EP0061117B1 - Filaments et fibres fixés en polyacrylonitrile, et procédé pour leur fabrication - Google Patents

Filaments et fibres fixés en polyacrylonitrile, et procédé pour leur fabrication Download PDF

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Publication number
EP0061117B1
EP0061117B1 EP82102086A EP82102086A EP0061117B1 EP 0061117 B1 EP0061117 B1 EP 0061117B1 EP 82102086 A EP82102086 A EP 82102086A EP 82102086 A EP82102086 A EP 82102086A EP 0061117 B1 EP0061117 B1 EP 0061117B1
Authority
EP
European Patent Office
Prior art keywords
fibers
threads
filaments
tex
shrinkage
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
Application number
EP82102086A
Other languages
German (de)
English (en)
Other versions
EP0061117A2 (fr
EP0061117A3 (en
Inventor
Walter Dr. Fester
Bernd Dr. Huber
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.)
Hoechst AG
Original Assignee
Hoechst AG
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
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=4221620&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0061117(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Hoechst AG filed Critical Hoechst AG
Priority to AT82102086T priority Critical patent/ATE14757T1/de
Publication of EP0061117A2 publication Critical patent/EP0061117A2/fr
Publication of EP0061117A3 publication Critical patent/EP0061117A3/de
Application granted granted Critical
Publication of EP0061117B1 publication Critical patent/EP0061117B1/fr
Expired 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
    • D01F6/02—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
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber

Definitions

  • the invention relates to threads and fibers made of polyacrylonitrile. whose thread-forming substance consists of at least 98% by weight of acrylonitrile building blocks and has a high average molecular weight.
  • a special drawing and fixing process can be used to obtain threads and fibers which show increased resistance to swelling and hydrolysis processes, even at elevated temperatures.
  • threads and fibers made of acrylonitrile polymers are already claimed, the thread-forming substance of which is 70 to 100% by weight, preferably at least 90 or even 99 % By weight is made up of acrylonitrile building blocks and these threads or fibers have an initial modulus of more than 1300 cN / tex, based on 100% elongation, and possibly a tensile strength of at least 50 cN / tex with an elongation at break of max. Should have 15%.
  • Such threads can be obtained by spinning a solution of thread-forming polymer and solvent either by a dry spinning process or using a precipitation bath of solvent and water. After a wet drawing, preferably at temperatures a little below the boiling point of the bath liquid and a washing treatment, the spun threads are then dried on hot rollers under tension, possibly with a low degree of shrinkage, and then subjected to a contact drawing of at least 1: 1.5.
  • the effective total drawing of the threads should be at least 1: 9, preferably 1:10 to 1:25.
  • Such fibers and threads can be used with great success in technical fields of application, for example for the production of filters and filter fabrics, for use as a base fabric for the production of coated fabrics and in particular also for reinforcing organic and inorganic materials.
  • the aqueous phase reacts alkaline. It is believed that the action of the solvent residues and monomers leads in particular to swelling at higher temperatures and also the reinforcing properties of the threads, i. H. in particular their initial modulus and fiber strength are reduced.
  • threads and fibers made of acrylonitrile polymers the thread-forming substance of which is composed of at least 98% by weight of acrylonitrile units, the relative viscosity of the thread-forming substance (measured as a 0.5% by weight solution in dimethylformamide at 25 ° C. ) is between 2.5 and 6.0.
  • the fibers and threads have tensile strengths of more than 50 cN / tex with a boiling shrinkage of less than 5% and an elongation at break of at most 15% and in which the initial modulus after an aqueous alkaline treatment at 90 ° C. for 24 hours is greater than 900 cN / tex, based on 100% elongation.
  • a method is suitable for producing such threads, in which the threads drawn off from the nozzle, obtained by a wet or dry spinning process, are wet drawn before or after washing, dried under tension on hot rollers and under the action of dry heat at 140 to 200 ° C. are post-stretched, with a post-drawing of at least 1 1.5 the total drawing is at least 1: 9 and the threads after post-drawing are fixed without the approval of shrinkage by exposure to dry heat at 170 to 280 ° C, preferably 180 to 250 ° C .
  • organic composite systems e.g. B. based on epoxy resins or unsaturated polyester resins as well as in inorganic systems with hydraulic binders.
  • threads and fibers which have high tensile strengths of 50 to 100 cN / tex, preferably 55 to 80 cN / tex, low boiling shrinkage of less than 5%, preferably less than 3% and elongations at break of up to 15 , preferably a maximum of 12%.
  • the fibers and threads obtained also have excellent stability against the action of swelling and hydrolytically attacking media.
  • aqueous alkaline medium produced by extracting 150 g of Portland cement with 1 liter of water, and then washing and drying, the fibers still have an initial modulus of at least 900 cN / tex, preferably of at least 1 000 cN / tex, based on 100% elongation.
  • the threads and fibers according to the invention are particularly suitable as reinforcing threads or fibers or in the form of woven, knitted or non-woven fabrics for the production of reinforced organic or inorganic materials. These products are particularly advantageous for the production of hydraulic binder-containing products with a fine cavity structure. But they are also suitable for the production of filters or filter fabrics or as a base fabric for the production of coated fabrics.
  • the invention is also based on a process for the production of fibers and threads by a wet or dry spinning process, the wet stretching of the spun threads being able to take place before, during or after the washing treatment, the threads then being dried and then subjected to hot stretching.
  • the process according to the invention is characterized in that the threads are optionally dried in cable or strand form on hot rollers under tension and then subjected to a contact stretching of at least 1 1.5, the effective total stretching having to be at least 1: 9. Under a contact stretching, the stretching in the dry hot state, e.g. B. be understood by using panel radiators.
  • the threads are fixed by exposure to dry heat. This can be done, for example, on rotating hot rollers, on irons, in a hot air duct or by infrared radiation.
  • the precipitation or solution polymers prepared by the customary processes can be used as polymer raw materials. Depending on the requirements for the areas of application, both homo- and copolymers of acrylonitrile can be used. The highest possible purity should be ensured for the monomers used. Suitable comonomers are all unsaturated compounds copolymerizable with acrylonitrile.
  • Polymers can be used whose relative solution viscosities - measured in 0.5% dimethylformamide solutions - are in the range from 2.5 to 6.0. Particularly good results under economic conditions are achieved with polymers which are in a viscosity range from about 2.6 to 3.5.
  • the polymers used should preferably have a content of at least about 99% by weight of acrylonitrile units.
  • the dissolving conditions When producing the spinning solutions, the dissolving conditions must be selected so that the most homogeneous, gel particle-free spinning solutions are obtained. Scattered light measurements using a laser as the light source are particularly suitable for checking the quality of the spinning solution. Only flawless spinning solutions which show very low scattered light values enable the high draws required according to the invention.
  • the spinning solutions can be prepared both continuously and discontinuously.
  • inorganic or organic additives can be incorporated, such as. B. Niating agents, stabilizers, flame retardants, etc.
  • the spinning process according to the invention is characterized by a high effective total drawing of at least 1: 9.
