EP1568818A1 - Method for manufacturing cross-linked polyacrylonitrile fibers - Google Patents

Method for manufacturing cross-linked polyacrylonitrile fibers Download PDF

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Publication number
EP1568818A1
EP1568818A1 EP05370002A EP05370002A EP1568818A1 EP 1568818 A1 EP1568818 A1 EP 1568818A1 EP 05370002 A EP05370002 A EP 05370002A EP 05370002 A EP05370002 A EP 05370002A EP 1568818 A1 EP1568818 A1 EP 1568818A1
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Prior art keywords
solution
fibers
order
process according
stage
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German (de)
French (fr)
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Juan Batlle Marti
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
    • D06M11/40—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table combined with, or in absence of, mechanical tension, e.g. slack mercerising
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/63—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with hydroxylamine or hydrazine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D06M13/338—Organic hydrazines; Hydrazinium compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process

Definitions

  • the present invention relates to the field of technical textiles and more particularly, textiles which have, on the one hand, a remarkable inertia a large number of reagents and, on the other hand, excellent resistance to heat. It relates more specifically to a manufacturing process of cross-linked polyacrylate fire-resistant fibers.
  • Polyacrylate fibers are known for their excellent fire characteristics and their resistance not only to the action of heat but also to that of chemicals.
  • Such polyacrylate fibers have been used in the production a fireproof textile barrier including FR-2.602.429.
  • Such fibers are proposed by the company COURTAULDS under the name INIDEX®.
  • the polyacrylate fibers proposed are necessarily in the form of wadded tablecloths or needles, of non-woven type, since their technical characteristics are not not allow them to be spun by conventional techniques of spinning.
  • the aim of the present invention is to propose a method of manufacture of polyacrylate fibers that is not based on a co-polymer crosslinked acrylic acid and acrylamide.
  • the second object of the present invention is to propose a method of manufacture of polyacrylate fibers whose technical characteristics are such that they can be spun by conventional spinning techniques.
  • the operating conditions are such that the titration of the fibers treated is at least 1.5 times the titration of the starting fibers.
  • the temperature is of the order of 105 ° C.
  • Acrylic fiber cable that is processed according to the different stages mentioned above is a standard cable, ie a cable that has not been subjected to prior transformations and which is conventionally implemented for the conventional uses of acrylic fibers, for example in clothing, furniture ....
  • the hydrazine-based solution which is implementation in the first crosslinking step is a hydrate solution of hydrazine and the corresponding stage has a duration of the order of three hundred sixty minutes at the determined temperature, between 100 and 120 ° C and preferably of the order of 105 ° C.
  • the soda solution that is used in the second hydrolysis step is a 4% sodium hydroxide solution and the corresponding step has a duration of the order of one hundred and twenty minutes to one temperature of the order of 90 ° C.
  • the acid solution that is used in the third neutralization step is a 5% sulfuric acid solution and the corresponding third step has a duration of the order of thirty minutes to a temperature of the order of 60 ° C.
  • the metal salt solution which is used implemented in the fourth step is a solution of zinc acetate 6% zinc by weight relative to the weight of fibers.
  • this fourth step has a duration of the order of sixty minutes at a temperature of the order of 100 ° C.
  • the cross-linked polyacrylate fiber cable which is obtained by the process of the invention is pink, being a solution of zinc salt during the fourth step.
  • the operating conditions are determined so that the Titration of the treated fibers is in the order of 1.8 to 2.6 times the titration of the fibers of departure.
  • the crosslinked polyacrylate fibers obtained by the above process, may have a toughness greater than 15 cN / tex and an elongation greater than 30%, which makes them particularly suitable to be transformed into yarns by conventional spinning techniques.
  • these fibers have average thermal conductivity of 45 mW / m ° C, a calorific value average of 4500 Kcal / kg and an average temperature of auto-flammability (at 100% oxygen) at 435 ° C.
  • the starting material is in the form of a fiber rope acrylic products as proposed on the market, for example under the name LEACRYL®, DRALON®, COURTELLE® ....
  • the cable is loaded in the holders; he is compressed to get uniformity of the desired density, then the material carriers are introduced into the autoclave.
  • the autoclave is filled with a hydrazine hydrate solution at 10% at a temperature of 20 ° C. Temperature the solution is gradually brought to 105 ° C where it is kept about three hours. The solution is then cooled and emptied from the autoclave. After this first crosslinking step, involves rinsing with hot water to remove leftover hydrazine hydrate solution that would not have reticle. The autoclave is then emptied of the rinsing water.
  • the autoclave is filled with a solution 4% sodium hydroxide. This solution is brought to a temperature of the order of 95 ° C and is maintained at this temperature for a period of the order of two hours. It is then cooled and removed from the autoclave. After this second step involves a hot rinse so as to eliminate the leftover sodium hydroxide solution that has not reacted during the step hydrolysis.
  • the autoclave is filled with a solution of sulfuric acid at 5%. This solution is brought to a temperature of 60 ° C which is maintained for about thirty minutes, before being evacuated of the autoclave.
  • a hot rinse remove the remaining sulfuric acid that has not been used for neutralization.
  • the autoclave is filled with an acetate solution of zinc and acetic acid.
  • concentration of this solution is determined by so that the amount by weight of zinc is of the order of 6% by weight of cable introduced into the autoclave.
  • This solution is brought to a temperature of the order of 100 ° C, which temperature is maintained for about an hour before being cooled and removed from the autoclave.
  • rinsing with a rinsing solution which may include finishing compounds, especially antistatic, softeners.
  • the initial titration is 2.2 dtex and the final titre being 4.87 dtex, the weight loss observed during the test was was 1.43%.
  • the resulting fibers have excellent heat resistance; they char without melting, do not shrink, do not emit toxic smoke, are very rich in oxygen and have a remarkable chemical inertness to a large number of reagents.
  • the fibers had a titration of 1.3 dtex, the titration of the obtained fibers was 2.29 dtex and had a tenacity of 16.6 cN / tex and an elongation of 37.5% with a initial module of 449 cN / tex.
  • the treated fibers have a humidity recovery of about 12% with an absorption rate of around 47%.
  • the fibers thus treated do not exhibit any shrinkage with boiling water, can experience thermal shock up to 300 ° C and have a very good resistance to both acids and bases, not soluble in any of the usual solvents.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Artificial Filaments (AREA)

