Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0066—Flame-proofing or flame-retarding additives
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/152—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
  • D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
  • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
  • D06M13/21—Halogenated carboxylic acids; Anhydrides, halides or salts thereof

Definitions

• An acrylonitrile polymer such as an acrylonitrile fiber having improved flame resistance contains a halogenated aromatic compound having the formula wherein R is hydrogen, chlorine, bromine or an alkyl radical having from 1 to 9 carbon atoms, R is an alkyl radical having 1 to 22 carbon atoms and the sum of the carbon atoms of R and R is greater than 9, R is methylene, isopropylidene, oxygen or sulfur; R is an alkyl radical containing at least one carbon atom; R is a 2,3- dibromopropyl group; X is bromine or chlorine; m is an integer of from 0 to 22 and n is an integer of from 0 to 4 with the proviso that each formula contains at least two aromatically bound halogen atoms.
• This invention relates generally to acrylonitrile polymers and more particularly to acrylonitrile polymers having improved flame resistance.
• Fibers of acrylonitrile polymers are used extensively in various home furnishings such as carpets, draperies, upholstery and the like. To be entirely acceptable, the home furnishings must be flame resistance or self-extinguishing. While it is relatively easy to provide temporary flame resistance, it has been found to be very diflicult to provide permanent protection.
• the more successful processes heretofore proposed have involved adding halogen bearing aliphatic compounds to the solution from which the fibers are spun. By selecting a hologenated aliphatic compound which is soluble in organic solvents, it is possible to improve to some extent the flame resistance of fibers spunfrom organic solvent solutions of the polymer.
• halogenated parafiines, oils and the like are dispersed in the saline spinning solution, a large amount thereof is lost during spinning and subsequent dyeing of the fiber. While this loss can be somewhat reduced by using finely divided, solid, high melting halo-aliphatic compounds which become entrapped in the fiber matrix, such compounds also tend to reduce the luster of the fiber.
• an object of this invention to provide an improved flame resistance acrylonitrile polymer.
• Another object of the invention is to provide shaped, lustrous and flame resistant acrylonitrile polymers.
• Still another object of the invention is to provide shaped acrylonitrile polymers prepared from saline solutions thereof which have improved flame resistance.
• a still further object of the invention is to provide a process for making flame resistant shaped acrylonitrile polymers by wet spinning saline solutions of the polymer.
• R may be, for example, methyl, ethyl, hexyl, nonyl or the like.
• R and R may be, for example, methyl, ethyl, butyl, octyl, octadecyl or the like.
• halogenated aromatic compounds dispersed in the spinning solution in accordance with this invention are not removed from the fiber during spinning or in subsequent dyeing steps in sufficient quantity to eflect significantly the flame resistant properties of 3 the fiber. In fact, more than 90 percent of the halogenated compound dispersed in the spinning solution often remains in the fiber after spinning and dyeing.
• the flame retardant compounds of this invention are liquids or waxes having a melting point of less than about 100 C. It is surprising that although such compounds are liquids or low melting waxes and are not soluble in the spinning dope, they can be heterogeneously dispersed in the dope and very little if any loss will occur during wet spinning, washing and other processing of the resulting fibers. As indicated by the formula, the number of halogen atoms will vary from one compound to another but the total number of aromatically bound chlorine or bromine atoms in the compound should be at least two and preferably at least three with not more than five per aromatic ring.
• Any compound having one of the formulae set forth above may be used such as, for example, di(2,4,-6- tribromophenyl)adipate, di(2,4,6-tribromophenyl) sebacate, di(4-octanoyl dibromophenyl) propane, 4-nonyl, 2,6-dibromophenyl acetate, pentabromophenyl oleate, tribromophenyl stearate, pentabromophenyl stearate, di- (2,4,6-trichlorophenyl) sebacate, di(4-octanoyl dichlorophenyl) propane, trichlorophenyl stearate, di(2,4,6-trichlorophenyl) malonate, di(4 bromopropoxy 2,3,5,6- tetrabromophenyl) propane and the like. It is pointed out that compounds containing both aliphatically and aromatically bound halogen
