Flame retarded fibers and filaments and process of production therefor

Abstract

A fiber or filament which is formed from ingredients comprising (a) at least one fiber-forming thermoplastic polymer, and (b) at least one polybrominated anionic styrenic polymer is provided. The polybrominated anionic styrenic polymer has a bromine content of at least about 50 wt %. Processes for producing such fibers or filaments are also provided.

1 . A fiber or filament formed from ingredients comprising (a) at least one fiber-forming thermoplastic polymer, and (b) at least one polybrominated anionic styrenic polymer, wherein the polybrominated anionic styrenic polymer has a bromine content of at least about 50 wt %.  
     
     
         2 . A fiber or filament according to  claim 1  wherein said fiber-forming thermoplastic polymer is a polyester.  
     
     
         3 . A fiber or filament according to  claim 2  wherein said polyester is polyethylene terephthalate, polybutylene terephthalate, or polytrimethylene terephthalate.  
     
     
         4 . A fiber or filament according to  claim 1  wherein said fiber-forming thermoplastic polymer is a polyamide.  
     
     
         5 . A fiber or filament according to  claim 4  wherein said polyamide is nylon-6 (polycaprolactam), nylon-6,6, nylon-6,12, nylon-12 (polylauryllactam), or a high temperature nylon.  
     
     
         6 . A fiber or filament according to  claim 1  wherein said fiber-forming thermoplastic polymer is a polyolefin.  
     
     
         7 . A fiber or filament according to  claim 6  wherein said polyolefin is polypropylene.  
     
     
         8 . A fiber or filament according to  claim 1  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %.  
     
     
         9 . A fiber or filament according to  claim 1  wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene.  
     
     
         10 . A fiber or filament according to  claim 2  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %, wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene, and wherein said polyester is polyethylene terephthalate, polybutylene terephthalate, or polytrimethylene terephthalate.  
     
     
         11 . A fiber or filament according to  claim 2  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 67 wt %, wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene, and wherein said polyester is polyethylene terephthalate, polybutylene terephthalate, or polytrimethylene terephthalate.  
     
     
         12 . A fiber or filament according to  claim 4  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %, wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene, and wherein said polyamide is nylon-6 (polycaprolactam), nylon-6,6, nylon-6,12, nylon-12 (polylauryllactam), or a high temperature nylon.  
     
     
         13 . A fiber or filament according to  claim 4  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 67 wt %, wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene, and wherein said polyamide is nylon-6 (polycaprolactam), nylon-6,6, nylon-6,12, nylon-12 (polylauryllactam), or a high temperature nylon.  
     
     
         14 . A fiber or filament according to  claim 6  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %, wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene, and wherein said polyolefin is polypropylene.  
     
     
         15 . A fiber or filament according to  claim 6  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 67 wt %, wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene, and wherein said polyolefin is polypropylene.  
     
     
         16 . A fiber or filament according to  claim 1  wherein the linear density of said fiber or filament is in the range of about 2 to about 25 denier.  
     
     
         17 . A fiber or filament according to  claim 1  wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene, and wherein the linear density of said fiber or filament is in the range of about 2 to about 25 denier.  
     
     
         18 . A thread or yarn formed from a fiber or filament of  claim 1 .  
     
     
         19 . A blend of fibers or filaments wherein a fiber or filament of  claim 1  is a component of said blend.  
     
     
         20 . A fiber or filament according to  claim 1  wherein said polybrominated anionic styrenic polymer has at least one of the following characteristics: 
 (i) a thermal stability in the Thermal Stability Test of 200 ppm HBr or less;    (ii) a chlorine content, if any, of less than about 700 ppm Cl;    (iii) a TGA temperature for 1% weight loss which is 340° C. or higher;    (iv) a ΔE color value, measured using 10 wt % solutions in chlorobenzene, of less than about 10;    (v) a melt flow index in the Melt Flow Index Test of at least about 20 g/10 min; and/or    (vi) a GPC weight average molecular weight in the range of about 8000 to about 20,000.    
     
     
         21 . A fiber or filament according to  claim 20  wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene.  
     