Abstract

A method of manufacturing fire-proof fibers of crosslinked polyacrylate by treating in an autoclave a standard cable of acrylic fibers with hydrazine, sodium hydroxide, acid and metal salt solutions interspersed by rinsings in such a way that the titre of the treated fiber is 1.5 times that of the starting fibers. In the first, crosslinking, step a hydrazine based solution is used at 100-120[deg]C. In the second, hydrolysis, step a solution of NaOH is used. In the third, neutralization, step an acid solution is used. In the fourth step a solution of a salt of a metal, especially zinc is used. An independent claim is included for fibers produced by the method with a strength 15cN/tex and elongation greater than 30%.

Description

La présente invention concerne le domaine des textiles techniques et, plus particulièrement, des textiles qui présentent, d'une part, une remarquable inertie chimique vis à vis d'un grand nombre de réactifs et, d'autre part, une excellente résistance à la chaleur. Elle concerne plus précisément un procédé de fabrication de fibres non feu de polyacrylate réticulé.The present invention relates to the field of technical textiles and more particularly, textiles which have, on the one hand, a remarkable inertia a large number of reagents and, on the other hand, excellent resistance to heat. It relates more specifically to a manufacturing process of cross-linked polyacrylate fire-resistant fibers.

Les fibres de polyacrylate sont connues pour leurs excellentes caractéristiques anti-feu et leur résistance non seulement à l'action de la chaleur mais également à celle des produits chimiques.Polyacrylate fibers are known for their excellent fire characteristics and their resistance not only to the action of heat but also to that of chemicals.

