Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
  • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
  • C08J3/096—Nitrogen containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
  • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
  • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
  • C08J3/097—Sulfur containing compounds
• • 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
  • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2333/00—Characterised by the use 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; Derivatives of such polymers
  • C08J2333/18—Homopolymers or copolymers of nitriles
  • C08J2333/20—Homopolymers or copolymers of acrylonitrile

Definitions

• acrylonitrile and up to 20*perc"e'xit"dfo"ther monomers such as vinyl acetate, met'hyl'methacrylate, methyl acrylate, styrene, vinylide'rie chloride, and methacrylonitr ile are capable of production into fibers with superior physicalproperties.
• these compositions and the fibers-prepared therefrom do not-have suflicient dye ,affinity to enable the development of satisfactory colored fibers.
• a stillfurther purpose is tceliminate the-cloudiness and other heterogeneous irregularitiesiri mer may be'dissolved in conyentional solventsfor' fiber forming acrylonitrile polymers to producesolutions of unusual-quality with respect to homo,- geneity'and' spinnabi-lity if the solutions a re grade in thepresence of a;minor proportion of sulfuricacid; for exampleirom 0.01 to; 3.90 weight per cent based on the solution.
• Preferred practice ultilizes from-0.05 to"1.00-percent.
• Theinverition isapplicable to both blends and copolymers which are comprised of from two to ten per cent of a vinylpyridiiie' or an" alkyl sub"- sftituted vinylpyri'dihe ⁇ said percentage lcieirie' based on th'e torn-mar ners o' hicli the' cofioly mer or blendof copdlyiners' are empnsea;
• the blends may have as the principal polymer from to 98' per c'entoi a c'opolym'er of or more" per cent acrylonitrile' and minor proportions of monomers"copolymerizable' therewith.
• the other" blend constltiient is a poyvinylpyridine'or aico' polymer-jot 3pm" more per cn'tof Tavinylpy'ridin'e' or alkyl substituted vinylpyr'idine" and 'up't'd'l'fl per cent of another ,copolyn erizable mono: er;
• the two components of the" blended copolyterrorism'sf are proportioned such .asto' provide the requir' quantity or I acrylonitrile and reactivevinylpyii dine.
• rne' vinylpyridin'elinboth thec' poiyhiiiaiir blend copolymers may be anyyiliyl'py o'r' alkyl' s'ubstituted vinylpyridinel restrain '-2- viny1pyridine aturate-nin 'r-v i-yip id 119; aunts-endp int 1 a i sthynt.
• alkyl radical has up to four carbon atoms, styrene and other vinyl substituted aromatic hydrocarbons, vinylidene chloride and methacrylonitrile.
• These non-functional monomers may be present as a third monomer with acrylonitrile and a vinylpyridinein a terpolymeric system, or they may be used in the blended composition either as a comonomer with acrylonitrile in the principal polymer or as a comonomer with a vinylpyridine in the blending polymer.
• the principal acylonitrile polymers and copolymers thereof may be prepared in any of the manners well-known to the art.
• emulsion or dispersion polymerizations which take place in a'n aqueous'medium in the presence of water-soluble peroxy compounds or other free radical type of catalysts and with a suitable dispersing agent.
• Such polymerizations may take place at elevated temperatures utilizing reflux conditions to eliminate the heat of polymerization or the reaction may be conducted by the Redox" methods in lower ternperatures.
• regulators for example the various mercaptans, such as tert.'-dodecyl mercaptan, mercapto acetic acid, and the esters of mercapto acetic acid.
• the separation of the acrylonitrile polymers from the aqueous medium may be accomplished by filtration or decantation followed by drying in the manner well-known to the art.
• the vinylpyridine polymers may'be bymass polymerization methods, solution polymerization methods, or aqueous emulsion procedures, the latter being the preferred manner of preparation.
