US3180845A - Method of preparing void free fibers from acrylonitrile polymers - Google Patents

Method of preparing void free fibers from acrylonitrile polymers Download PDF

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Publication number
US3180845A
US3180845A US146555A US14655561A US3180845A US 3180845 A US3180845 A US 3180845A US 146555 A US146555 A US 146555A US 14655561 A US14655561 A US 14655561A US 3180845 A US3180845 A US 3180845A
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percent
acrylonitrile
polymer
fibers
polymers
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Expired - Lifetime
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US146555A
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English (en)
Inventor
John P Knudsen
Iii Howard G Clark
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Monsanto Co
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Monsanto Co
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Publication date
Priority to NL132471D priority Critical patent/NL132471C/xx
Priority to NL284543D priority patent/NL284543A/xx
Priority to BE623827D priority patent/BE623827A/xx
Priority to US146555A priority patent/US3180845A/en
Application filed by Monsanto Co filed Critical Monsanto Co
Priority to GB37591/62A priority patent/GB987303A/en
Priority to FR912407A priority patent/FR1337614A/fr
Priority to CH1221862A priority patent/CH413219A/fr
Priority to DK451862AA priority patent/DK107050C/da
Priority to DEM54571A priority patent/DE1292310B/de
Application granted granted Critical
Publication of US3180845A publication Critical patent/US3180845A/en
Anticipated expiration legal-status Critical
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • This invention relates to the preparation of improved fibers from acrylonitrile polymers through control of the coagulation properties of spinning solutions of these polymers. More particularly, this invention relates to the use of certain easily soluble alkylene glycol polymers compatible in solution with polyacrylonitrile to control the formation of internal voids in the fibers during coagulation.
  • Certain acrylonitrile polymers, copolymers, and polymer blends containing at least 80% acrylonitrile commonly used for the preparation of synthetic fibers by wet spinning yield fibers containing large numbers of internal voids when solutions of these polymers in organic solvents are coagulated in aqueous spin baths particularly at high spinning speeds. These voids appear to form at the instant of coagulation due to rapid skin formation and inward diffusion of spin bath liquors. Voids so formed persist in the fiber throughout its further processing and contribute undesirable properties such as poor abrasion resistance and reduced luster to the finished fiber.
  • these and other objects of the invention are accomplished by incorporating into the spinning solution a suitable small quantity of a polymer which is both compatible with the acrylonitrile polymer and also soluble or highly swellable by the coagulation medium employed.
  • a suitable amount of polyethylene glycol, polypropylene glycol or polybutylene glycol may then be wet spun into a. coagulation bath according to the usual well known methods, and will result in fibers of improved characteristics
  • the mode of addition of the polyglycol is unimportant. That is the polyglycol may be blended with the acrylonitrile polymer during preparation of the spinning solution by any convenient means.
  • the polymers may be dissolved sequentially in either order, or the two may be dissolved separately and the solutions mixed. However, both polymer and polyglycol must be completely and uniformly dispersed throughout the solution on order to ensure proper performance of the invention.
  • the polymerpolyglycol solution is then extruded into a coagulation bath.
  • the improved character of acrylonitnile fibers produced in this manner is evident by an examination of the accompanying drawings.
  • FIGURE 1a shows a drawing of a mricrophotograph cross-section view of polyacrylonitrile fibers spun with 2.5% polyethylene glycol of 1,000 molecular weight in the spinning solution and subjected to a jet stretch of 1.04. Jet stretch is the rate of filament take-up divided by the extrusion rate.
  • FIGURE 1 shows polyacrylonitrile fibers spun without polyethylene glycol and subjected to the tear shaped areas which characteristically form while the filament is coagulating, is greatly reduced in FIGURE la using polyethylene glycol.
  • FIGURES 2a and 2 compare polyacrylonitrile fibers spun with 2.5% polyethylene glycol of 1,000 molecular weight in the spinning solution and none respectively, to which a 2.01 jet stretch has been applied.
  • FIGURES 3a and 3 show polyacrylonitrile fibers prepared with 2.5% polyethylene glycol of 1,000 molecular weight in the spinning solution and none respectively, to which a 3.10 jet stretch was applied. In all three comparisons the reduction of voids when polyethylene glycol is present in the spinning solution is clearly evident. A reduced occurrence of voids improves the abrasion resistance and other desirable qualities.
  • the polyglycols of this invention may be employed in an amount of from about 2 to 25 percent of the polymer by weight.
  • the molecular weight of these polyglycols may vary from about 400 to 4,000, preferably around 600 to 2,000.
  • Any organic polyacrylonitrile solvent which does not undergo side reactions with the polyglcols of this invention can be used in the practice of this invention.
  • the preferable solvents are N,N-dimethylacetamide, dimethylsulfoxide, ethylene carbonate, and the like.
  • polyethylene glycol, polypropylene glycol or polybutylene glycol effects improvements in properties of fiber spun from all suitable solutions of acrylonitrile polymers.
  • the invention is applicable not only topolyacrylonitrlle but also to copolymers, interpolymers, and blends thereof, particularly those containing at least 80 percent by weight of polymerized or copolyrnerized acrylonitrile.
  • Such polymeric materials include acrylonitrile fiber forming polymers with readily dyeable basic copolyrners, the blend having an overall polymerized acrylonitrile content of at least 80 percent by weight.