En cas d'incendie, leur dégradation est minime, ce qui évite la formation de fumée et de gaz.In case of fire, their degradation is minimal, which avoids the formation of smoke and gas.

De telles fibres de polyacrylate ont été mises en oeuvre dans la réalisation d'une barrière textile anti-feu notamment par le document FR-2.602.429.Such polyacrylate fibers have been used in the production a fireproof textile barrier including FR-2.602.429.

De telles fibres sont proposées par la société COURTAULDS sous l'appellation INIDEX®.Such fibers are proposed by the company COURTAULDS under the name INIDEX®.

Comme stipulé dans ce document FR-2.602.429, les fibres de polyacrylate proposées se présentent nécessairement sous forme de nappes ouatinées ou aiguilletées, de type non tissé, puisque leurs caractéristiques techniques ne permettent pas qu'elles puissent être filées par les techniques classiques de filature.As stipulated in this document FR-2.602.429, the polyacrylate fibers proposed are necessarily in the form of wadded tablecloths or needles, of non-woven type, since their technical characteristics are not not allow them to be spun by conventional techniques of spinning.

La société COURTAULDS n'a pas divulgué le procédé qu'elle a mis en oeuvre pour fabriquer les fibres INIDEX®.The company COURTAULDS did not disclose the process it has implemented to make INIDEX® fibers.

Dans la littérature, il est fait état de fibres de polyacrylate utilisées avec succès dans les étoffes résistant à la flamme, lesdites fibres étant basées sur un co-polymère réticulé d'acide acrylique et d'acrylamide dans lequel certains des groupes acide carboxylique sont traités avec des ions métalliques divalents tels que des ions zinc ou calcium.In the literature, reference is made to polyacrylate fibers used with success in flame resistant fabrics, said fibers being based on a crosslinked co-polymer of acrylic acid and acrylamide in which some of the carboxylic acid groups are treated with divalent metal ions such than zinc or calcium ions.

Le but visé par la présente invention est de proposer un procédé de fabrication de fibres de polyacrylate qui ne soit pas à base d'un co-polymère réticulé d'acide acrylique et d'acrylamide. The aim of the present invention is to propose a method of manufacture of polyacrylate fibers that is not based on a co-polymer crosslinked acrylic acid and acrylamide.

Le second but de la présente invention est de proposer un procédé de fabrication de fibres de polyacrylate dont les caractéristiques techniques sont telles qu'elles puissent être filées par les techniques classiques de filature.The second object of the present invention is to propose a method of manufacture of polyacrylate fibers whose technical characteristics are such that they can be spun by conventional spinning techniques.

Chacun de ces buts est parfaitement atteint par le procédé de la présente invention qui consiste à traiter, en autoclave, un câble de fibres acryliques standard selon les étapes suivantes, entrecoupées de rinçage :

  • une première étape, dite de réticulation, par une solution à base d'hydrazine à une température comprise entre 100 et 120°C,
  • une deuxième étape, dite d'hydrolyse, par une solution de soude,
  • une troisième étape, dite de neutralisation, par une solution acide et,
  • une quatrième étape par une solution d'un sel métallique, notamment de zinc.
Each of these objects is perfectly achieved by the method of the present invention which consists in treating, in an autoclave, a standard acrylic fiber cable according to the following steps, interspersed with rinsing:
  • a first step, called crosslinking, with a solution based on hydrazine at a temperature of between 100 and 120 ° C.
  • a second step, called hydrolysis, with a sodium hydroxide solution,
  • a third stage, called neutralization stage, with an acid solution and,
  • a fourth step with a solution of a metal salt, especially zinc.

De plus, les conditions opératoires sont telles que le titrage des fibres traitées est d'au moins 1,5 fois le titrage des fibres de départ.In addition, the operating conditions are such that the titration of the fibers treated is at least 1.5 times the titration of the starting fibers.

En-dessous de 100°C, la réticulation n'est pas satisfaisante. Au-dessus de 120°C, il se produit une dégradation des fibres qui est rédhibitoire.Below 100 ° C, the crosslinking is not satisfactory. Above 120 ° C, there is a degradation of the fibers which is unacceptable.