     
         22 . A fiber or filament according to  claim 20  wherein said fiber-forming thermoplastic polymer is a polyester, and wherein said polyester is polyethylene terephthalate, polybutylene terephthalate, or polytrimethylene terephthalate.  
     
     
         23 . A fiber or filament according to  claim 22  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %, and wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene.  
     
     
         24 . A fiber or filament according to  claim 20  wherein said fiber-forming thermoplastic polymer is a polyamide, and wherein said polyamide is nylon-6 (polycaprolactam), nylon-6,6, nylon-6,12, nylon-12 (polylauryllactam), or a high temperature nylon.  
     
     
         25 . A fiber or filament according to  claim 24  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %, and wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene.  
     
     
         26 . A fiber or filament according to  claim 20  wherein said fiber-forming thermoplastic polymer is a polyolefin, and wherein said polyolefin is polypropylene.  
     
     
         27 . A fiber or filament according to  claim 26  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %, and wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene.  
     
     
         28 . A fiber or filament according to  claim 1  wherein said polybrominated anionic styrenic polymer is produced by bromination of an anionic styrenic polymer, which anionic styrenic polymer is produced by a batch process, which process comprises charging a liquid saturated hydrocarbon diluent and an ether promoter into a reactor; and then 
 A) (i) charging a saturated hydrocarbon solution of organolithium initiator into the reactor, in an amount to provide in the range of about 1 to about 10 mol % of organolithium initiator based on the total amount of a styrenic monomer to be added followed by (ii) the controlled addition of the styrenic monomer such that the temperature of the resultant reaction mixture is maintained at or below about 55° C., or    B) concurrently feeding separate feeds of (i) a styrenic monomer and (ii) a saturated hydrocarbon solution of organolithium initiator into the reactor, the feeds being maintained at rates to provide for the addition of an amount of organolithium initiator in the range of about 1 to about 10 mol % based on the total amount of styrenic monomer to be added, the temperature of the resultant reaction mixture being maintained at or below about 55° C. and feed (ii) being of a shorter duration than feed (i).    
     
     
         29 . A fiber or filament according to  claim 28  wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene.  
     
     
         30 . A fiber or filament according to  claim 28  wherein said fiber-forming thermoplastic polymer is a polyester, and wherein said polyester is polyethylene terephthalate, polybutylene terephthalate, or polytrimethylene terephthalate.  
     
     
         31 . A fiber or filament according to  claim 30  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %, and wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene.  
     
     
         32 . A fiber or filament according to  claim 28  wherein said fiber-forming thermoplastic polymer is a polyamide, and wherein said polyamide is nylon-6 (polycaprolactam), nylon-6,6, nylon-6,12, nylon-12 (polylauryllactam), or a high temperature nylon.  
     
     
         33 . A fiber or filament according to  claim 32  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %, and wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene.  
     
     
         34 . A fiber or filament according to  claim 28  wherein said fiber-forming thermoplastic polymer is a polyolefin, and wherein said polyolefin is polypropylene.  
     
     
         35 . A fiber or filament according to  claim 34  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %, and wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene.  
     
     
         36 . A masterbatch which comprises (a) at least one fiber-forming thermoplastic polymer, and (b) at least one polybrominated anionic styrenic polymer, wherein the polybrominated anionic styrenic polymer has a bromine content of at least about 50 wt %, wherein said polybrominated anionic styrenic polymer is at least about 70 wt % of said masterbatch.  
     
     
         37 . A process for producing a fiber or filament, which process comprises melt spinning (a) at least one fiber-forming thermoplastic polymer, and (b) at least one polybrominated anionic styrenic polymer, wherein the polybrominated anionic styrenic polymer has a bromine content of at least about 50 wt %.  
     
     
         38 . A process according to  claim 37  wherein said thermoplastic fiber-forming polymer and said polybrominated anionic styrenic polymer are simultaneously mixed and melted.  
     
     
         39 . A process according to  claim 37  wherein said fiber-forming thermoplastic polymer is a polyester.  
     
