Patent GB-656643-A (GB)
Title: Modifying the properties of polymeric organic substances with polyisocyanates and polyisothiocyanates
IPC: C08G18/67
Filed: 1947-08-08
Abstract: Cellulose derivatives, synthetic resins and synthetic linear polyamides are reacted with an organic compound having a plurality of but preferably two separate and distinct reactive groups of the formula -N=C=Y, wherein Y is O or S.  Further, natural or regenerated cellulose, e.g. cotton, wood or paper, is reacted with a like organic compound containing reactive groups of formula -N=C=Y, wherein Y is O or S, other than an isocyanate or an isothiocyanate having an aliphatic carbon chain containing at least 8 carbon atoms.  Organic compounds having a plurality of -N=C=Y groups include polymethylene diisocyanates and diisothiocyanates, alkylene, alkylidene and cycloalkylene diisocyanates and diisothiocyanates, and aromatic diisocyanates and diisothiocyanates.  A list of suitable compounds is given. The reaction may take place either in the presence or absence of solvents or diluents and at atmospheric pressure or pressures above or below atmospheric.  Generally it is desirable to operate at temperatures between 100 DEG  and 250 DEG  C., but room temperature may be sufficient in some cases.  Substances which may be treated include cellulose esters and ethers containing free hydroxyl groups, partially hydrolysed polyvinyl acetate and nylon.  In an example, 15 parts by weight of cellulose acetate flake containing 54.5 per cent combined acetic acid is dissolved in 85 parts of acetone. Hexamethylene diisocyanate (1.5 parts) is added and the mixture agitated.  After three hours, the viscosity of the solution is increased, and within 24 hours the solution has turned into a gel. Evaporation of the acetone yields a hard infusible modified cellulose acetate insoluble in both acetone and pyridine.  The Specification as open to inspection under Sect. 91 describes a process for modifying the properties of organic substances containing a plurality of groups containing reactive hydrogen which comprises reacting said substances with reagents containing as the sole reacting groups a plurality of separate and distinct groups having the formula -X=C=Y, wherein X is C or N and Y is O, S or NR, R being hydrogen or a monovalent hydrocarbon radical. The products are polymeric, being linear polymers when one reagent contains two -X=C=Y groups and the other contains two groups containing reactive hydrogen, and modified polymers of high molecular weight when one reagent is already polymeric.  Suitable compounds containing -X=C=Y groups (as defined above) include diketenes, dithioketenes, diketenimines, and dicarbodiimides, as well as compounds of mixed functions such as isocyanate - isothiocyanates.  Compounds with which these may be reacted include those containing two hydroxyls, whether phenolic or alcoholic; two sulphhydryls, whether thiophenolic or mercaptan; two amino groups, whether primary or secondary; two or more carboxyl groups, and combinations of these such as compounds containing one alcoholic hydroxyl group and one phenolic hydroxyl, or one mercaptan and one carboxylic or one carbothiolic group. Many reagents of both kinds are specified.  The reaction may be conducted in a solvent in the absence of oxygen or moisture, e.g. in a partial vacuum or an atmosphere of nitrogen.  The product may be freed from solvent by distillation under reduced pressure or it may be precipitated from solution by addition of a non-solvent, or the reaction may be carried out in a non-solvent medium for the product.  The polymers so prepared may be used for the production of artificial filaments, hair, bristles, threads or ribbons, as coating agents for cloth, paper and leather, and they may be admixed with other polymers, resins, plasticizers, pigments and dyes.  Filaments prepared from them may be cold-drawn. Examples describe the treatment of: (1) polyvinyl formal films with decamethylene diisocyanate (this example also refers to polyvinyl butyral and the polyvinyl ketal of methyl ethyl ketone); (2) decamethylenediamine with decamethylene diisocyanate in m-cresol; (3) hexamethylenediamine with hexamethylene diisocyanate in m-cresol; (4) m-phenylene diamine with m-phenylene diisocyanate; (5) decamethylene glycol (containing lauryl alcohol as a viscosity stabilizing agent) with decamethylene diisocyanate; (6) hexamethylene glycol with m - phenylene diisocyanate; (7) 2 : 2 - bis - (4 - hydroxyphenyl)-propane with decamethylene diisocyanate; (8) hexamethylene-bis-glycolamide with decamethylene diisocyanate; (9) decamethylene dithiol with decamethylene diisocyanate; (10) decamethylene glycol with hexamethylene diisothiocyanate; (11) decamethylene dithiol with hexamethylene diisothiocyanate; (12) decamethylene diamine with decamethylene diisothiocyanate; (13) adipic acid with hexamethylene diisothiocyanate; (14) sebacic acid with decamethylene diisocyanate; and (15) dihydromuconic acid with decamethylene diisocyanate.  