  • the effective total drawing should be at least 1: 9 by the method according to the invention. Effective total draw ratios of 1:10 to 1:25 are preferred.
  • the method according to the invention can be carried out on conventional thread or fiber spinning systems. New techniques that were not previously common are not required. In particular, it is not necessary to use a special drawing chamber in which the threads, for. B. exposed in cable form to the action of steam under pressure. The process is characterized by high total draw values of the freshly spun threads, whereby an effective minimum draw of 900% is required. This effective total drawing takes place in several stages. First, the threads are stretched wet before or after washing out the residual solvent content in one or gradually in several hot baths. The temperature of the stretching bath media, which generally consist of mixtures of water and the solvent, should be kept as high as possible. Temperatures a little below the boiling point of the bath liquid are preferred.
  • baths which contain other stretching bath media are also possible, e.g. B. glycol or glycerin, optionally in a mixture with the polymer solvent, at which stretching temperatures above 100 ° C can be selected.
  • the threads are prepared in a preparation bath and then freed as much as possible of adhering water by the action of rotating pairs of press rollers.
  • the preparation applied in the preparation bath can influence the stretching behavior of the threads. It should therefore be selected from known preparation mixtures that shows a low thread-thread friction.
  • the threads are then dried under tension on hot rollers.
  • a small amount of shrinkage which often proves to be advantageous for the subsequent stretching, can be permitted;
  • care must be taken that the cables always run under tension over the drying rollers.
  • the temperature of the rollers should be chosen so that the cable leaves the dryer with a very low residual moisture content of less than 1%. Temperatures in the range from 140 to 200 ° C. have proven particularly favorable for these rolls, but this does not exclude the use of higher or lower temperatures. It is also possible to dry on the rollers at stepped temperatures.
  • the spun tow is stretched again using dry heat at least 1.5 times its length.
  • the stretching can also take place in one or more stages.
  • the heating of the cable can be done according to the usual methods in the art, e.g. B. by rotating hot rollers, by contact over hot plates, in a hot air duct or by radiation, especially infrared radiation. Gradual stretching, in which different heating methods are used, can also be used.
  • the drawing temperatures are influenced by the type of polymer used and in part by the previous drawing and the drying conditions.
  • a temperature range of about 120 to 250 ° C. is generally suitable, and the range of 140 to 200 ° C. is particularly favorable.
  • the threads are exposed to dry heat at temperatures of 170 to 280, preferably 180 to 250 ° C fixed without approval of shrinkage.
  • the fixation can be done according to the usual methods in the art, for. B. by rotating hot rollers, by contact with hot plates, in a hot air duct or by radiation, especially by infrared radiation.
  • the threads are cooled, either wound up into continuous material by known methods or cut into fibers with the desired cutting length. If required by the field of application, a special preparation can be applied to the threads or fibers before or after cutting.
  • the selection of the temperatures and the residence time of the threads during fixing can have a significant influence on the physical properties of the threads treated in this way and on their resistance to swelling and / or hydrolytically active substances.
  • the optimal conditions in individual cases can, however, be determined by simple tests. They are influenced, for example, by the titer of the individual filaments, the total thread thickness, the quality of the contact with the heated surfaces, etc. Under the conditions of Example 4, optimal values at temperatures of the first duo of 190 ° C. and 230 to 250 ° C. for the second duo and residence times of in total about 40 seconds were observed on the surfaces of the rolls.
  • a polymer of 99.4% acrylonitrile and 0.6% methyl acrylate was continuously dissolved in a 17% spinning solution in dimethylformamide, filtered and degassed. From this spinning solution, 351 g / min were pressed through a 2500 hole nozzle, hole diameter 0.06 mm, into a precipitation bath which contained 56% dimethylformamide (DMF) and 44% water and was 50 ° C. warm.
  • the threads obtained were drawn off the nozzle at 6.5 m / min, drawn in baths containing 56% DMF and 44% water at 98 ° to six times their length and then washed. When washing in hot water, 9% shrinkage was allowed. After passing through an Aviva bath, the threads were dried at 165 ° C. and stretched 2.4 times their length in several stages at 180 ° C. The total draw was 1: 13.1.
  • the individual filaments produced in this way had the following properties:
  • Threads with these properties were fixed after the second drawing over hot plates with a surface temperature of 230 ° C. while keeping their length constant. After fixing, the individual filaments had the following properties.
  • the fixed and, as a comparison, the unfixed fibers were each treated for 24 hours with a cement filtrate, made from 150 g of Portland cement and 1 liter of water, at different temperatures.
  • the aqueous cement extract had a pH of approximately 11.6.
  • the tested filaments were briefly rinsed with water and air-dried at room temperature. Force expansion diagrams were then recorded on the individual filaments at an elongation rate of 100% / min and the initial moduli were determined.
  • a polymer was spun according to Example 1, but consisting of 95% acrylonitrile and 5% methyl acrylate. With these threads, the stretching had to be reduced somewhat after drying, so that the total stretching was only 1: 11.7.
  • the unfixed fibers had an initial modulus of 1,340 cN / tex, those fixed at 230 ° C an initial modulus of 1,020 cN / tex. After a 24-hour treatment at 90 ° C. in the Portland cement filtrate described, the unfixed fiber had an initial modulus of 720 cN / tex and the fixed one an initial modulus of 740 cN / tex. After this treatment, both fibers had a slightly sticky surface in the moist state, which suggests that the fibers had already been slightly saponified in the hot, alkaline medium.
  • the threads were then washed, finished and dried on 2 duos with surface temperatures of 140 and 185 ° C with a .shrinkage of 0.6 m / min.
  • the threads were drawn from the second duo at 33.3 m / min and stretched over 4 hot plates at temperatures of 150, 160, 160 and 175 ° C. to 91.9 m / min. The total draw was therefore 1: 16.5.

