EP0360708B1 - Fils à base de polyamide imide et leur procédé d'obtention - Google Patents

Fils à base de polyamide imide et leur procédé d'obtention Download PDF

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Publication number
EP0360708B1
EP0360708B1 EP89420348A EP89420348A EP0360708B1 EP 0360708 B1 EP0360708 B1 EP 0360708B1 EP 89420348 A EP89420348 A EP 89420348A EP 89420348 A EP89420348 A EP 89420348A EP 0360708 B1 EP0360708 B1 EP 0360708B1
Authority
EP
European Patent Office
Prior art keywords
units
solvent
yarns
filaments
polyamide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP89420348A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0360708A1 (fr
Inventor
Pascal Barthelemy
Bruno Testard
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhone Poulenc Fibres SA
Original Assignee
Rhone Poulenc Fibres SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhone Poulenc Fibres SA filed Critical Rhone Poulenc Fibres SA
Publication of EP0360708A1 publication Critical patent/EP0360708A1/fr
Application granted granted Critical
Publication of EP0360708B1 publication Critical patent/EP0360708B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
    • 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
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products

Definitions

  • the present invention relates to thermostable synthetic yarns based on polyamide-imide with improved properties.
  • the yarns according to the invention are also characterized by a polydispersity index I ⁇ 2, 2 a toughness ⁇ 45 CN / tex, a Young's modulus ⁇ 3.8 GPa, an elongation ⁇ 25% and a color defined by the luminance Y> 25%, the degree of white DB ⁇ 30, the yellow index IJ> 170.
  • the toughness is of the order of 50 to 55 cN / tex, the module ⁇ 4 GPa, the luminance Y> 30%, the degree of white ⁇ 28, the index of yellow> 190.
  • the light stability of PAIs according to the invention can also be greatly improved compared to that of PAI yarns known hitherto. It is evaluated by the retention of mechanical properties: tenacity at break ⁇ 50%, working at break ⁇ 18%, elongation ⁇ 35%. The light stability is measured according to the method described below.
  • the yarns according to the invention have a chemical structure as defined above in which R is a radical such that: and preferably and R1 preferably a radical R2 preferably a radical and M is preferably Na or K.
  • the PAI wires are also characterized by a value of the polydispersity index I ⁇ 2.2.
  • This index corresponds to the ratio Mw / Mn , the values of Mn and Mw being determined by gel exclusion chromatography (GPC) in the NMP at 80 ° C. and 0.1 mole / liter of lithium bromide, the masses being expressed relative to a polystyrene calibration.
  • the polydipersity index of the PAI yarns according to the invention remains low: it corresponds to a narrowing of the distribution of the molecular masses. Surprisingly, it remains low at the level of the finished threads despite the various treatments undergone by the filaments during their preparation.
  • the threads according to the invention also have excellent mechanical and thermal characteristics, much superior to those of the polyamide-imide threads according to FR 2 079 785.
  • the toughness is greater than or equal to 45 cN / tex, of preferably 50 or 55 cN / tex.
  • the measurement is carried out on a manual or automatic dynamometer with constant gradient of elongation on a wire test piece subjected to longitudinal traction until it breaks.
  • the elongation at break is measured as indicated above. It is less than or equal to 25%.
  • the longitudinal Young E modulus of the PAI wires according to the invention is ⁇ 3.8 GPa, preferably ⁇ 4 GPa. This is the report obtained at the start of the force / elongation curve.
  • the specific force (tenacity) corresponds to the ratio: ⁇ l being the increase in the length of the test piece at time t to which the actual titer corresponds and lo the initial length of the test piece.
  • the degree of white defines a point of color in the chromaticity plane.
  • the yellow index is an expression of color purity in yellow.
  • the light stability measurements are carried out in an enclosure which makes it possible to experimentally study the photoaging of polymers in a dry atmosphere.
  • the samples to be tested are placed on a cylindrical turret animated by a circular rotational movement located in the center of a parallelepipedic enclosure, the four corners of which are occupied by a "medium pressure" mercury vapor lamp type MAZDA MA 400 Watts.
  • the envelope only lets through radiation above 300 nm (solar spectrum).
  • the temperature in the enclosure is 60 ° C.
  • Procedure The 1.4 cm paper window to which the sample is fixed when determining the mechanical properties on INSTRON is itself placed on one of the 24 supports of the chamber turret. After the exposure, we recover the paper window and determine the mechanical characteristics monofilament according to the method for determining the mechanical properties indicated above.
  • the yarns according to the invention have a clear superiority compared to known PAI yarns.
  • the yarns according to the invention also have a much better thermal resistance than that of known PAI yarns: it is evaluated by the rate of degradation corresponding to a percentage of weight loss as a function of time at a temperature of 375 °, in air.
  • the isothermal degradation of PAI yarns according to the invention is generally ⁇ 3% per hour, and preferably ⁇ 2% per hour.