De préférence, pour obtenir des fibres ayant de bonnes propriétés mécaniques et aptes à être filées , la température est de l'ordre de 105°C.Preferably, to obtain fibers having good properties mechanical and able to be spun, the temperature is of the order of 105 ° C.

Il est à noter que l'évolution de ce titrage est due à plusieurs facteurs, en particulier, le retrait qui intervient notamment lors de la deuxième étape d'hydrolyse et également la prise de poids due à la réticulation lors de la première étape et à la fixation de l'ion zinc lors de la quatrième étape.It should be noted that the evolution of this titration is due to several factors, in particular particular, the withdrawal which occurs especially during the second stage hydrolysis and also the weight gain due to the crosslinking during the first step and fixing the zinc ion in the fourth step.

Le câble de fibres acryliques qui est traité selon les différentes étapes précitées est un câble standard, c'est à dire un câble qui n'a pas subi de transformations préalables et qui est classiquement mis en oeuvre pour les utilisations conventionnelles des fibres acryliques, par exemple dans l'habillement, l'ameublement ....Acrylic fiber cable that is processed according to the different stages mentioned above is a standard cable, ie a cable that has not been subjected to prior transformations and which is conventionally implemented for the conventional uses of acrylic fibers, for example in clothing, furniture ....

Dans une variation de réalisation, la solution à base d'hydrazine qui est mise en oeuvre dans la première étape de réticulation est une solution d'hydrate d'hydrazine et l'étape correspondante a une durée de l'ordre de trois cent soixante minutes à la température déterminée , comprise entre 100 et 120°C et de préférence de l'ordre de 105°C. In a variation of embodiment, the hydrazine-based solution which is implementation in the first crosslinking step is a hydrate solution of hydrazine and the corresponding stage has a duration of the order of three hundred sixty minutes at the determined temperature, between 100 and 120 ° C and preferably of the order of 105 ° C.

Dans une variante de réalisation, la solution de soude qui est mise en oeuvre dans la deuxième étape d'hydrolyse est une solution de soude à 4% et l'étape correspondante a une durée de l'ordre de cent vingt minutes à une température de l'ordre de 90°C.In an alternative embodiment, the soda solution that is used in the second hydrolysis step is a 4% sodium hydroxide solution and the corresponding step has a duration of the order of one hundred and twenty minutes to one temperature of the order of 90 ° C.

Dans une variante de réalisation, la solution acide qui est mise en oeuvre dans la troisième étape de neutralisation est une solution d'acide sulfurique à 5% et la troisième étape correspondante a une durée de l'ordre de trente minutes à une température de l'ordre de 60°C.In an alternative embodiment, the acid solution that is used in the third neutralization step is a 5% sulfuric acid solution and the corresponding third step has a duration of the order of thirty minutes to a temperature of the order of 60 ° C.

Dans une variante de réalisation, la solution de sel métallique qui est mise en oeuvre dans la quatrième étape est une solution d'acétate de zinc à 6% de zinc en poids par rapport au poids de fibres.In an alternative embodiment, the metal salt solution which is used implemented in the fourth step is a solution of zinc acetate 6% zinc by weight relative to the weight of fibers.

Avantageusement, dans ce cas, cette quatrième étape a une durée de l'ordre de soixante minutes à une température de l'ordre de 100°C.Advantageously, in this case, this fourth step has a duration of the order of sixty minutes at a temperature of the order of 100 ° C.

Le câble de fibres de polyacrylate réticulé qui est obtenu selon le procédé de l'invention est de couleur rose, s'agissant d'une solution de sel de zinc lors de la quatrième étape.The cross-linked polyacrylate fiber cable which is obtained by the process of the invention is pink, being a solution of zinc salt during the fourth step.

Il est cependant possible de modifier ce coloris en procédant à une étape complémentaire de teinture, notamment à partir de colorant métallifère, cette étape étant intercalée entre la troisième étape de neutralisation et la quatrième étape.However, it is possible to modify this color by proceeding to a step complementary dyeing, especially from metalliferous dye, this step being interspersed between the third neutralization step and the fourth step.