Landscapes

  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Nonwoven Fabrics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Inorganic Fibers (AREA)

Claims (2)

1. Fils et fibres de polymères de l'acrylonitrile, dans lesquels la substance formant des fils est constituée d'au moins 98 % en poids de motifs acrylonitrile, la viscosité relative de la substance formant des fils (mesurée sur une solution à 0,5 % en poids dans du diméthylformamide à 25 °C) est dans l'intervalle de 2,5 à 6,0, les fibres et fils présentent des résistances à la rupture par traction de plus de 50 cN/tex, un retrait à l'ébullition inférieur à 5 % et un allongement à la rupture de 15 % au maximum, et le module initial des fibres et fils après un traitement aqueux-alcalin à 90 °C pendant 24 heures est supérieur à 900 cN/tex, pour un allongement de 100 %.
2. Procédé de fabrication de fils et fibres suivant la revendication 1, caractérisé en ce que les fils retirés de la filière, obtenus par un procédé de filature au mouillé ou à sec, sont étirés au mouillé avant ou après le lavage, séchés sous tension sur des cylindres chauffés et soumis à un post-étirage sous l'action de la chaleur sèche à 140 à 200 °C, l'étirage total, pour un post-étirage d'au moins 1 : 1,5, étant d'au moins 1 : 9, et les fils sont fixés après le post-étirage, sans laisser aucun retrait s'effectuer, par action de la chaleur sèche à 170 à 280 °C, de préférence à 180 à 250 °C.
EP82102086A 1981-03-20 1982-03-15 Filaments et fibres fixés en polyacrylonitrile, et procédé pour leur fabrication Expired EP0061117B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82102086T ATE14757T1 (de) 1981-03-20 1982-03-15 Fixierte polyacrylnitrilfaeden und -fasern sowie verfahren zu ihrer herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1918/81 1981-03-20
CH1918/81A CH647271A5 (de) 1981-03-20 1981-03-20 Fixierte faeden und fasern aus acrylnitrilhomo- oder -copolymeren sowie verfahren zu ihrer herstellung.

Publications (3)

Publication Number Publication Date
EP0061117A2 EP0061117A2 (fr) 1982-09-29
EP0061117A3 EP0061117A3 (en) 1983-09-07
EP0061117B1 true EP0061117B1 (fr) 1985-08-07

Family

ID=4221620

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82102086A Expired EP0061117B1 (fr) 1981-03-20 1982-03-15 Filaments et fibres fixés en polyacrylonitrile, et procédé pour leur fabrication

Country Status (13)

