primary and secondary Sulfonamides with at least two sulfonamide groups according to the general formula R- (SO2NHR1) 2, in which R and R1 have the meaning given above for R.

These polymers contain @@ - N bonds. It is known that To-N bonds, in which the nitrogen is bound as a sulfonamide or imide, are stable (Luijten and Van der Kerk, Investigations in the Field of Organotin Chemistry, published by Tin esearch Institute1England, 1955).

According to the invention, polyorganotin sulfonic esters can be prepared from naphthol di- or make trisulfonic acids.

Copolymers are obtained by reacting mixtures of salts of the compounds described above and / or of various organotin compounds.

The invention leads to new polymers that can be used for various purposes are usable. The fungicidal, fungustatic, bacteriocidal and bacteriostatic Properties of organotin esters are known.

Plastics resistant to insects and bacteria are obtained from Trialkyltin halides and organotin polyesters (Kochkin et al. G.A. 54, 5150 (1960).

Also the polymers produced according to the invention, the organotin ester groups contained in the main chain have such biological activity.

Another factor is the resistance of the anti-fungal tin compounds like tributyl or triphenyl tin acetate due to hydrolysis.

The new polyorganotin esters, on the other hand, are much more stable, since the tin is bound in the main polymer chain. The polymers are too particularly water-repellent. They are also used as plasticizers for plastics usable. Fibers and coating compounds can also be produced from the process products will.

The multitude of execution options then become given some examples.

Example Polydi-n-butyltin adipate 1.46 g (0.01 mol) of adipic acid were added Suspended in 5 ocm water and neutralized with 5 N sodium solution brought. Then 3.03 g (0.01 mol) of n-dibutyltin dichloride in 50 com of petroleum ether (Boiling point 40-60 ° C) added with vigorous stirring at OOC. After 20 minutes were 100 cm of acetone were added to precipitate the polymer, and the reaction mixture was then added filtered.

The following equation applies to the implementation The solid polymer was washed several times with water, ethanol and acetone. 3.2 g of polydibutyltin adipate with a melting point of 220 ° C. were obtained in a yield of 85%.

The intrinsic viscosity in trifluoroethanol was 0.05.

Analysis for Calculated C, 44.6., H, 6.9i Sn, 31.5, found C, 44.5 ; H, 6.5; Sn, 32.4.

The same yields are obtained if adipic acid is used instead of sodium hydroxide is neutralized with the equivalent amount of triethylamine.

When using xylene, tetralin, decalin, chloroform, carbon tetrachloride and methylene chloride as a solvent for the dibutyltin dichloride are obtained in the same way Results.

In the case of the last three solvents mentioned, the polymer separates all viscous paste that coagulates quickly when acetone is added.

Example 2 Polydi-n-butyltin fumarate 1.16 g (0.01 mole) fumaric acid were suspended in water as above and neutralized with NaOH. Then it became 3.03 g (0§01 mol) n-dibutyltin dichloride in 50 com petroleum ether with strong stirring added at 00a. After 20 minutes the polymer was filtered off. It melted not below 300 ° C. The yield was 3.15 g (91%).

Analysis calculated for C12H20SnO4: C, 41.5; H, 5.76; Sn, 34.3 found: C, 41.27; H, 5.78; Sn, 33.15.

Example 3 Polydi-n-butyltin-N-carbobenzoxyglutamate 1.2 g of N-carbobenzoxyglutamic acid were placed in 5 com of water and neutralized with 5nNaOH. 1.7 g of n-dibutylsinndiohlorld were dissolved in 50 com petroleum ether and added at 0 ° C. with stirring. After 1 hour, acetone was added and the reaction mixture filtered. The yield was 1.8 g (82%). The polymer had a melting point of 163-16500.

Analysis for C21H31NSnO6 calculated I Sn, 23.2 found: Sn, 24.3.

