Flame retarding linear polyesters and shaped articles thereof

Abstract

Flame-repellant linear polyesters are obtained by incorporating by condensation phosphorus-compounds having the formula ##STR1## wherein R and R 1 are organic radicals which may also contain hereto atoms into the linear polyesters, preferably those from terephthalic acid and ethylene glycol. These polyesters are materials of which flame-repellent filaments, fibers, sheets, press-moulded and injection-moulded articles may be made. Products of the invention can be used whereever especially acute risks of ignition and fire exist.

We claim: 
     
       1. A linear polyester which is the polycondensation product of a dicarboxylic acid, a diol and a flame-retarding carboxy-phosphinic acid monomer, said monomer being used in an amount of from 3 to 20 mol percent, based on the total amount of dicarboxylic acid and monomer, said monomer being a source of structural units in said polyester of the formula ##STR18## wherein R is saturated, open-chain or cyclic alkylene, arylene or aralkylene having one to 15 carbon atoms, and may contain one or more hetero atoms selected from F, Cl, Br, O and S, and R 1  is alkyl having up to six carbon atoms, aryl, or aralkyl and may contain one or more hetero atoms selected from F, Cl, Br, O and S, provided that in the R and R 1  groups the O, if present, is the oxygen of an ether group, and the S, if present, is the sulfur of a thioether, sulfoxide, sulfone or sulfonate group. 
     
     
       2. A linear polyester according to claim 1 wherein R is --CH 2  --CH 2  -- or --C 6  H 4  - and   R 1  is CH 3  -- or C 6  H 5  --.   
     
     
       3. A linear polyester according to claim 1 wherein the radical R or R 1  contains a hetero atom O or S. 
     
     
       4. A linear polyester according to claim 1 wherein the units derived from dicarboxylic acid are essentially terephthalic acid units and the units derived from the diol are essentially units of a diol of the formula HO (CH 2 ) n  OH wherein n is 2 to 10, or the diol units are derived from 1,4-cyclohexane-dimethanol.     
     
     
       5. A linear polyester according to claim 1 wherein the units derived from dicarboxylic acid are essentially terephthalic acid units and the units derived from diol are essentially ethylene glycol units. 
     
     
       6. A method of making a linear polyester which comprises polycondensing a dicarboxylic acid or a lower alkyl ester thereof with a diol in the presence of a flame-retarding phosphorus containing monomer of the general formula ##STR19## or a lower alkyl ester or cyclic anhydride of said monomer in an amount of about 3 to 20 mole percent of the total acid components wherein the symbol R of said formula is saturated, open-chain or cyclic alkylene having one to 15 carbon atoms, arylene or aralkylene, and R 1  of the formula is alkyl having up to 6 carbon atoms, aryl or aralkyl, and wherein R and R 1  may further contain one or more hetero atoms selected from F, Cl, Br, O and S, provided that in the R and R 1  groups the O, if present, is the oxygen of an ether group, and the S, if present, is the sulfur of a thioether, sulfoxide, sulfone or sulfonate group. 
     
     
       7. A process according to claim 6 wherein the dicarboxylic acid is terephthalic acid and the diol is ethylene glycol. 
     
     
       8. Shaped articles made by molding or extrusion of the linear polyester of claim 1. .Iadd. 
     
     
       9.  A linear polyester which is effectively a polycondensation product of a dicarboxylic acid, a diol and a flame-retarding amount of a carboxy-phosphinic acid monomer, said monomer being a source of structural units in said polyester of the formula ##STR20## wherein R is saturated, open-chain or cyclic alkylene, arylene or aralkylene having one to 15 carbon atoms, and may contain one or more hetero atoms selected from F, Cl, Br, O and S and R 1  is alkyl having up to six carbon atoms, aryl, or aralkyl and may contain one or more hetero atoms selected from F, Cl, Br, O and S, provided that in the R and R 1  groups the O, if present, is the oxygen of an ether group, and the S, if present, is the sulfur of a thioether, sulfoxide, sulfone or sulfonate group. .Iaddend. .Iadd. 
     
     
       10.  A flame-repellant linear polyester obtained by incorporating in said polyester by condensation a phosphorus-containing compound having the formula: ##STR21## wherein R is saturated, open-chain or cyclic alkylene, arylene or aralkylene having one to 15 carbon atoms, and may contain one or more hetero atoms selected from F, Cl, Br, O and S, and R 1  is alkyl having up to six carbon atoms, aryl or aralkyl and may contain one or more hetero atoms selected from F, Cl, Br, O and S, provided that in the R and R 1  groups the O, if present, is the oxygen of an ether group, and the S, if present, is the sulfur of a thioether, sulfoxide, sulfone or sulfonate group. .Iaddend. .Iadd.   
     
     
       11.  A flame-retarding linear polymer which comprises a modified polyethylene terephthalate having structural units of the formula ##STR22## present in an amount sufficient to impart flame-repellant properties thereof, wherein R is saturated, open-chain or cyclic alkylene, arylene or aralkylene having one to 15 carbon atoms and may contain one or more hetero atoms selected from F, Cl, Br, O and S, and R 1  is alkyl having up to six carbon atoms, aryl or aralkyl and may contain one or more hetero atoms selected from F, Cl, Br, O and S, provided that in the R and R 1  groups the O, if present, is the oxygen of an ether group and the S, if present, is the sulfur of a thioether, sulfoxide, sulfone or sulfonate group. .Iaddend. .Iadd. 
     
     
       12.  A flame-retarded linear polyester which is effectively a polycondensation product of a dicarboxylic acid, a diol and a carboxy-phosphinic acid monomer present in an amount sufficient to impart flame-retardant properties to said polyester, said monomer being a source of structural units in said polyester of the formula ##STR23## wherein R is saturated, open-chain or cyclic alkylene, arylene or aralkylene having one to 15 carbon atoms, and may contain one or more hetero atoms selected from F, Cl, Br, O and S and R 1  is alkyl having up to six carbon atoms, aryl or aralkyl and may contain one or more hetero atoms selected from F, Cl, Br, O and S, provided that in the R and R 1  groups the O, if present, is the oxygen of an ether group, and the S, if present, is the sulfur of a thioether, sulfoxide, sulfone or sulfonate group. .Iaddend. .Iadd. 
     
     
       13.  The polyester as defined in claim 12 which comprises a polyethylene terephthalate. .Iaddend.