Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/18—Homopolymers or copolymers of nitriles
  • C08L33/20—Homopolymers or copolymers of acrylonitrile
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
  • D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S525/916—Polymer from ethylenic monomers only, having cationic group

Definitions

• Fiber-forming acrylonitrile polymers which normally contain greater than about 75 percent acrylonitrile have been used extensively in textile applications. Fabric formed from such materials, as is true of most other large volume synthetic polymers employed in textile applications, may be readily burned. When fabrics formed from filaments of acrylonitrile polymers are exposed to an open flame they will burn and globules of molten tarry materials are formed as a product of the combustion. This condition is quite pronounced with fabrics such as non-woven and loosely woven materials. These molten tarry globules constitute hazards in addition to the flame itself of the burning material. For example, these molten tarry materials contain volatile matter and are quite flammable, and in this form have a tendency to run or drip and thus spread the burning material.
• Useful polymers or copolymers are those which contain 100 percent vinyl chloride or vinylidine chloride, or copolymers of the two in any proportion, or copolymers of vinyl chloride and/or vinylidine chloride which contain less than 2.0 percent of other copolymerizable monoolefinic monomers including such monomers as vinyl esters such as vinyl acetate; the lower dialkyl esters of maleic and fumaric acid such as the diethyl and dibutyl esters; acrylic and methacrylic acid esters such as methyl acrylate, butyl acrylate, octyl acrylate, methyl methacrylate, butyl methacrylate and the like; vinyl alkyl ethers such as vinyl ethyl ether and vinyl isobutyl ether; isobutylene; isopropenyl acetate; alkyl vinyl ketones; and other monoolefinic monomers which arecopolymerizable with vinyl chloride and vinylidine chloride. More preferred are polyvinyl
• the amount of halogen-containing polymer employed in the acrylonitrile polymer composition normally will range from about 5' to about 30 weight percent of halogen-containing polymer based on the total polymer content, and more preferably about 10 to 20 weight percent with a corresponding 90 to weight percent of the acrylonitrile polymer.
• the amount of halogen-containing polymer to be employed may also be calculated on the basis of total halogen-content of the polymeric composition.
• the blended polymer compositions ordinarily will contain from about 5 to about 20 weight percent chlorine, and more preferably about 10 to about 15 weight percent.
• halogen-containing polymers which normally will be polymers of vinyl chloride ordinarily will contain a stabilizer, as is well known.
• stabilizers are dibutyl tin dilaurate, tin mercaptide, epoxidized fatty acid esters, dibasic lead phthalate, lead carbonate, cadmium and barium compounds and the like.
• the chlorine-containing polymer is intimately blended with the fiber-forming acrylonitrile polymer by any of the methods known to those skilled in the art.
• the most straightforward method will be to dis-" solve both the acrylonitrile polymer and the chlorine containing polymer in the desired solvent for the acrylonitrile polymer.
• the defined acrylonitrile and chlorine-containing polymers in the defined ratios form compatible. mixtures in the solvents set forth hereinafter to provide stable solutions which are useful in large scale spinning operations.
• Another method is to mix water dispersions of the chlorinecontaining polymer and acrylonitrile polymer, which mixture is then dried and dissolved in the desired solvent.
• the method employed for obtaining the mixture of the two polymeric materials is not critical so long as an intimate mixture is obtained. I
• the acrylonitrile materials which are to be en'tployed taining at least 80 Weight percent of acrylonitrile'inthe polymer molecule and up to 20 Weight percent of mono-i mers copolymerizable therewith; or blends comprising polyacrylonitrile or copolymers comprising acrylonitrile, the blend having an overall polymerized acrylonitrile content of at least 80 percent by weight as will be set forth in more detail hereinafter.