• the preferred procedure involves the use of efficient emulsion stabilizing agents for the purpose of preventing a lomeration with the polymer particles.
• the details of polymerization procedure and separation of the polymer from the reaction medium may be practiced by anyof the numerous methods known to the art.
• the fiber forming acrylonitrile polymer and vinylpyridine polymers are physically blendedby a wide variety of procedures. If desired the emulsions or dispersions of polymers in aqueous media, just as received from the polymerization reactors may. be blended. Physical mixtures of the separated solid polymers may also be'utilized.
• a preferred manner of preparing "the mixtures involves'the dispersion of the: polymers, or the emulsions thereof, in a solvent, with the distilla tion or evaporation of the water, if present in proportions large enough to interfere with the complete dissolution of the solid polymers.
• Example 1 polymer of 97 per cent acrylonitrile and three per cent vinyl acetate with 16 per cent of a copolymer of 50 per cent vinyl pyridine and 50 per cent acrylonitrile in sufficient N,N-dimethylacetamide to yield an 18 per cent solids solution.
• the resulting solutions were found to be turbid and to have a viscosity of 117 poises at 50 C.
• Several samples of this spinning solution were treated with varying proportions of sulfuric acid. The following table demonstrates that improvements in viscosity and clarity of the solution are obtained by the addition of sulfuric acid to the spinning solution.
• Example 3 A mixture of 622.5 parts by weight of N,N-dimethylacetamide, 112.2 parts of a copolymer of 97 per cent of acrylonitrile and three per cent vinyl acetate and 15.3 parts of a copolymer of 50 per cent of pyridine and 50 per cent acrylonitrile was prepared by stirring the mixture at C. for one hour. Sulfuric acid in the amount of 0.38 part by weight was added thereto, thereby forming a clear and homogeneous spinning solution. The solution was spun through a spinneret having 30 apertures each 0.005 inch in diameter into a mixture of 60 per cent N,N-di- 'methacetamide'and 40 per cent water.
• a fiber spinning solution comprising a solvent for fiber-forming acrylonitrile polymers, polymer of monomeric substances of which from two to ten percent of the total monomer is a vinylpyridine and at least 80 percent is acrylonitrile, and from 0.01 to 3.0 per cent by weight (based on the solution) of sulfuric acid.
• a fiber spinning solution comprising a solvent for fiber-forming acrylonitrile polymers, polymer of monomeric substances of which from two to ten percent of the total monomer is a vinylpyridine and at least 80 percent is acrylonitrile, in polymeric form, and from 0.05 to 1.0 percent by weight (based on the solution) of sulfuric acid.
• a fiber spinning solution comprising a solvent for fiber-forming acrylonitrile polymers, a copolymer of 90 to 98 percent acrylonitrile and from two to ten percent vinylpyridine, and from 0.01 to 3.0 percent by weight (based on the solution) of sulfuric acid.
• a fiber spinning solution comprising a solvent for fiber-forming acrylonitrile polymers, a blend of a polymer of at least 90 percent acrylonitrile and a polymer of at least 30 percent of vinylpyridine, said polymers being so propora n on conm'ri in a N di ehvlaeta l l ion o po y er o .bsta" cesc hich fr m tw tot thet tali ionomer a.
• vinylpyridi and at least '80 percent is acrylonitrile in polye1jic Iprm. and from. 0.05 to, 1.0, percent by ed or'i'th "'luti' oiisulfuric acid.
• a fiber spinning composition comprising a N,N-dimethy1acetamide solution of a blend of polymer of at least percent acrylonitrile and a polymer of at least 30 percent vinylpyridine, said polymers being blended in such proportions so as to produce polymer having from two to ten percent vinylpyridine in polymeric form, and from 0.05 to 1.0 percent by weight (based on the solution) of sulfuric acid.