Example 4 Polydi-n-butylsin terephthalate (method A) According to the in Example 3 given instructions, this polymer is obtained from 1.66 g (0.01 mol) Terphthalic acid and 3.03 g (0.01 mol) of di-n-butyltin dichloride in a yield of 70%. The polymer does not melt up to 300 ° C.

Analysis for C16H22SnO4 calculated: C, 48.4; H, 5.5; Sn, 30.0, found: C, 48.1; H, 5. 7 Sn, 4/30.

Example 5 Polydi-n-butyltin acetylenedicarboxylate 1.52 g (0. OiMol) Monecalium salt of acetylenedicarboxylic acid were dissolved in 7 com water with 20% KOH neutralized.

0.03 g (0.01 mol) of dibutyltin dichloride in 50 com petroleum ether (Siued point 40-60 ° C) were added at 0 ° C with stirring. After one hour, it was filtered and the residue is washed with water, ethanol and acetone. The yield of the up to 30,000 non-melting polymer was 81%.

Analysis calculated for C12H18SnO4: C, 41.7; H, 5.2; Sn, 34.4 found 0.30.4; H, 5.3; Sn, 3 Example 6 Polydi-n-butyltin succihat 1.08 g (0.01 mole) succinic acid were suspended in 50 com ater and neutralized with 5n NaCH. 3.03 @ (0.01 moles) Dibutyltin dichloride in 50 com @ water point 40-60 ° C) were stirred vigorously b d room temperature admitted. After 20 minutes e was filtered and the solid polymer washed with Aet @ anol, water and acetone. The yield was 2.7 g (78%).

Melting point 235 ° C.

Example 7 Polydiisobutyltin adipate Following the procedure of the example 1 were 1.46 g (0.01 mol) of adipic acid with 3.03 g (0.01 mol of diisobutyl chloride implemented. Yield 85%, melting point about 210 ° C.

Example 8 Polydi-n-Butyltin Temperate (Method B) 4.5 g (0.015 mol) Di-n-butyltin dichloride in a mixture of 50 cc of toluene and 50 cm of petroleum ether was stirred with a solution of 2 g (0.03 mol) of sodium formate in 10 cc of water. After 30 minutes the organic layer was separated and a solution of disodium terephthalate (from 1.66 g = 0.01 mol of terephthalic acid) in 10 ccm of water at room temperature Stir added.

After a few hours it was filtered and the solid polymer sat with Washed ethanol, water and acetone.

The polymer to be melted up to 30,000 was obtained in a yield of 3.7 g (93%) recovered. ui e previous implementation of the dibutyltin dichloride with the sodium formate is used to exchange the chlorine get @ n the formate residue. The subsequently the separated aqueous layer had a chloride concentration which was 57% of the theoretical Amount corresponded.

If sodium acetate is used instead of sodium formate, it is obtained 3.2 g of the same polymer are obtained in 80.5% yield. The gliloridion concentration the aqueous layer showed that 85% of the chlorine had been replaced by acetate residues.

The structure of the polymer was determined by infrared spectroscopy confirms.

Example 9 Di-n-butyltin diadipate terephthalate copolymer 0.7 g (0.005 Mole) of adipic acid and 0.8 g (0.005 mole) of terephthalic acid were dissolved in 10 cc of water suspended and neutralized with base. The implementation with t dibutyltin dichloride he successes according to Example 1. The copolymer which did not melt up to 3000C was obtained in a yield of 52%.

The structure was confirmed by infrared spectroscopy.

Example 10 Polydiisobutyltin p-sulfamoylbenzoate 2 g (o, d1 mol) p-sulfamoylbenzoic acid were suspended in 10 ocm water, neutralized with 2.7 N KOH and then at -10 ° C. reacted with a solution of 3.5 g (0.0116 mol) of diisobutyltin dichloride in 150 cc of petroleum ether.

After 1 hour, the mixture was filtered and the solid polymer with water and washed petroleum ether.