  • the polymer may be a copolymer of 80 to 98 percent of acrylonitrile and from 2 to 20 percent of another copolymerizable monoolefinic monomer.
  • Suitable copolymerizable mono-olefinic monomers include acrylic, alpha-chloroacrylic and methacrylic acids;
  • acrylates such as methylmethacrylate, ethylmethacrylate,
  • chloroethyl methacrylate and the corresponding esters of acrylic and alpha-chloroacrylic acids
  • the polymer can also be a blend of polyacrylonitrile or a copolymer of from 80 to 98 percent acrylonitrile and from 1 to 20 percent of at least one other mono-olefinic copolymerizable monomeric substance with from 2 to 50 percent of the weight of the blend of a copolymer of from 30 to 90 percent of a vinyl-substituted tertiary heterocyclic amine and from to 70 percent of at least one other mono-olefinic copolymerizable monomer preferl0 ably, when the polymeric material comprises a blend, it will be a blend of from 80 to 99 percent of a copolyrner of 80 to 98 percent acrylonitrile and from 2 to 20 percent of another mono-olefinic monomer, such as vinyl acetate, which is not receptive to dye stuff, with from 1 to percent of a copolymer of from 30 to 90 percent of a vinyl-substituted tertiary heterocyclic amine such as vinylpyridine
  • the preferred polymers employed in the instant invention are those containing at least 80 percent acrylonitrile, generally recognized as the fiber-forming acrylonitrile polymers, it will be understood that the invention is likewise applicable to polymers containing less than 80 percent of acrylonitrile when such polymers are useful in forming fibers.
  • the polymers useful in the practice of the present invention may be prepared by any conventional polymerization procedures, such as mass polymerization methods, solution polymerization methods or aqueous emulsion procedures. If it is desired to produce shaped articles from the acrylonitrile polymer solutions of the present invenlow.
  • the fibrillation measurement is comparative and such measurement is made on a fabric formed from the fibers. The degree of fibrillation is determined on a tricot knit tape and the value obtained is called a tricot rating or TR.
  • the tape is flex abraded for 150 cycles on a Stroll abrader or Universal wear tester using the flexing bar with a 2 lb. tenison and /2 lb. weight on the head.
  • agents may be added to the solutions to accomplish these effects either prior or after the addition of one of the polyglycols of this invention thereto without any ill effects thereon.
  • Such added agents might be pigments, dyes, anti-static agents, fire-retarding agents, and the like.
  • Solutions containing from 8 to 30 percent by weight of acrylonitrile polymers may be employed, with the preferred concentration range being from 15 to 25 percent.
  • the invention is further illustrated by the following examples showing the improvements obtained by adding polyethylene glycol to acrylonitrile polymer solutions.
  • all parts and percents are by weight.
  • EXAMPLE I This example involves preparing a spinning dope in the normal fashion to which polyethylene glycol (PEG) has been added.
  • a solution was prepared by mixing 25 percent of an acrylonitrile copolyrner containing 93.7 percent acrylonitrile and 6.3 percent vinyl acetate and 2.5 percent of PEG having an average molecular Weight of 7 0 1,000 with N,N-dimethylacetamide and stirring at about 50 C. until a solution was formed.
  • the solution was then spun to fiber according to normal wet spinning processes. Typical tensile properties of fibers spun from this solution and the corresponding control are tabulated be-
  • These results clearly indicate a region of maximum efficacy in the range of 4004,000 molecular weight for the PEG additive. They show the reduction in void number and improvement in abrasion character which marks the present invention. They also suggest the unsuitability of polymers incompatibility with the acrylonitrile polymer for the present invention.
  • Claim 1 wherein said polymer is a copolymer com prising at least 85 percent polyacrylonitrile and up to percent of a copolymerizable mono-olefinic monomer.
  • Claim 1 wherein said polymer is a blend of 80 to 99 percent of (A) a copolymer containing from 80 to 98 percent of acrylonitrile and 2 to percent of a copolymerizable mono-olefinic monomer and from 1 to 20 percent of (B) a copolymer containing 10 to 70 percent of acrylonitrile and to 90 percent of a Vinyl substituted tertiary heterocyclic amine said blend having an overall vinyl substituted tertiary heterocyclic amine content of from 2 to 20 percent based on the weight of the blend.
  • Substantially void free fibers and filaments are also obtained when polypropylene or polybutylene glycols of suitable molecular weight are employed.
  • a process for the production of void free fibers and filaments from acrylonitrile polymers comprising mixing an acrylonitrile polymer comprising at least 85 percent acrylonitrile, an organic solvent therefor, and from about 1 to about 25 percent based on the weight of the polymer of a polyglycol of from 1 to 4 carbon atoms and having an average molecular weight of from 400 to 4,000, stirring and thereafter extruding the resultant polyglycol polymer spinning solution through a Table VI shows the results of each glycol is from 400 to 2,000.
  • Claim 1 wherein the polyglycol is polyethylene glycol of 400 molecular Weight.
  • Claim 1 wherein the polyglycol is polyethylene glycol of 1,000 molecular weight.
  • Claim 1 wherein the polyglycol is polyethylene glycol of 4,000 molecular Weight.
  • a process for the production of void free fibers and filaments from acrylonitrile polymers comprising mixing 25 percent by weight of an acrylonitrile polymer comprising 93.7 percent acrylonitrile and 6.3 percent vinyl acetate, percent by weight of N,N- dimethylacetamide and 2.5 percent by weight of polyethylene glycol of 1,000 molecular weight, stirring and extruding the resultant polyethylene glycol polymer spinning solution through a suitable extrusion orifice to effect the formation of fibers and filaments therefrom.