  • the filaments, threads, fibers according to the present invention can be used alone or mixed with natural or synthetic threads or fibers in order to modify or improve certain properties. They are particularly interesting for the production of work and protective clothing, thanks to their mechanical properties and their thermal and light resistance. In addition, the yarns obtained are easy to dye in all colors with basic dyes.
  • the PAI yarns according to the present invention are obtained by wet spinning from solutions of polymer in a solvent or solvent mixture.
  • concentration of the spinning solutions is between 4 and 35%, preferably between 5 and 35%.
  • the polymers are dissolved in a solvent or solvent mixture containing from 5 to 100% by weight of dimethylethylene urea of pH ⁇ 7 and 0 to 55% of an anhydrous aprotic polar solvent such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide, tetramethylurea or ⁇ butyrolactone.
  • the solutions which can be used in the process according to the invention must have a viscosity of between 100 and 200 poises, preferably between 150 and 160 poises. They can also contain various adjuvants such as pigments, matifiers to improve certain properties.
  • the PAI solutions are spun in a binary or ternary aqueous coagulating bath containing a solvent or solvent mixture in proportion of 30 to 80% of solvent and 20 to 70% of water, preferably 40 to 70% of solvent (s).
  • the solvent used can be dimethylformamide, dimethylethylene urea or a mixture thereof.
  • the spinning bath is maintained between 15 and 40 ° C, preferably 20 to 30 ° C.
  • the length of the coagulating bath is adaptable generally depending on the solvent concentration and the temperature. Baths with a higher solvent content generally make it possible to obtain yarns with better stretchability, therefore better final properties. However, when the solvent concentration is higher, a longer bath length is necessary.
  • the filaments leaving the coagulating bath in the gel state are then drawn, for example in air at a rate defined by the ratio V2 V1 x 100, V2 being the speed of the stretching rollers, V1 those of the delivery rollers.
  • the rate of drawing of the strands in the gel state is at least 100%, preferably at least 110% or even more.
  • the washed filaments are then dried by known means, for example in a dryer or on rollers.
  • the temperature of this drying can vary within wide limits as well as the speed which is higher the higher the temperature. It is generally advantageous to carry out drying with gradual rise in temperature, this temperature possibly reaching and even exceeding 200 ° C. for example.
  • the filaments are then subjected to hot over-stretching to improve their mechanical qualities and in particular their toughness, which may be advantageous for certain jobs.
  • This hot over-drawing can be carried out by any known means: oven, plate, roll, roll and plate, preferably in a closed enclosure. It must be carried out at a temperature of at least 150 ° C, which can reach and even exceed 200 to 300 ° C. Its rate is generally at least 150% but it can vary within wide limits depending on the qualities desired for the finished yarn. The total draw rate is at least 250%, preferably at least 260%.
  • the drawing and overdrawing assembly can be carried out in one or more stages, continuously or discontinuously with the preceding operations.
  • secondary stretching can be combined with drying. For this, it is sufficient to provide, at the end of the drying, a higher temperature zone allowing overstretching.
  • a PAI solution is prepared from: - trimellic anhydride (ANTM) 40 mole% - isophthalic acid (AI) 8 mole% - sodium salt of 5 isophthalic acid (AiSNa) 2 mole% - 4,4 ′ diphenyl ether diisocyanate (DIDE) 50 mole% in dimethylethylene urea of pH ⁇ 7 so as to obtain a concentration of 21%, the polydispersity index of the polymer is 1.78.
  • the solution of viscosity 598 poises, is extruded in an aqueous coagulating bath containing dimethylethylene urea.
  • the filaments come out of the coagulating bath in the gel state and are drawn into air at ordinary temperature. They are washed with water in a bath to remove the solvent and dried on rollers.
  • M w goes from 116,400 to 99,720, ie a loss of 16,680.
  • the polydispersity index of the polymer according to the invention after exposure goes from 2.05 to 2.13 whereas, according to example 3C, the polydispersity index goes from 3 to 4.12.
  • the solution of this polymer in the DMEU has a concentration of 21% and a viscosity of 781 poises. It is spun under the following conditions:
  • the mechanical properties of the wires are as follows: Ex. Elongation% Tenacity cN / tex GPa module Temperature TG ° C Polydipersity index. I 4 23 51 6.3 265 2.2
  • a solution of PAI with the same chemical structure as that described in Example 1 is prepared in a mixture of DMEU / DMF in proportion 72/28.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Organic Insulating Materials (AREA)
  • Hydrogenated Pyridines (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Materials For Medical Uses (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
EP89420348A 1988-09-21 1989-09-14 Fils à base de polyamide imide et leur procédé d'obtention Expired - Lifetime EP0360708B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8812560 1988-09-21
FR8812560A FR2643089B1 (fr) 1988-09-21 1988-09-21 Fils a base de polyamide-imide et leur procede d'obtention