De préférence, les conditions opératoires sont déterminées en sorte que le titrage des fibres traitées est de l'ordre de 1,8 à 2,6 fois le titrage des fibres de départ.Preferably, the operating conditions are determined so that the Titration of the treated fibers is in the order of 1.8 to 2.6 times the titration of the fibers of departure.

Selon les conditions opératoires retenues, les fibres de polyacrylate réticulé, obtenues par le procédé précité, peuvent avoir une tenacité supérieure à 15 cN/tex et un allongement supérieur à 30%, ce qui les rend particulièrement aptes à être transformées en fils par des techniques conventionnelles de filature.Depending on the operating conditions used, the crosslinked polyacrylate fibers, obtained by the above process, may have a toughness greater than 15 cN / tex and an elongation greater than 30%, which makes them particularly suitable to be transformed into yarns by conventional spinning techniques.

En ce qui concerne les propriétés thermiques de ces fibres, elles ont en moyenne une conductibilité thermique de 45 mW/m°C, un pouvoir calorifique moyen de 4500 Kcal/kg et une température moyenne d'auto-inflammabilité (à 100% d'oxygène) de 435°C. As regards the thermal properties of these fibers, they have average thermal conductivity of 45 mW / m ° C, a calorific value average of 4500 Kcal / kg and an average temperature of auto-flammability (at 100% oxygen) at 435 ° C.

La présente invention sera mieux comprise à la lecture de la description qui va être faite d'un exemple de fabrication de fibres non-feu de polyacrylate réticulé mettant en oeuvre quatre étapes successivement de réticulation, d'hydrolyse, de neutralisation et d'action d'une solution d'un sel de zinc.The present invention will be better understood on reading the description which will be made of an example of manufacture of cross-linked polyacrylate non-fire fibers implementing four successively stages of crosslinking, hydrolysis, neutralization and action of a solution of a zinc salt.

La matière de départ se présente sous la forme d'un câble de fibres acryliques tel que proposé sur le marché, par exemple sous la dénomination LEACRYL®, DRALON®, COURTELLE® ....The starting material is in the form of a fiber rope acrylic products as proposed on the market, for example under the name LEACRYL®, DRALON®, COURTELLE® ....

Le traitement qui permet de transformer ce câble de fibres acryliques en fibres non-feu de polyacrylate réticulé est réalisé dans une unité de teinture conventionnelle.The treatment that makes it possible to transform this cable of acrylic fibers into Cross-linked polyacrylate non-fire fibers are made in a dyeing unit conventional.

Le câble est chargé dans les porte-matières ; il est comprimé pour obtenir une uniformité de la densité désirée, puis les porte-matières sont introduits dans l'autoclave.The cable is loaded in the holders; he is compressed to get uniformity of the desired density, then the material carriers are introduced into the autoclave.

Pour la première étape de réticulation, l'autoclave est remplie avec une solution d'hydrate d'hydrazine à 10% à une température de 20°C. La température de la solution est portée progressivement à 105°C où elle est maintenue pendant environ trois heures. La solution est ensuite refroidie et vidée de l'autoclave. Après cette première étape de réticulation, intervient un rinçage avec de l'eau chaude pour éliminer les reliquats de solution d'hydrate d'hydrazine qui n'aurait pas réticulé. L'autoclave est ensuite vidée de l'eau de rinçage.For the first crosslinking step, the autoclave is filled with a hydrazine hydrate solution at 10% at a temperature of 20 ° C. Temperature the solution is gradually brought to 105 ° C where it is kept about three hours. The solution is then cooled and emptied from the autoclave. After this first crosslinking step, involves rinsing with hot water to remove leftover hydrazine hydrate solution that would not have reticle. The autoclave is then emptied of the rinsing water.