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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)
US146555A 1961-10-20 1961-10-20 Method of preparing void free fibers from acrylonitrile polymers Expired - Lifetime US3180845A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
NL132471D NL132471C (fr) 1961-10-20
NL284543D NL284543A (fr) 1961-10-20
BE623827D BE623827A (fr) 1961-10-20
US146555A US3180845A (en) 1961-10-20 1961-10-20 Method of preparing void free fibers from acrylonitrile polymers
GB37591/62A GB987303A (en) 1961-10-20 1962-10-04 Improved filaments and staple fibers of acrylonitrile polymers and a method of preparing same
FR912407A FR1337614A (fr) 1961-10-20 1962-10-16 Perfectionnements à la fabrication d'articles en polymères d'acrylonitrile
CH1221862A CH413219A (fr) 1961-10-20 1962-10-18 Procédé de fabrication de fibres et filaments polymères d'acrylonitrile
DK451862AA DK107050C (da) 1961-10-20 1962-10-19 Fremgangsmåde til fremstilling af hulrumsfri fibre og filamenter af acrylonitrilpolymeropløsninger.
DEM54571A DE1292310B (de) 1961-10-20 1962-10-20 Verfahren zur Herstellung von Fasern und Faeden aus Acrylnitrilpolymerisaten

Applications Claiming Priority (1)

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US146555A US3180845A (en) 1961-10-20 1961-10-20 Method of preparing void free fibers from acrylonitrile polymers

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US (1) US3180845A (fr)
BE (1) BE623827A (fr)
CH (1) CH413219A (fr)
DE (1) DE1292310B (fr)
DK (1) DK107050C (fr)
GB (1) GB987303A (fr)
NL (2) NL132471C (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3388202A (en) * 1965-09-27 1968-06-11 Monsanto Co Method for melting acrylonitrile polymers and copolymers
US3455862A (en) * 1966-03-28 1969-07-15 Monsanto Co Dispersions in acrylonitrile polymer solutions
US3846833A (en) * 1970-04-14 1974-11-05 Celanese Corp Acrylic filaments which are particularly suited for thermal conversion to carbon filaments
US3860567A (en) * 1971-04-05 1975-01-14 Monsanto Co Epoxide and polyhydroxyl-containing acrylic fiber
US4051300A (en) * 1973-09-03 1977-09-27 Gulf South Research Institute Hollow synthetic fibers
US4239722A (en) * 1976-12-16 1980-12-16 Bayer Aktiengesellschaft Process for the production of hydrophilic fibres
EP0207721A2 (fr) 1985-06-27 1987-01-07 A/G Technology Corporation Membranes anisotropes pour la séparation de gaz
US5762798A (en) * 1991-04-12 1998-06-09 Minntech Corporation Hollow fiber membranes and method of manufacture
USRE36914E (en) * 1992-10-07 2000-10-17 Minntech Corp Dialysate filter including an asymmetric microporous, hollow fiber membrane incorporating a polyimide
US6143411A (en) * 1995-09-14 2000-11-07 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Apparatus and method for spinning hollow polymeric fibres