U.S.A. Specifications 2,071,253 and 2,130,948 are referred to.  This subject-matter does not appear in the Specification as accepted.ALSO:Proteins are reacted with an organic compound having a plurality of, but preferably two, separate and distinct reactive groups of the formula -N=C=Y, wherein Y is O or S.  Such compounds include polymethylene diisocyanates and diisothiocyanates, alkylene, alkylidene and cycloalkylene diisocyanates and diisothiocyanates, and aromatic diisocyanates and diisothiocyanates.  A list of suitable compounds is given. The reaction may take place either in the presence or absence of solvents or diluents and at atmospheric pressure or pressures above or below atmospheric.  Generally it is desirable to operate at temperatures between 100 DEG  C. and 250 DEG  C., but room temperature may be sufficient in some cases.  Substances which may be treated include wool, gelatin, silk, zein, and casein.  The Specification as open to inspection under Sect. 91 describes a process for modifying the properties of organic substances containing a plurality of groups containing reactive hydrogen which comprises reacting said substances with reagents, containing as the sole reacting groups a plurality of separate and distinct groups having the formula -X=C=Y, wherein X is C or N and Y is O, S or NR, R being hydrogen or a monovalent hydrocarbon radical. Suitable compounds containing -X=C=Y groups (as defined above) include diketenes, dithioketenes, diketenimines, and dicarbodiimides, as well as compounds of mixed functions such as isocyanate-isothiocyanates.  Compounds with which these may be reacted include those containing two hydroxyls, whether phenolic or alcoholic; two sulphhydryls, whether thiophenolic or mercaptan; two amino groups whether primary or secondary; two or more carboxyl groups; and combinations of these such as compounds containing one alcoholic hydroxyl group and one phenolic hydroxyl, or one mercaptan and one carboxylic or one carbothiolic group.  A number of reagents of both kinds are specified.  The reaction may be conducted in a solvent in the absence of oxygen or moisture, e.g. in a partial vacuum or an atmosphere of nitrogen. The product may be freed from solvent by distillation under reduced pressure or it may be precipitated from solution by addition of a non-solvent, or the reaction may be carried out in a non-solvent medium for the product. The examples describe treatment of (1) decamethylenediamine with decamethylene diisocyanate in m-cresol; (2) hexamethylenediamine with hexamethylene diisocyanate in m-cresol; (3) m-phenylene diamine with m-phenylene diisocyanate; (4) decamethylene glycol (containing lauryl alcohol as a viscosity stabilizing agent) with decamethylene diisocyanate; (5) hexamethylene glycol with m-phenylene diisocyanate; (6) 2:2 - bis - (4-hydroxyphenyl)-propane with decamethylene diisocyanate; (7) hexamethylene-bis-glycolamide with decamethylene diisocyanate; (8) decamethylene dithiol with decamethylene diisocyanate; (9) decamethylene glycol with hexamethylene diisothiocyanate; (10) decamethylene dithiol with hexamethylene diisothiocyanate; (11) decamethylene diamine with decamethylene diisothiocyanate; (12) adipic acid with hexamethylene diisothiocyanate; (13) sebacic acid with decamethylene diisocyanate; and (14) dihydromuconic acid with decamethylene diisocyanate.  U.S.A. Specifications 2,071,253 and 2,130,948 are referred to.  This subject-matter does not appear in the Specification as accepted.ALSO:Cellulose derivatives, natural and synthetic resins, proteins, and synthetic linear polyamides are reacted with an organic compound having a plurality of but preferably two separate and distinct reactive groups of the formula -N=C=Y, wherein Y is O or S. Further natural or regenerated cellulose, e.g. cotton, is reacted with a like organic compound containing reactive groups of formula -N=C=Y, wherein Y is O or S, other than an isocyanate or an isothiocyanate having an aliphatic carbon chain containing at least 8 carbon atoms.  Organic compounds having a plurality of -N=C=Y groups include polymethylene diisocyanates and diisothiocyanates, alkylene, alkylidene and cycloalkylene diisocyanates and diisothiocyanates, and aromatic diisocyanates and diisothiocyanates.  A list of suitable compounds is given. The reaction may take place either in the presence or absence of solvents or diluents and at atmospheric pressure or pressures above or below atmospheric.  Generally it is desirable to operate at temperatures between 100 DEG  and 250 DEG C., but room temperature may be sufficient in some cases.  Substances which may be modified include cellulose esters and ethers containing free hydroxyl groups, partially hydrolysed polyvinyl acetate, and proteins such as wool, gelatine, silk, zein casein and nylon. Examples are given in which (1) cellulose acetate tricot is soaked in a benzene solution of hexamethylene diisocyanate, allowed to dry and then baked at 140-145 DEG  C., whereby an acetone-insoluble fabric which can be ironed at