Patent GB-496443-A (GB)
Title: Improvements in the manufacture and production of artificial rubber-like substances
IPC: C08F36/04
Filed: 1938-03-03
Abstract: Butadiene and its homologues and halogen substitution products are polymerized alone or with each other or with other polymerizable compounds when emulsified with aqueous salts of compounds of the type X-CH2-CH2.Y. CH2-CH2-NZ where Y is oxygen or sulphur and NZ is the radicle of a secondary amine or a quaternary ammonium compound and X is the radicle of a secondary amine, an acid amide, an ester, ether, quaternary ammonium compound or a hydroxyl group, at least one of the radicles X, Z being an open chain of at least 8 carbon atoms. Compounds of this type may be made by reacting 2 molecules of high-molecular alkylamines (which may be derived from fats or oils or paraffin oxidation products or from montanic acids) with one molecule of b -b 1-dichlordiethyl ether or reacting 1 molecule of such an amine with 1 molecule of b -chlor-b 1-hydroxy diethyl ether or by reacting 1 molecule of such an amine and 1 molecule of a tertiary nitrogen base such as pyridine, triethylamine or triethanolamine with 1 molecule of dichlordiethyl ether, in the last case quaternary ammonium compounds being formed.  Corresponding sulphur compounds are produced by using dichlordiethyl sulphide instead of the ether. Suitable compounds to be polymerized with the butadiene are unsaturated hydrocarbons such as styrene, and isobutylene, unsaturated esters such as vinyl esters, acrylic acid esters and a -cyanosorbic esters, and also acrylic nitrile and vinyl chloride. The polymerized emulsions may be coagulated by electrolytes, especially alkalies, or by water-soluble organic solvents such as methanol, ethanol, or acetone.  In examples: (1) butadiene is polymerized in emulsion with potassium persulphate and the reaction product of b -b 1-dichlordiethyl ether and amines from train oil; (2) butadiene and acrylic nitrile are polymerized in emulsion with potassium persulphate and the reaction product of b -chlor-b 1-hydroxy-diethyl ether and amines from train oil; (3) butadiene and styrene are polymerized in a similar manner using the reaction product of b -b 1-dichlordiethyl ether and an amine from a paraffin oxidation product of 14-17 carbon atoms; (4) butadiene and vinyl-methyl ketone are polymerized in emulsion with potassium persulphate and the reaction product of b -b 1-dichlordiethyl sulphide and amines from train oil; (5) butadiene and a -methylvaleric vinyl esters are polymerized in a similar manner using the reaction product of b -chlor-b 1-hydroxydiethyl ether, and octodecenylamine, which has been esterified with chloracetic acid and converted into the corresponding pyridinium chloride by reaction with pyridine.ALSO:Butadiene and its homologues and halogen substitution products are polymerized alone or with each other or with other polymerizable compounds when emulsified with aqueous salts of compounds of the type X-CH2-CH2.Y.CH2-CH2-NZ where Y is oxygen or sulphur and NZ is the radicle of a secondary amine or a quaternary, ammonium compound and X is the radicle of a secondary amine, an acid amide, an ester, ether, quaternary ammonium compound or a hydroxyl group, at least one of the radicles X, Z being an open chain of at least 8 carbon atoms.  Compounds of this type may be made by reacting 2 molecules of high-molecular alkylamines (which may be derived from fats or oils or paraffin oxidation products or from montanic acids) with one molecule of b -b 1-dichlordiethyl ether or reacting 1 molecule of such an amine with 1 molecule of b -chlor-b 1-hydroxy diethyl ether or by reacting 1 molecule of such an amine and 1 molecule of a tertiary nitrogen base such as pyridine, triethylamine or triethanolamine with 1 molecule of dichlordiethyl ether, in the last case quaternary ammonium compounds being formed. Corresponding sulphur compounds are produced by using dichlordiethyl sulphide instead of the ether.  Suitable compounds to be polymerized with the butadiene are unsaturated hydrocarbons such as styrene and isobutylene, unsaturated esters such as vinyl esters, acrylic acid esters and a -cyano sorbic esters, and also acrylic nitrile and vinyl chloride.  The polymerized emulsions may be coagulated by electrolytes, especially alkalies, or by water-soluble organic solvents such as methanol, ethanol, or acetone.  In examples: (1) butadiene is polymerized in emulsion with potassium persulphate and the reaction product of b -b 1-dichlordiethyl ether and amines from train oil; (2) butadiene and acrylic nitrile are polymerized in emulsion with potassium persulphate and the reaction product of b -chlor-b 1-hydroxydiethyl ether and amines from train oil; (3) butadiene and styrene are polymerized in a similar manner, using the reaction product of b -b 1-dichlordiethyl ether and an amine from a paraffin oxidation product of 14-17 carbon atoms; (4) butadiene and vinyl methyl ketone are polymerized in emulsion with potassium persulphate and the reaction product of b -b 1-dichlordiethyl sulphide and amines from train oil; (5) butadiene and a -methylvaleric vinyl ester are polymerized in a similar manner, using the reaction product of b  - chlor - b 1-hydroxydiethyl ether and octodecenylamine which has been esterified with chloracetic acid and converted into the corresponding pyridinium chloride by reaction with pyridine.