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2517694A (en) * 1943-09-14 1950-08-08 American Viscose Corp Crimped artificial filament
US2715763A (en) * 1950-06-27 1955-08-23 American Viscose Corp Synthetic textile fiber
US2752317A (en) * 1953-02-24 1956-06-26 Du Pont Chlorosulfonated hydrocarbon polymer compositions containing antigelling agents
US2801982A (en) * 1951-12-15 1957-08-06 Hoechst Ag Acrylonitrile polymer pastes
US2878226A (en) * 1956-12-17 1959-03-17 Chemstrand Corp Acrylonitrile polymer composition stabilized with metal formaldehyde sulfoxylate and methylol sulfonic acid and method of making same
US2904391A (en) * 1956-09-10 1959-09-15 Courtaulds Ltd Production of polyacrylonitrile threads, fibres, filaments and the like
US2916348A (en) * 1956-08-21 1959-12-08 American Cyanamid Co Production of polyacrylonitrile filaments
DE1085645B (de) * 1959-05-06 1960-07-21 Hans J Zimmer Verfahrenstechni Verfahren zur Herstellung von Polyacrylnitrilfaeden oder -fasern mit hoher Festigkeit
US3008793A (en) * 1961-11-14 Variable coupling electromagnetic
US3080210A (en) * 1961-12-01 1963-03-05 Monsanto Chemicals Spinning of acrylonitrile polymers
US3088188A (en) * 1960-01-04 1963-05-07 Monsanto Chemicals Manufacture of shaped objects of acrylonitrile polymer by wet spinning
US3124619A (en) * 1964-03-10 Certificate of correction

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1085292B (de) * 1959-04-25 1960-07-14 Wolfen Filmfab Veb Verfahren zur Herstellung von Gebilden aus Polyacrylnitril und bzw. oder seinen Mischpolymerisaten

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3008793A (en) * 1961-11-14 Variable coupling electromagnetic
US3124619A (en) * 1964-03-10 Certificate of correction
US2517694A (en) * 1943-09-14 1950-08-08 American Viscose Corp Crimped artificial filament
US2715763A (en) * 1950-06-27 1955-08-23 American Viscose Corp Synthetic textile fiber
US2801982A (en) * 1951-12-15 1957-08-06 Hoechst Ag Acrylonitrile polymer pastes
US2752317A (en) * 1953-02-24 1956-06-26 Du Pont Chlorosulfonated hydrocarbon polymer compositions containing antigelling agents
US2916348A (en) * 1956-08-21 1959-12-08 American Cyanamid Co Production of polyacrylonitrile filaments
US2904391A (en) * 1956-09-10 1959-09-15 Courtaulds Ltd Production of polyacrylonitrile threads, fibres, filaments and the like
US2878226A (en) * 1956-12-17 1959-03-17 Chemstrand Corp Acrylonitrile polymer composition stabilized with metal formaldehyde sulfoxylate and methylol sulfonic acid and method of making same
DE1085645B (de) * 1959-05-06 1960-07-21 Hans J Zimmer Verfahrenstechni Verfahren zur Herstellung von Polyacrylnitrilfaeden oder -fasern mit hoher Festigkeit
US3088188A (en) * 1960-01-04 1963-05-07 Monsanto Chemicals Manufacture of shaped objects of acrylonitrile polymer by wet spinning
US3080210A (en) * 1961-12-01 1963-03-05 Monsanto Chemicals Spinning of acrylonitrile polymers

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3388202A (en) * 1965-09-27 1968-06-11 Monsanto Co Method for melting acrylonitrile polymers and copolymers
US3455862A (en) * 1966-03-28 1969-07-15 Monsanto Co Dispersions in acrylonitrile polymer solutions
US3846833A (en) * 1970-04-14 1974-11-05 Celanese Corp Acrylic filaments which are particularly suited for thermal conversion to carbon filaments
US3860567A (en) * 1971-04-05 1975-01-14 Monsanto Co Epoxide and polyhydroxyl-containing acrylic fiber
US4051300A (en) * 1973-09-03 1977-09-27 Gulf South Research Institute Hollow synthetic fibers
US4239722A (en) * 1976-12-16 1980-12-16 Bayer Aktiengesellschaft Process for the production of hydrophilic fibres
EP0207721A2 (fr) 1985-06-27 1987-01-07 A/G Technology Corporation Membranes anisotropes pour la séparation de gaz
US5762798A (en) * 1991-04-12 1998-06-09 Minntech Corporation Hollow fiber membranes and method of manufacture
USRE36914E (en) * 1992-10-07 2000-10-17 Minntech Corp Dialysate filter including an asymmetric microporous, hollow fiber membrane incorporating a polyimide
US6143411A (en) * 1995-09-14 2000-11-07 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Apparatus and method for spinning hollow polymeric fibres
US6242093B1 (en) 1995-09-14 2001-06-05 The Secretary Of State For Defense In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Carbon fibers

Also Published As

Publication number Publication date
BE623827A (fr)
GB987303A (en) 1965-03-24
NL132471C (fr)
DK107050C (da) 1967-04-17
NL284543A (fr)
CH413219A (fr) 1966-05-15
DE1292310B (de) 1969-04-10

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