Patent GB-870292-A (GB)
Title: Improvements in and relating to substantially linear segmented polymer fibres
IPC: C08G18/42
Filed: 1959-01-02
Abstract: The invention comprises elastic fibres of substantially linear segmented polymers comprising (1) a plurality of polyester segments derived from hydroxy-terminated polyesters having a melting point below 60 DEG C. and a molecular weight of 600 to 5000 by the removal of terminal hydroxyl groups therefrom and (2) a plurality of non-polyester segments consisting of at least one repeating unit of a polyurea, polythiourea or polyurea-thiourea, which polyurea, polythiourea or polyurea-thiourea itself would have a melting point above 200 DEG C. in its fibre forming molecular weight range, wherein the polyester segments are connected to the non-polyester segments by urethane or thiourethane linkages, and the non-polyester segments contain, in the chain and directly united to the urethane or thiourethane linkages, symmetrical divalent aromatic radicals containing no fused rings.  The preferred fibres comprise repeating units of the structure: <FORM:0870292/IV (a)/1> where R is a symmetrical divalent aromatic radical containing no fused rings, the X's are oxygen or sulphur atoms, G is a polyester p  segment consisting of a residue derived from a hydroxyl-terminated polyester having a melting point below 60 DEG C. and a molecular weight of 600 to 5000, R1 is a divalent organic radical, n is an integer and p is zero or one.  R and R1 are chosen so that the polymer: <FORM:0870292/IV (a)/2> or, where p equals zero, the polymer: <FORM:0870292/IV (a)/3> melts above 200 DEG C. in its fibre-forming molecular weight range. The polymers are formed by reacting the polyester with excess of the compound R(NCX)2 and reacting the resulting -NCX- terminated polymer with an organic amine or water. The second reaction is preferably carried out in such solvents as dimethylformamide (alone or mixed with acetone), diethylacetamide, tetrahydrofuran or dimethylsulphoxide. Alternatively the polyester may be converted to a bischloroformate which is reacted with a symmetrical aromatic diamine, the product then being reacted with a biscarbamyl chloride.  Fibres of the product can be produced by wet or dry spinning.  Alternatively the -NCX terminated intermediate can be extruded into a bath of the diamine.  The products can be stabilized to heat and ultra-violet radiation by incorporating phenols and their derivatives, amines and their derivatives, compounds containing both hydroxyl and amino groups, hydroxyazines, oximes, polymeric phenolic esters and salts of multivalent metals in which the metal is in its lower valence state.  Carbon black, clay, silica, pigments, plasticizers and colouring agents may also be incorporated.  In Examples (1) an adipic acid-ethylene glycol polyester is reacted in methylene chloride with excess p, p1-methylenediphenyl diisocyanate, and the product is reacted in N, N-dimethylformamide solution with ethylene diamine.  The solution is wet-spun into a hot water bath.  Generally similar reactions are effected with polyesters from (2) 2, 2-dimethyl-1, 3-propanediol and sebacyl chloride; (3) 2, 2-diethyl-1, 3-propanediol and sebacic acid; (6) poly(ethylene adipate).  In Example (8) there are reacted poly(ethylene adipate), p, p1-methylenediphenyl diisocyanate and water. In (9) a polester from ethylene and propylene glycols and adipic acid is reacted with excess p, p1-methylenediphenyl diisocyanate.  The -NCO terminated product is mixed with additional diisocyanate and the mixture is reacted in dimethylformamide with 2, 5-dimethylpiperazine.  The product is dry-spun.  In Example (10) an NCO-terminated product from the same diisocyanate and a polyester from 2, 2-dimethyl-1, 3-propanediol and dimethyl sebacate is extruded into ethylene diamine to form fibres.  For comparison, products from polyethylene adipate and (4) 2, 4-tolylene diisocyanate and o-dichlorobenidine; (5) 1, 5-naphthylene diisocyanate and water; (7) 1, 5-naphthylene diisocyanate and ethylene diamine are described. Specification 847,673 is referred to.