The yield was 3 g (69%).

The melting point was between 170 and 180 ° C.

The structure was confirmed by infrared spectroscopy.

Example 11 Polydiisobutyl tin citrate 2.1 g (0.01 mole) citric acid monohydrate were dissolved in 10 cc of water and neutralized with 2.7 N KOH.

3.5 5 g (0.0116 mol) of diisobutyl tin dichloride were dissolved in petroleum ether (Boiling point 40-60 ° C) dissolved and added and stirring at room temperature.

After 3 hours it was filtered and the solid residue with water Washed ethanol and acetone. 3.2 g of polymer were obtained which did not reach 300.degree schmdz.

Example 12 Polydiisobutyltin-p -xylydithiol 16g (0.01 mole) of p -xylyldithiol were suspended in 20 cem water and neutralized under argon with 2.7 N KOH.

2.6 cc of diisobutyltin dichloride was added in a mixture of 75 cc Petroleum ether (boiling point 40-600C) and 25 ccm of chloroform dissolved and added. That The reaction mixture was stirred at room temperature overnight. Then the organic one Separated layer and added 500 com of alcohol. The polymer precipitates as transparent semi-solid precipitation. Yield 2.5g.

Example 13 Polydi-n-sutyltin-1,4-butanebisthioglycolate 2.38 & (0.01 mol) 1,4-butanebisthioglycolic acid were neutralized in 15 cm of water with 2.7 N KOH. A solution of 7 (0.0115 equivalents) di-n-butyltin dichloride in 50 cm of chloroform was admitted.

The reaction mixture was stirred at room temperature for 4 hours. yield 3.6 g (51.5%), melting point 138 ° C.

Example 14 Poly-n-butyltin pyromellitimi d A solution of 3.5 g (0.0115 mol) di-n-butyltin dichloride in 50 com petroleum ether (boiling point 90-100 ° C) @ Was a solution of 2.16 I (0.01 @ol) pyromellitimide, dic neutralized with 2.7 N KOH was, added @ ügt.

The reaction mixture was stirred overnight.

The precipitated polymer was filtered off.

Yield 3.1 g of example 15 polydiphenyl @ innadipate 1 5 g (0, oil Iol . ? i) nsäurc \ -rdc1i i: 5 t <? gö2 'J' () - I ö'-neutralized. A solution of 3.5 g (0.01 @ol) -i @ henyltin dichloride in 100 com benzene and 10 com Petroleum ether was added at 20 ° C. with stirring.

The polymer precipitated out immediately and was washed with water and petroleum ether and then washed with acetone. Yields 4 g (96%) m.p. 185-187 ° C.

Claims (5)

Claims 1) Process for the production of organotin polymers and copolymers, characterized in that an aqueous solution of salts of compounds that have at least two identical or different acidic functions, such as Carboxyl, sulfydryl, sulfonic acid, imide, primary or secondary sulfonamide groups or have heterocyclic groups with acidic hydrogen atoms, or for production an aqueous solution of various such salts is reacted by copolymers with an organotin compound of the general formula R1R2SnX1X2, wherein X1 and X2 Halogen atoms or anions vo) acids with a pKa value not exceeding 4.8 and R1 and R2 are identical or different unsubstituted or substituted alkyl, Mean aryl, aralkyl or heterocyclic groups. 2) Method according to claim 1, characterized in that the organotin compound as a solution in e @ em water-immiscible organic solvent with the aqueous solution is mixed. 3) Process according to claim 1 or 2, for the production of copolymers, characterized in that two or more different organotin compounds to be implemented. 4) Method according to claim 1 to 3, characterized in that the compounds with several acidic functions as a ketallic, ammonium or amine salt come into use. 5) Method according to claims 1-4, characterized by the use rather acid of the general formula R (COOH) n, in uer n a number v @ n 2 - 4 and R a unsubstituted or substituted alkyl, aryl, aryl, or heterocyclic Group is