• Suitable monoolefinic monomers include acrylic, alpha-chloroacrylic and methacrylic acids; the methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, methoxymethyl methacrylate, beta-chloroethyl methacrylate, and the corresponding esters of acrylic and alpha-chloroacrylic acids; vinyl chloride, vinyl fluoride, vinyl bromide, vinylidine chloride, l-chloro-l-bromoethylene; methacrylonitrile; acrylamide and methacrylamide, alpha-chloroacrylamide or monoalkyl substitution products thereof; methyl vinyl ketone; vinyl carboxylates such as vinyl acetate,
• the polymer may be a ternary interpolymer, for example, products obtained by the interpolymerization of acrylonitrile and two or more of any of the monomers enumerated above. More specifically, a useful ternary polymer comprises acrylonitrile, methacrylonitrile, and 2- vinylpyridine.
• the ternary polymers may contain, for example, from 80 to 97 percent of acrylonitrile, from 1 to percent of a vinylpyridine or a l-vinylimidazole, and from 1 to 18 percent of another substance, such as methacrylonitrile or vinyl chloride.
• the polymeric material when it comprises a blend, it will be a blend of a copolymer of 90 to 98 percent of acrylonitrile (more preferably 93 to 97 percent), and from 2 to 10 percent of another monoolefinic monomer (more preferably 3 to 7 percent), such as vinyl acetate, with a suflicient amount of a copolymer of from 10 to 70 percent of acrylonitrile or N-vinylcarbazole and the like and from 30 to 90 percent of a vinyl-substituted tertiary heterocyclic amine, such as vinylpyridine, methyl vinylpyridine or l-vinylimidazole, to give a dyeable blend having an overall vinyl-substituted tertiary heterocyclic amine content of from 2 to 10 percent and preferably about 6 percent, based on the Weight of the blend.
• a copolymer of 90 to 98 percent of acrylonitrile more preferably 93 to 97 percent
• the polymers useful in the practice of the present invention may be prepared by any conventional polymerization procedure, such as mass polymerization methods, solution polymerization methods, or aqueous emulsion procedures.
• the preferred practice utilizes suspension polymerization wherein the polymer is prepared in finely divided form for immediate use in the fiber fabrication operations.
• the preferred suspension polymerization may utilize batch procedures wherein monomers are charged with an aqueous medium containing the necessary catalyst and dispersing agents.
• a more desirable method involves the semi-continuous procedure in which the polymerization reactor containing the aqueous medium is charged 4 with the desired monomers gradually throughout the course of the reaction. Entirely continuous methods involving the gradual addition of monomers and the continuous withdrawal of polymer may also be employed.
• the most efiective polymers for the preparation of fibers are those of uniform physical and chemical properties and of relatively high molecular weight.
• the polymers should have molecular weights of at least about 10,000 and preferably between about 25,000 and 150,000.
• conventional equipment ordinarily employed in the manufacture of artificial and synthetic fibers and filaments may be used and particularly the equipment which is usually employed in the manufacture of fibers and filaments from acrylonitrile polymers.
• the present invention is applicable to the usual methods for forming synthetic filaments and fibers, such as dry spinning and wet spinning.
• a solution of acrylonitrile polymer and chlorine-containing polymer is first prepared.
• Any of the solvents for acrylonitrile polymers may be used in-v cluding N,N dimethylacetamide; N,N dimethylformamide; nitromethane and water; tris(dimethylamido)phosphate; N-nitropiperidine; mixtures of ethylene sulfite with N,N-dimethylacetamide, N,N-dimethylformamide, and nitromethane and water; tri(betacyanoethyl)nitromethane; trichloronitropropanol; mixtures of diethyl phosphate and N,N-dimethylacetamide and N,N-dimethylformamide, and the like; and such solvents as dimethyl methanephosphonate, gamma-butyrolactone, ethylene carbonate and the like.
• the dope is extruded through an orifice or a plurality of orifices in the face of a spinnerette submerged in a coagulating medium or bath.
• the bath comprises a non-solvent for the polymer which is also a solvent for or miscible with the solvent in the dope.
• the coagulating medium or bath will comprise an aqueous solution of a solvent for the polymer being spun, the concentration of the bath being such that the solvent becomes a nonsolvent for the polymer.
• amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and the like
• an aqueous coagulating bath containing 1 to 75 percent of the amide is satisfactory.
• the filaments are moved from the coagulating bath and passed through a washing medium where all residual solvent and coagulating liquid are removed therefrom.
• Water is the preferred washing medium and is usually contained in a bath through which the filaments are passed. In the bath the washing medium may flow concurrent or counter current to the direction of travel of the filaments therethrough. Washing rolls or like apparatus may also be employed, if desired. Thereafter the filaments are dried and steam stretched, if desired.
• the polymer molecules in the filaments are stretched while in the washing bath or coagulating bath or in both.
• a solvent stretch bath may be employed immediately following the coagulating bath wherein the polymer molecules in the filaments are oriented. It is to be noted, however, that the conditions of the bath where the stretching is to be done, such as tem perature, size, length of time that the filament remains therein, etc., are regulated as is well known to those skilled in the art. Normally, the solvent stretch or wash bath is maintained at a temperature in the range of to C. and the filaments remain therein for a period less than 15 seconds.
• any solvent for acrylonitrile polymers may be employed in the solvent stretch bath which may comprise a series of stages.
• concentration of the solvent in the bath will depend upon the chemical characteristics of the solvent used and the temperature of the bath. Obviously, the concentration must be such that the polymer article passing therethrough will not dissolve therein. Certain solvents may be used in higher concentrations than others.
• a solvent stretch bath containing from about to 85 percent solvent by weight, such as N,N- dimethylacetamide, N,N-dimethylformamide, and the like, is satisfactory for the purposes of the instant invention.
• the bath may contain varying concentrations of solvent at difierent stages during the stretching steps.
• Example I A series of spinning solutions or dopes were prepared by mixing together an acrylonitrile polymer-andchlorinecontaining polymers in N,N-dimethylacetamide to a concentration of 18 percent total solids, of which 16 percent was the chlorine-containing polymer, by mixing the ingredients for 45 minutes at 85 C. denier yarns were wet spun in a coagulating bath containing water and a slight excess of N,N-dimethylacetamide and were stretched about 3 times, washed, dride, annealed and crimped 12 to 14 crimps per inch.
• the acrylonitrile polymer employed in this example was a blend of (A) a copolymer of 94 percent acrylonitrile and 6 percent vinyl acetate and (B) a copolymer of 50 percent acrylonitrile and 50 percent Z-methyI-S-Vinylpyridine, said blend containing 6 percent Z-methyl-S-Vinylpyridine based on the total weight of the blend.
• the chlorinecontaining polymers in this example were as follows: (1) A copolymer of 95 percent vinyl chloride and 5 percent diethyl maleate (of intrinsic viscosity of 0.85); (2) A copolymer of about 90 percent vinylidene chloride and about 10 percent vinyl chloride; (3') A copolymer of about 80 percent vinyl chloride and percent vinylidene chloride; and (4) A copolymer of about 90 percent vinylidene chloride and 10 percent acrylonitrile. Filaments so produced had tenacity and elongation values as indicated in the table below.
• Example II 7 Another series of polymeric blends were prepared essentially following the procedure outlined in Example I.
• Acrylonitrile polymers employed were (1) a copolymer of about 93 percent acrylonitrile and about 7 percent vinyl acetate, and (2) an acrylonitrile polymer blend of (A) a copolymer of 94 percent acrylonitrile and '6 percent vinyl acetate and (B) a copolymer of 50 percent acrylonitrile and 50 percent Z-m'ethyl-S vinylpyridine, said blend containing 6 percent 2-methyl-5-vinylpyridine based on the total weight of the blend.