Publications (2)

Publication Number Publication Date
EP0360708A1 EP0360708A1 (fr) 1990-03-28
EP0360708B1 true EP0360708B1 (fr) 1995-11-29

Family

ID=9370402

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89420348A Expired - Lifetime EP0360708B1 (fr) 1988-09-21 1989-09-14 Fils à base de polyamide imide et leur procédé d'obtention

Country Status (15)

Country Link
US (1) US5159052A (ja)
EP (1) EP0360708B1 (ja)
JP (1) JP2744084B2 (ja)
CN (1) CN1031290C (ja)
AT (1) ATE130879T1 (ja)
BR (1) BR8904858A (ja)
CA (1) CA1334612C (ja)
DE (1) DE68924946T2 (ja)
DK (1) DK464489A (ja)
ES (1) ES2079384T3 (ja)
FI (1) FI894450A (ja)
FR (1) FR2643089B1 (ja)
IE (1) IE69380B1 (ja)
NO (2) NO893257D0 (ja)
RU (1) RU1838468C (ja)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7820151B2 (en) 2004-02-13 2010-10-26 L'oreal S.A. Composition for coating keratin fibers, comprising at least one tacky wax and fibers

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2685354B1 (fr) * 1991-12-24 1996-03-29 Rhone Poulenc Fibres Procede de filage de solutions de polyamides-imides (pai) a base de toluylene ou de metaphenylene diisocyanates et fibres ainsi obtenues.
US6258916B1 (en) 1991-12-24 2001-07-10 Rhone-Poulenc Fibres Process for spinning from solution of polyamide-imides (PAI) based on tolylene or meta-phenylene diisocyanates and fibers thus obtained
US5756635A (en) * 1991-12-24 1998-05-26 Rhone-Poulenc Fibres Process for spinning from solution of polyamide-imides (PAI) based on tolylene or met-phenylene diisocyanates and fibres thus obtained
JPH07310232A (ja) * 1994-05-13 1995-11-28 Toyobo Co Ltd バグフィルター用ポリアミドイミド繊維
DE60314963T2 (de) 2002-09-06 2008-04-10 L'oreal Verfahren zur dekorativen Behandlung der Wimpern mit einem Überzugsmittel, das ein klebriges Wachs enthält
US7923002B2 (en) 2002-09-06 2011-04-12 L'oreal S.A. Composition for coating keratin fibres comprising a tacky wax
JP2014031420A (ja) * 2012-08-02 2014-02-20 Hitachi Chemical Co Ltd ポリアミドイミド樹脂の合成方法、ポリアミドイミド樹脂およびポリアミドイミド樹脂組成物