• the amount of halogenated aromatic compound included in the saline solution of the acrylonitrile polymer will vary with the percentage halogen in the compound and to some extent upon the particular halogen present. Any amount of brominated or chlorinated aromatic compound having the above formula will improve the flame resistance of an acrylonitrile polymer so all suitable concentrations in the spinning solution are broadly contemplated. Best results have been obtained so far with from about 1 percent to about 15 percent bromine or from about 2 percent to about 30 percent chlorine, or equivalent mixtures of bromine and chlorine based on the weight of acrylonitrile fiber in the spinning solution so it is preferred to use an amount within these ranges.
• the required amount of bromine and/or chlorine is supplied by from about 1 percent to about 20 percent by weight of the halogenated aromatic compound.
• the halogenated aromatic compounds may be used alone or in combination with other fiame retardants such as antimony oxide and phosphorus compounds.
• the halogenated aromatic compound is mixed sufficiently uniformly with a saline spinning solution and the resulting mixture is wet spun by conventional methods.
• a spinning solution containing an acrylonitrile polymer, water and a saline solvent for the polymer such as sodium thiocyanate, zinc chloride or the like is stirred with the halogenated aromatic compound in a mixer adapted to impart a shearing action to the mixture until a substantially uniform dispersion of droplets of the halogenated compound in the spinning solution is obtained.
• the resulting mixture is then spun into an aqueous coagulating bath, stretched and dyed.
• the particles or droplets of liquid halogenated aromatic compound dispersed in the fiber are predominantly less than about 20 microns in cross-section.
• the invention contemplates improving the flame resistance of any acrylonitrile polymer including those disclosed in U.S. 3,028,371.
• acrylonitrile polymer is used herein to mean acrylonitrile homopolymers and copolymers containing at least about 70 percent by weight acrylonitrile copolymerized with other mono-olefinic compounds of the type disclosed in U.S. 3,028,371 and other prior publications.
• the halogenated aromatic compounds As indicated by the formula of the halogenated aromatic compounds found advantageous for improving the flame resistance of acrylonitrile polymers, the halogen atoms must be aromatically bound and the sum of the carbon atoms in R and R of Formulae 1 and 2 must be greater than 9.
• the halogenated aromatic compounds are more resistant to chemical attack by aqueous saline solutions than halogenated aliphatic compounds. Such compounds are also retained to a greater extent by the shaped acrylonitrile polymer than are halogenated aliphatic compounds. Maximum retention is important not only for optimum flame proofing but also because the presence of halogen compounds in the solvent interferes with solvent recovery and introduces corrosion problems.
• any suitable saline solvent may be used to prepare the spinning solution such as, for example, those disclosed in Rein U.S. 2,140,921 and Cresswell 2,558,730.
• suitable salts are sodium thiocyanate, zinc chloride and the like.
• the amount of acrylonitrile polymer dissolved in the aqueous solvent can vary depending upon the composition of the polymer, its molecular weight and the particular salt used. Generally, from about 10 percent to about 20 percent by weight of the spinning solution will be polymer although even greater percentages can be used.
• the solutions containing more than 20 percent polymer may be spun into air prior to washing with water to remove the salt.
• the spinning solution may contain, in addition to the flame retardant, other additives or modifying agents, if desired. Conventional spinning equipment used for making filaments and fibers may be used.
• the acrylonitrile polymers provided by this invention can be used to advantage in making draperies, carpets and other household furnishings.
• EXAMPLE I About 8 parts of 4-nonyl-2,6-dibromophenyl acetate are mixed with about 1000 parts of a spinning solution containing about 112 parts of an acrylonitrile copolymer, about 365 parts sodium thiocyanate and about 523 parts water and the mixture is agitated with a mixer adapted to impart a shearing action thereto until a substantially uniform dispersion of the bromine substituted compound in the spinning solution is obtained.
• the copolymer is about 10.7 percent methyl-methacrylate and about 89.3 percent acrylonitrile.
• the resulting mixture is wet spun from a wet-spinning apparatus into a coagulating bath containing about 10 percent sodium thiocyanate and about percent water at about 0 C.
• a spinnerette of the type disclosed by Cresswell in U.S. 2,558,730 may be used.
• the acrylic fiber thus produced contains the 4-nonyl- 2,6-dibromophenyl acetate as small particulate inclusions.