• a composition of matter comprising from about to about weight percent of (1) a polymer blend of a copolymer of 80 to 99 weight percent acrylonitrile and 20 to one weight percent of another monoolefinic monomer and a copolymer of 10 to 70 Weight percent acrylonitrile and 90 to 30 weight percent of a monovinylpyridine, said polymer blend having an overall monovinylpyridine content of 2 to 10 percent based on the weight of the blend, intimately blended with about 20 to about 10 weight percent of (2) a chlorine-containing polymer selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, a copolymer of greater than 80 weight percent vinyl chloride and less than 20 weight percent of another monoolefinic monomer and a copolymer of greater than 80 weight percent vinylidene chloride and less. than 20 weight percent of another monoolefinic monomer.
• a composition of matter comprising from about 80 to about 90 weight percent of (1) a polymer blend of a copolymer of 93 to 97 weight percent acrylonitrile and 7 to 3 Weight percent vinyl acetate and a copolymer of about 50 weight percent acrylonitrile and about 50 weight percent of a monovinylpyridine, said polymer blend having an overall monovinylpyridine content of 2 to 10 percent based on the weight of the blend, intimately blended with about 20 to about 10 weight percent of (2) a chlorine-containing polymer selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, a copolymer of greater than 80 weight percent vinyl chloride and less than 20 weight percent of another monoolefinic monomer and a copolymer of greater than 80 weight percent vinylidene chloride and less than 20 weight percent of another monoolefinic monomer.
• a composition of matter comprising from about 80 to about 90 weight percent of (1) a polymer blend of a "-7 copolymer of 93 to 97 Weight percent acrylonitrile and 7 to 3 weight percent vinyl acetate and a copolymer of about 50 weight percent acrylonitrile and about 50 weight percent of a monovinylpyridine, said polymer blend havcopolymer of 93 to 97 Weight-percent acrylonitrile and 7 to 3 weight percent vinyl acetate and a copolymer of about 50 weight percent acrylonitrile and about 50 weight percent of a monovinylpyridine, said polymer blend having an overall monovinylpyridine content of about 6 percent based on the weight of the blend, intimately blended with about 20 to about 10 Weight percent of (2) a copolymer of vinyl chloride and vinylidene chloride.
• a composition of matter comprising from about 80 to about 90 weight percent of (1) a polymer blend of a copolymer of 93 to 97 weight percent acrylonitrile and 7 to 3 weight percent vinyl acetate and a copolymer of about 50 weight percent acrylonitrile and about 50 weight percent Z-methyl-S-vinylpyridine, said polymer blend having an overall vinylpyridine content of 6 percent based on the weight of the blend, intimately blended with about 20 to about 10 weight percent of (2) a chlorine-containing polymer selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, a copolymer of greater than 80 weight percent vinyl chloride and less than 20 Weight percent of another monoolefinic monomer and a copolymer of greater than 80 weight percent vinylidene chloride and less than 20 weight percent of another monoolefinic monomer.
• polymer blend having an overall vinylpyridine content of 6 percent based on the weight of the blend, intimately blended with about 20 to about 10 weight percent of (2) polyvinyl chloride.
• a composition of matter comprising from about to about weight percent of (1) a polymer blend of a copolymer of 93 to 97 weight percent acrylonitrile and 7 to 3 weight percent vinyl acetate and a copolymer of about 50 weight percent acrylonitrile and about 50 weight percent Z-methyl-S-vinylpyridine, said polymer blend having an overall vinylpyridine content of 6 percent based on the weight of the blend, intimately blended with about 20 to about 10 weight percent of (2) a copolymer of vinyl chloride and vinylidene chloride.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Artificial Filaments (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)

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  • BE BE571716D patent/BE571716A/xx unknown
  • NL NL231903D patent/NL231903A/xx unknown
  • NL NL111530D patent/NL111530C/xx active
• 1957
  • 1957-10-02 US US687623A patent/US2949437A/en not_active Expired - Lifetime
• 1958
  • 1958-09-11 GB GB29187/58A patent/GB897310A/en not_active Expired
  • 1958-09-29 FR FR1211700D patent/FR1211700A/fr not_active Expired
  • 1958-09-30 DE DEC17581A patent/DE1279889B/de active Pending
  • 1958-09-30 CH CH6451558A patent/CH410399A/de unknown

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