     
         40 . A process according to  claim 39  wherein said polyester is polyethylene terephthalate, polybutylene terephthalate, or polytrimethylene terephthalate.  
     
     
         41 . A process according to  claim 37  wherein said fiber-forming thermoplastic polymer is a polyamide.  
     
     
         42 . A process according to  claim 41  wherein said polyamide is nylon-6 (polycaprolactam), nylon-6,6, nylon-6,12, nylon-12 (polylauryllactam), or a high temperature nylon.  
     
     
         43 . A process according to  claim 37  wherein said fiber-forming thermoplastic polymer is a polyolefin.  
     
     
         44 . A process according to  claim 43  wherein said polyolefin is polypropylene.  
     
     
         45 . A process according to  claim 37  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %.  
     
     
         46 . A process according to  claim 37  wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene.  
     
     
         47 . A process according to  claim 39  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %, wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene, and wherein said polyester is polyethylene terephthalate, polybutylene terephthalate, or polytrimethylene terephthalate.  
     
     
         48 . A process according to  claim 41  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %, wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene, and wherein said polyamide is nylon-6 (polycaprolactam), nylon-6,6, nylon-6,12, nylon-12 (polylauryllactam), or a high temperature nylon.  
     
     
         49 . A process according to  claim 44  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %, wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene, and wherein said polyolefin is polypropylene.  
     
     
         50 . A process according to  claim 37  wherein the linear density of the produced fiber or filament is in the range of about 2 to about 25 denier.  
     
     
         51 . A process according to  claim 37  wherein said polybrominated anionic styrenic polymer is brominated anionic polystyrene, and wherein the linear density of the produced fiber or filament is in the range of about 2 to about 25 denier.  
     
     
         52 . A process according to  claim 37  wherein said polybrominated anionic styrenic polymer is a component of a masterbatch.  
     
     
         53 . A process according to  claim 37  wherein said polybrominated anionic styrenic polymer has at least one of the following characteristics: 
 (i) a thermal stability in the Thermal Stability Test of 200 ppm HBr or less;    (ii) a chlorine content, if any, of less than about 700 ppm Cl;    (iii) a TGA temperature for 1% weight loss which is 340° C. or higher;    (iv) a ΔE color value, measured using 10 wt % solutions in chlorobenzene, of less than about 10;    (v) a melt flow index in the Melt Flow Index Test of at least about 20 g/10 min; and/or    (vi) a GPC weight average molecular weight in the range of about 8000 to about 20,000.    
     
     
         54 . A process according to  claim 53  wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene.  
     
     
         55 . A process according to  claim 53  wherein said fiber-forming thermoplastic polymer is a polyester, and wherein said polyester is polyethylene terephthalate, polybutylene terephthalate, or polytrimethylene terephthalate.  
     
     
         56 . A process according to  claim 55  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %, and wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene.  
     
     
         57 . A process according to  claim 53  wherein said fiber-forming thermoplastic polymer is a polyamide, and wherein said polyamide is nylon-6 (polycaprolactam), nylon-6,6, nylon-6,12, nylon-12 (polylauryllactam), or a high temperature nylon.  
     
     
         58 . A process according to  claim 57  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %, and wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene.  
     
     
         59 . A process according to  claim 53  wherein said fiber-forming thermoplastic polymer is a polyolefin, and wherein said polyolefin is polypropylene.  
     
     
         60 . A process according to  claim 59  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %, and wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene.  
     
     
         61 . A process according to  claim 37  wherein said polybrominated anionic styrenic polymer is produced by bromination of an anionic styrenic polymer, which anionic styrenic polymer is produced by a batch process, which process comprises charging a liquid saturated hydrocarbon diluent and an ether promoter into a reactor; and then 
 A) (i) charging a saturated hydrocarbon solution of organolithium initiator into the reactor, in an amount to provide in the range of about 1 to about 10 mol % of organolithium initiator based on the total amount of a styrenic monomer to be added followed by (ii) the controlled addition of the styrenic monomer such that the temperature of the resultant reaction mixture is maintained at or below about 55° C., or    B) concurrently feeding separate feeds of (i) a styrenic monomer and (ii) a saturated hydrocarbon solution of organolithium initiator into the reactor, the feeds being maintained at rates to provide for the addition of an amount of organolithium initiator in the range of about 1 to about 10 mol % based on the total amount of styrenic monomer to be added, the temperature of the resultant reaction mixture being maintained at or below about 55° C. and feed (ii) being of a shorter duration than feed (i).    
     