Pour la seconde étape d'hydrolyse, l'autoclave est remplie avec une solution d'hydroxyde de sodium à 4%. Cette solution est portée à une température de l'ordre de 95°C et est maintenue à cette température pendant une durée de l'ordre de deux heures. Elle est ensuite refroidie et évacuée de l'autoclave. Après cette seconde étape, intervient un rinçage à chaud de manière à éliminer le reliquat de solution d'hydroxyde sodium qui n'aurait pas réagi au cours de l'étape d'hydrolyse.For the second hydrolysis step, the autoclave is filled with a solution 4% sodium hydroxide. This solution is brought to a temperature of the order of 95 ° C and is maintained at this temperature for a period of the order of two hours. It is then cooled and removed from the autoclave. After this second step involves a hot rinse so as to eliminate the leftover sodium hydroxide solution that has not reacted during the step hydrolysis.

Lors de la troisième étape de neutralisation, l'autoclave est remplie avec une solution d'acide sulfurique à 5%. Cette solution est portée à une température de 60°C qui est maintenue pendant environ trente minutes, avant d'être évacuée de l'autoclave. Après cette troisième étape, intervient un rinçage à chaud pour éliminer le reliquat d'acide sulfurique qui n'aurait pas été utilisé pour la neutralisation.During the third neutralization step, the autoclave is filled with a solution of sulfuric acid at 5%. This solution is brought to a temperature of 60 ° C which is maintained for about thirty minutes, before being evacuated of the autoclave. After this third step, a hot rinse remove the remaining sulfuric acid that has not been used for neutralization.

Pour la quatrième étape, l'autoclave est remplie d'une solution d'acétate de zinc et d'acide acétique. La concentration de cette solution est déterminée en sorte que la quantité en poids de zinc soit de l'ordre de 6% par rapport au poids de câble introduit dans l'autoclave. Cette solution est portée à une température de l'ordre de 100°C, laquelle température est maintenue pendant environ une heure avant d'être refroidie et évacuée de l'autoclave. Après cette quatrième étape, intervient un rinçage avec une solution de rinçage qui peut comporter des composés de finition, notamment antistatiques, adoucissants.For the fourth step, the autoclave is filled with an acetate solution of zinc and acetic acid. The concentration of this solution is determined by so that the amount by weight of zinc is of the order of 6% by weight of cable introduced into the autoclave. This solution is brought to a temperature of the order of 100 ° C, which temperature is maintained for about an hour before being cooled and removed from the autoclave. After this fourth step, rinsing with a rinsing solution which may include finishing compounds, especially antistatic, softeners.

Les conditions données ci-dessus le sont à titre d'exemple non exhaustif, devant être adaptées en fonction de la matière de départ et des caractéristiques techniques qui sont recherchées pour le produit final.The conditions given above are as a non-exhaustive example, to be adapted according to the starting material and the characteristics techniques that are sought for the final product.

De manière générale, on cherche à ce que, lors de la première étape, la réticulation soit la plus complète possible.In general, it is sought that, during the first stage, the crosslinking is as complete as possible.

On teste l'efficacité de cette réticulation en plongeant un échantillon de fibre traitée dans un solvant habituel des fibres acryliques dans des conditions telles que les fibres acryliques non traitées sont totalement dissoutes et en constatant qu'elle est la perte de poids pour les fibres traitées. Si cette perte de poids est inférieure à 5%, on considère que la première étape de réticulation a été menée dans des conditions satisfaisantes.The effectiveness of this crosslinking is tested by dipping a sample of fiber treated in a usual solvent of acrylic fibers under conditions such as untreated acrylic fibers are totally dissolved and in finding that it is losing weight for processed fiber. If this loss of weight is less than 5%, it is considered that the first crosslinking step has been conducted under satisfactory conditions.

Dans un exemple précis de réalisation, le titrage initial étant de 2,2 dtex et le titrage final étant de 4,87 dtex, la perte de poids constatée au cours du test a été 1,43%.In a specific embodiment, the initial titration is 2.2 dtex and the final titre being 4.87 dtex, the weight loss observed during the test was was 1.43%.