• a fiber spinning solution comprising a solvent for fiber-forming acrylonitrile polymers, a blend of a polymer of at least 90 percent acrylonitrile and up to ten percent of a monomer oi the group consisting of vinyl acetate and other, vinyl esters of carboxylic acids having up to four carbon atoms, vinylchloroacetate, methyl methacrylate, methyl acrylate, other alkyl acrylates and methacrylates wherein the alkyl radical has up to four carbon atoms, styrene, other vinyl substituted aromatc hydrocarbons, vinylidene chloride, diethyl fumarate, diethyl maleate, other alkyl fumarates and alkyl maleates wherein the alkyl radical has up to four carbon atoms and methacrylonitrile; and a polymer of at least 30 percent of vinylpyridine and up to 70 percent of acrylonitrile; and from 0.01 to 3.0 percent by weight (based on the solution) of sulfuric acid said
• a fiber spinning solution comprising a solvent for fiber-forming acrylonitrile polymers, a blend of a polymer of at least 90 percent acrylonitrile and up to ten percent of a monomer of the group consisting of vinyl acetate and other vinyl esters of carboxylic acids having up to four carbon atoms, vinylchloroacetate; methyl methacrylate; methyl acrylatefother alkyl acrylates and methacrylates wherein the alkyl radical has up to four carbon atoms, styrene,',other vinyl substituted aromatic hydrocarbons, vinylidene chloride, diethyl' fumarate, diethyl maleate, other alkyl fumarates and'alkylmaleates wherein the alkyl radical has up to four carbon atoms and methacrylonitrile; and a polymer of at least 30 percent of vinylpyridine and up to '70 percent of acrylonitrile; and from 0.05 to 1.0 percent by weight (based on the solution) of sulfuric acid
• a fiber spinning composition comprising a N,N-dimethylacetamide solution of a blender a polymer of at least 90 percent acrylonitrile and up to ten percent of a monomer of the group'consisting of vinyl acetate and other vinyl esters of carboxylic acids having'up to four carbon atoms, vinylchloroacetate, methyl methacrylate, methyl acrylate, other alkyl acrylates and methacrylates wherein thealkyl' radical has up to four carbon atoms, styrene, otheryinyl substituted aromatic hydrocarbons, vinylidene chloride, diethyl inmarate, diethyl maleate, other 'alkyl fumarates-and alkyl maleates wherein the alkyl radical has up to four carbon atoms and methacrylonitrilef and a polymer of at least 30per cent of vinylpyridine and up to 70 percent of acrylonitrile; andgfrom 0.01 to 3.0 percentby weight (
• 'A fiber spinningcomposition comprising a N,N-dimethylacetamide solution of a, blend of a polymer of at least 90 percent acrylonitrile and up" totenpercent of a monomer of the group consisting of vinyl acetate and other vinyl esters of carboxylic acids having up to four carbon atoms, vinylchloroacetate, methyl methacrylate, methyl acrylate, other alkyl acrylates and methacrylates wherein .the alkyl radical has up to four carbon atoms, styrene, other vinyl substituted aromatic hydrlocarbons, vinylidene chloride, diethyl', vfumarate, diethyl maleate, other alkyl fumarates and alkyl maleates wherein the alkyl radical has up to' four carbon atoms and methacrylonitrile; and a polymer of at least percent of vinylpyridine and up to percent of acrylonitrile; and from 0.05 to 1.0 percent by weightv (based

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Toxicology (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Artificial Filaments (AREA)

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Citations (1)

• 0
  • NL NL78751D patent/NL78751C/xx active
  • BE BE503453D patent/BE503453A/xx unknown
• 1950
  • 1950-09-26 US US186909A patent/US2613194A/en not_active Expired - Lifetime
• 1951
  • 1951-05-10 GB GB11006/51A patent/GB700565A/en not_active Expired
  • 1951-05-16 FR FR1180602D patent/FR1180602A/fr not_active Expired
  • 1951-08-27 CH CH315548D patent/CH315548A/de unknown
  • 1951-08-27 CH CH315284D patent/CH315284A/de unknown
  • 1951-08-27 CH CH318120D patent/CH318120A/de unknown

Patent Citations (1)

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