     
         62 . A process according to  claim 61  wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene.  
     
     
         63 . A process according to  claim 61  wherein said fiber-forming thermoplastic polymer is a polyester, and wherein said polyester is polyethylene terephthalate, polybutylene terephthalate, or polytrimethylene terephthalate.  
     
     
         64 . A process according to  claim 63  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %, and wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene.  
     
     
         65 . A process according to  claim 61  wherein said fiber-forming thermoplastic polymer is a polyamide, and wherein said polyamide is nylon-6 (polycaprolactam), nylon-6,6, nylon-6,12, nylon-12 (polylauryllactam), or a high temperature nylon.  
     
     
         66 . A process according to  claim 65  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %, and wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene.  
     
     
         67 . A process according to  claim 61  wherein said fiber-forming thermoplastic polymer is a polyolefin, and wherein said polyolefin is polypropylene.  
     
     
         68 . A process according to  claim 67  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %, and wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene.  
     
     
         69 . A composition which is a carrier blend, which blend is formed from ingredients comprising (i) at least one polybrominated anionic styrenic polymer, wherein the polybrominated anionic styrenic polymer has a bromine content of at least about 50 wt %, and (ii) at least one synergist or at least one other flame retardant.  
     
     
         70 . A composition according to  claim 69  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %, and wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene.  
     
     
         71 . A process for forming a carrier blend, which process comprises mixing and melting together (i) at least one polybrominated anionic styrenic polymer, wherein the polybrominated anionic styrenic polymer has a bromine content of at least about 50 wt %, and (ii) at least one synergist or at least one other flame retardant.  
     
     
         72 . A process according to  claim 71  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %, and wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene.  
     
     
         73 . A process for producing a fiber or filament, which process comprises melt spinning (a) at least one fiber-forming thermoplastic polymer, and (b) a carrier blend of  claim 69 .  
     
     
         74 . A process according to  claim 73  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %, and wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene.  
     
     
         75 . A process according to  claim 71  which further comprises melt spinning said carrier blend together with at least one fiber-forming thermoplastic polymer to form a fiber or filament.  
     
     
         76 . A process according to  claim 75  wherein said bromine content of said polybrominated anionic styrenic polymer is at least about 60 wt %, and wherein said polybrominated anionic styrenic polymer is a brominated anionic polystyrene.  
     
     
         77 . A carrier blend according to  claim 69  wherein said polybrominated anionic styrenic polymer has at least one of the following characteristics: 
 (i) a thermal stability in the Thermal Stability Test of 200 ppm HBr or less;    (ii) a chlorine content, if any, of less than about 700 ppm Cl;    (iii) a TGA temperature for 1% weight loss which is 340° C. or higher;    (iv) a ΔE color value, measured using 10 wt % solutions in chlorobenzene, of less than about 10;    (v) a melt flow index in the Melt Flow Index Test of at least about 20 g/10 min; and/or    (vi) a GPC weight average molecular weight in the range of about 8000 to about 20,000.    
     
     
         78 . A process according to  claim 71  wherein said polybrominated anionic styrenic polymer has at least one of the following characteristics: 
 (i) a thermal stability in the Thermal Stability Test of 200 ppm HBr or less;    (ii) a chlorine content, if any, of less than about 700 ppm Cl;    (iii) a TGA temperature for 1% weight loss which is 340° C. or higher;    (iv) a ΔE color value, measured using 10 wt % solutions in chlorobenzene, of less than about 10;    (v) a melt flow index in the Melt Flow Index Test of at least about 20 g/10 min; and/or    (vi) a GPC weight average molecular weight in the range of about 8000 to about 20,000.