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3843587A (en) * 1969-05-16 1974-10-22 Schenectady Chemical Polyamide-imide resins prepared from the reaction of aromatic diisocyanates with mixtures of polycarboxylic acids and anhydrides
FR2079785A5 (en) * 1970-02-12 1971-11-12 Rhodiaceta Lustrous polyamide-imide based fibres by new process
BE787500A (fr) * 1971-08-12 1973-02-12 Rhone Poulenc Textile Procede pour l'obtention de fils brillants
FR2165236A5 (en) * 1971-12-21 1973-08-03 Rhone Poulenc Textile Non-inflammable fibres - from copolymers with amide-imide and acrylonitrile recurring units
US4001186A (en) * 1974-11-07 1977-01-04 The Upjohn Company Preparation of polyimide from organic diisocyanate with alkali metal salt of alcohol as catalyst
JPS51143724A (en) * 1975-06-02 1976-12-10 Asahi Chem Ind Co Ltd A multifilament yarn of an aromatic polymer and the manufacturing proc ess thereof
JPS52151393A (en) * 1976-06-11 1977-12-15 Toyobo Co Ltd Poly-(n-ethylenetrimellitateimide) fiber or film its preparation
FR2478116B1 (fr) * 1980-03-14 1985-06-14 Rhone Poulenc Textile Solutions conformables a partir de melanges de cellulose et polyamide-imide et articles en forme obtenus
US4640972A (en) * 1985-11-15 1987-02-03 E. I. Du Pont De Nemours And Company Filament of polyimide from pyromellitic acid dianhydride and 3,4'-oxydianiline
US4758649A (en) * 1986-05-21 1988-07-19 Kuraray Co., Ltd. Heat resistant organic synthetic fibers and process for producing the same
FR2627497B1 (fr) * 1988-02-22 1990-06-15 Rhone Poulenc Fibres Solutions de polyamides-imides et leur procede d'obtention

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7820151B2 (en) 2004-02-13 2010-10-26 L'oreal S.A. Composition for coating keratin fibers, comprising at least one tacky wax and fibers

Also Published As

Publication number Publication date
DK464489D0 (da) 1989-09-20
CN1041406A (zh) 1990-04-18
JPH02104721A (ja) 1990-04-17
IE893013L (en) 1990-03-21
NO893499D0 (no) 1989-08-31
ES2079384T3 (es) 1996-01-16
NO893499L (no) 1990-03-22
BR8904858A (pt) 1990-05-08
DE68924946T2 (de) 1996-07-04
ATE130879T1 (de) 1995-12-15
EP0360708A1 (fr) 1990-03-28
FR2643089A1 (fr) 1990-08-17
IE69380B1 (en) 1996-09-04
CN1031290C (zh) 1996-03-13
NO893257D0 (no) 1989-08-14
DK464489A (da) 1990-03-22
FI894450A (fi) 1990-03-22
CA1334612C (fr) 1995-03-07
US5159052A (en) 1992-10-27
RU1838468C (ru) 1993-08-30
JP2744084B2 (ja) 1998-04-28
FI894450A0 (fi) 1989-09-20
FR2643089B1 (fr) 1991-05-10
DE68924946D1 (de) 1996-01-11

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