• the fiber is completely lustrous and is self-extinguishing. From about 92 percent to about 96 percent or more of the 4-nonyl-2,6-dibromophenyl acetate added to the spinning solution is retained in the coagulated fiber and very little, if any, is lost as the fiber is dyed in water at C. for about one hour.
• Example II Example I is repeated except about 4.1 percent (based on the weight of copolymer) of di(2,4,6-tribromophenyl) sebacate are substituted for the 4-nonyl-2,6-dibromophenyl acetate. About 99 percent of the di(2,4,6-tribromo phenyl) sebacate is retained in the fiber after spinning and about 92.5 percent thereof is retained after dyeing the fiber.
• a fiber isobtained which retains only 88 percent of the halogen compound after spinning and64 percent after dyeing whenabout 7 percent of a brominated fatty acid ester sold under the trademark Brominex are substituted for the di(2,4,6-tribror'nophenyl) sebacate of this Example II.
• EXAMPLE III percent bromine and about 0.25 percent antimony after drying. After mock dyeing, the fiber contains about 2.54 percent bromine and about 0.25 percent antimony. The fiber is self-extinguishsing.
• a solid shaped acrylonitrile polymer product pre- TABLE I Number carbon Percent Percent retained atoms inbased on Y weight of After After Flame retardant R R2 eopolymer spin dyeing
• B 4-n0nyl 2,61iibromophenol 9 0 6. 2 79. 5 69. 5
• the total number of carbon atoms in R and R of the flame retardant compound used in preparing fibers A through C is 9 or less and that the retention of the compounds by the fibers both after spinning and after dyeing is substantially less than the retention of the compounds by the fibers D through G.
• R of the flame retardant compound used in preparing fibers D through G contains more than 9 carbon atoms.
• Example IV Example I is repeated except about 8.4 parts of 4- nonyl, 2,6-dibromophenyl acetate and about 0.6 part of antimony trioxide are mixed with the 1000 parts spinning solution. The resulting fiber is self-extinguishing.
• Example I is repeated except a solution of about 2 parts of trioctylphosphate and about 7 parts of 4-nonyl 2,6-d1- I bromophenyl acetate is dispersed in the spinning solution instead of the flame retardant of Example I.
• the fiber is self-extinguishing.
• Example I is repeated except about 7 parts of di(4- octanoyltetrabromophenyl) propane are substituted for the 4-nonyl, 2,6-dibromo-phenyl acetate. About 100 percent of the di(4-octanoyltetrabromophenyl) propane is retained by the filament after spinning and about 99 percent thereof remains in the fiber after drying.
• EXAMPLE VII An intimate mixture is prepared containing about 50 parts di(4-bromopropoxy-2,3,5,6 tetrabromophenyl) propane, about 4 parts antimony oxide, about 22.5 parts of the copolymer of Example I, about 82 parts sodium thiocyanate and about 95.5 parts water. About 50 parts of the resulting mixture are substituted for the 4-nonyl, 2,6- dibromophenyl sebacate in the 1000 parts spinning solution of Example I and a fiber is prepared by the process of Example I. The fiber thus obtained contains about 2.6
• R is hydrogen, chlorine, bromine or an alkyl radical having from 1 to 9 carbon atoms; R is a alkyl radical having 1 to 22 carbon atoms and the sum of the carbon atoms of R and R is greater than 9; R is methylene, isopropylidene, oxygen or sulfur; R is an alkyl radical containing at least one carbon atom; R is a 2,3- dibromopropyl group; X is bromine or chlorine; m is an inter of from 0 to 22 and n is an integer of from 0 to 4 with the proviso that each formula contains at least two aromatically bound halogen atoms.
• halogenated aromatic compound is 4-nonyl-2,6-dibromophenyl acetate.
• halogenated aromatic compound is di(4-octanoyl dibromophenyl propane, di(2,4,6-tribromophenyl) sebacate, pentabromophenyl oleate, tribromophenyl stearate, pentabromophenyl stearate or nonyldibromophenyl sebacate.
• R is hydrogen, chlorine, bromine or an alkyl radical having from 1 to 9 carbon atoms;
• R is an alkyl radical having 1 to 22 carbon atoms and the sum of the carbon atoms of R and R is greater than 9;
• R is methylene, isopropylidene, oxygen or sulfur;
• R is an alkyl radical containing at least one carbon atom;
• R is a 2,3- dibromopropyl group;
• X is bromine or chlorine;
• m is an integer of from 0 to 22 and n is an integer of from 0 to 4 with the proviso that each formula contains at least two aromatically bound halogen atoms.

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• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
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• Compositions Of Macromolecular Compounds (AREA)

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Cited By (16)

• 1970
  • 1970-03-12 US US19124A patent/US3660351A/en not_active Expired - Lifetime
• 1971
  • 1971-02-26 JP JP46009316A patent/JPS5029049B1/ja active Pending

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