Country Link
US (2) US4446206A (fr)
EP (1) EP0061117B1 (fr)
JP (1) JPS57161117A (fr)
AT (1) ATE14757T1 (fr)
BR (1) BR8201530A (fr)
CA (1) CA1171214A (fr)
CH (1) CH647271A5 (fr)
DD (1) DD202187A5 (fr)
DE (1) DE3265153D1 (fr)
DK (1) DK125282A (fr)
IL (1) IL65294A (fr)
NO (1) NO156698C (fr)
ZA (1) ZA821849B (fr)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58120811A (ja) * 1982-01-05 1983-07-18 Toray Ind Inc セメント補強用アクリル系繊維およびその製造法
JPS59199809A (ja) * 1983-04-20 1984-11-13 Japan Exlan Co Ltd 高強力ポリアクリロニトリル系繊維及びその製造法
JPH0672036B2 (ja) * 1983-05-09 1994-09-14 東レ株式会社 セメントスラリー組成物
JPH0711086B2 (ja) * 1983-07-15 1995-02-08 東レ株式会社 高強度、高弾性率アクリル系繊維の製造法
DE3406910A1 (de) * 1984-02-25 1985-09-05 Hoechst Ag, 6230 Frankfurt Monofile und borsten aus homo- oder copolymerisaten des acrylnitrils und verfahren zu ihrer herstellung
JPS616160A (ja) * 1984-06-19 1986-01-11 東レ株式会社 繊維補強水硬性物質
JPS61152811A (ja) * 1984-12-26 1986-07-11 Toray Ind Inc 高強度アクリル系繊維糸条およびその製造法
JPH0764605B2 (ja) * 1985-01-09 1995-07-12 東レ株式会社 補強用アクリル系繊維
JPS61118731U (fr) * 1985-01-14 1986-07-26
JPS6233817A (ja) * 1985-08-05 1987-02-13 Japan Exlan Co Ltd 高強度高弾性率アクリル系繊維の製造法
US5434002A (en) * 1990-06-04 1995-07-18 Korea Institute Of Science And Technology Non-spun, short, acrylic polymer, fibers
EP0554775A2 (fr) * 1992-02-01 1993-08-11 Hoechst Aktiengesellschaft Fils, fils retardus ou tissus post-étirés à base de fibres discontinues, procédé pour leur fabrication et matériaux composites fabriqués à partir de ceux-ci
EP0645479A1 (fr) * 1993-09-24 1995-03-29 Hoechst Aktiengesellschaft Fibres de polyacrylonitrile ayant une haute tenacité et un haut module, procédé de leur préparation et leur utilisation
SG73992A1 (en) * 1995-12-18 2000-07-18 Standard Oil Co Melt spun acrylonitrile olefinically unsaturated fibers and a process to make fibers
DE19651440A1 (de) 1996-12-11 1998-06-18 Hoechst Ag Hochfeste Polyacrylnitrilfasern hohen Moduls, Verfahren zu deren Herstellung und deren Verwendung
JP4911334B2 (ja) * 2001-08-03 2012-04-04 日本エクスラン工業株式会社 湿式摩擦材用繊維基材
DE102009019120A1 (de) * 2009-04-29 2010-11-04 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Formkörper aus Polyacrylnitril und Verfahren zu deren Herstellung
JP5700240B2 (ja) * 2010-09-29 2015-04-15 三菱レイヨン株式会社 アクリル繊維紙およびその製造方法
EP2647745A4 (fr) * 2010-11-30 2014-06-11 Toray Industries Procédé de fabrication de fibres de polyacrylonitrile et procédé de fabrication de fibres de carbone

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3846833A (en) * 1970-04-14 1974-11-05 Celanese Corp Acrylic filaments which are particularly suited for thermal conversion to carbon filaments
US3984601A (en) * 1971-10-14 1976-10-05 E. I. Du Pont De Nemours And Company Acrylonitrile polymer filaments
US3814739A (en) * 1971-12-27 1974-06-04 Toray Industries Method of manufacturing fibers and films from an acrylonitrile copolymer
DE2658916A1 (de) * 1976-12-24 1978-07-06 Bayer Ag Polyacrylnitril-filamentgarne
JPS5473922A (en) * 1977-11-16 1979-06-13 Japan Exlan Co Ltd Production of pilling-resistant acrylic synthetic fiber
GB2018188A (en) * 1978-04-06 1979-10-17 American Cyanamid Co Wet spinning process for acrylonitrile polymer fiber
US4331732A (en) * 1978-05-24 1982-05-25 Monsanto Company Acrylic fibers having improved moisture transport properties
JPS54160820A (en) * 1978-06-05 1979-12-19 Mitsubishi Rayon Co Ltd Production of acrylonitrile fiber
DE2922667A1 (de) * 1979-06-02 1980-12-11 Hoechst Ag Faeden und fasern aus acrylnitril- copolymer-mischungen sowie verfahren zu ihrer herstellung
DE3027844A1 (de) * 1980-07-23 1982-02-18 Hoechst Ag, 6000 Frankfurt Hochmodul-polyacrylnitrilfaeden und -fasern sowie verfahren zu ihrer herstellung
DE3105360C2 (de) * 1981-02-13 1991-07-18 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung hochfester Fäden aus Polyacrylnitril

Also Published As

Publication number Publication date
ZA821849B (en) 1983-02-23
NO820916L (no) 1982-09-21
ATE14757T1 (de) 1985-08-15
NO156698C (no) 1987-11-04
EP0061117A2 (fr) 1982-09-29
CA1171214A (fr) 1984-07-24
DD202187A5 (de) 1983-08-31
EP0061117A3 (en) 1983-09-07
CH647271A5 (de) 1985-01-15
IL65294A (en) 1986-01-31
DE3265153D1 (en) 1985-09-12
DK125282A (da) 1982-09-21
NO156698B (no) 1987-07-27
US4446206A (en) 1984-05-01
US4536363A (en) 1985-08-20
BR8201530A (pt) 1983-02-08
IL65294A0 (en) 1982-05-31
JPS57161117A (en) 1982-10-04

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