Dans un autre exemple de réalisation, dans lequel le titrage initial était de 17 dtex et le titrage final de 30,63 dtex, la perte de poids constaté était de 3,92%.In another embodiment, in which the initial titration was 17 dtex and the final titration of 30.63 dtex, the weight loss found was 3.92%.

Les fibres obtenues possèdent une excellente résistance à la chaleur ; elles carbonisent sans fondre, ne se rétractent pas, ne dégagent pas de fumée toxique, sont très riches en oxygène et possèdent une remarquable inertie chimique à un grand nombre de réactifs. The resulting fibers have excellent heat resistance; they char without melting, do not shrink, do not emit toxic smoke, are very rich in oxygen and have a remarkable chemical inertness to a large number of reagents.

Elles sont tout particulièrement destinées au domaine de la protection contre le feu, pour la réalisation de barrières thermiques, de vêtements de protection, ou encore de rembourrage.They are particularly aimed at the field of protection against fire, for the realization of thermal barriers, clothing of protection, or padding.

Elles peuvent être utilisées en tant que fibres, notamment dans des non tissés utilisés conformément au document FR-2.602.429 et FR-2.625.441.They can be used as fibers, especially in non woven fabrics used in accordance with document FR-2,602,429 and FR-2,625,441.

Elles peuvent également être transformées en fils selon les techniques de filature conventionnelle, en pur ou en mélange pour la réalisation d'articles tissés ou tricotés de protection contre le feu.They can also be transformed into threads according to the techniques of conventional spinning, pure or blended for making woven articles or knitted fire protection.

Dans un exemple précis de réalisation, dans le câble de départ, les fibres avaient un titrage de 1,3 dtex, le titrage des fibres obtenues était de 2,29 dtex et possédaient une tenacité de 16,6 cN/tex et un allongement de 37,5% avec un module initial de 449 cN/tex.In a specific embodiment, in the starting cable, the fibers had a titration of 1.3 dtex, the titration of the obtained fibers was 2.29 dtex and had a tenacity of 16.6 cN / tex and an elongation of 37.5% with a initial module of 449 cN / tex.

En moyenne les fibres traitées ont une reprise d'humidité de l'ordre de 12% avec un taux d'absorption de l'ordre de 47%.On average, the treated fibers have a humidity recovery of about 12% with an absorption rate of around 47%.

Leur densité est d'environ 1,5 gr/cm3 et leur Indice Limite d'Oxygène (L.O.I.) est de l'ordre de 42%.Their density is about 1.5 gr / cm 3 and their Oxygen Limit Index (LOI) is of the order of 42%.

Les fibres ainsi traitées ne présentent aucune rétraction à l'eau bouillante, peuvent subir des chocs thermiques jusqu'à 300°C et présentent une très bonne résistance à la fois aux acides et aux bases, n'étant solubles dans aucun des solvants habituels.The fibers thus treated do not exhibit any shrinkage with boiling water, can experience thermal shock up to 300 ° C and have a very good resistance to both acids and bases, not soluble in any of the usual solvents.

Elles conservent 100% de leurs propriétés mécaniques lorsqu'elles sont soumises vingt quatre heures à une température de 200°C.They retain 100% of their mechanical properties when they are twenty-four hours at a temperature of 200 ° C.

Claims (10)

Procédé de fabrication de fibres non feu de polyacrylate réticulé caractérisé en ce qu'il consiste à traiter, en autoclave, un câble de fibres acryliques standard selon les étapes suivantes, entrecoupées de rinçage : une première étape, dite de réticulation, par une solution à base d'hydrazine à une température comprise entre 100° et 120°C, une deuxième étape, dite d'hydrolyse, par une solution de soude, une troisième étape, dite de neutralisation, par une solution acide et, une quatrième étape par une solution d'un sel métallique, notamment de zinc, et en ce que les conditions opératoires sont telles que le titrage des fibres traitées est d'au moins 1,5 fois le titrage des fibres de départ.Process for the production of cross-linked polyacrylate fire-resistant fibers, characterized in that it consists in treating, in an autoclave, a cable of standard acrylic fibers according to the following steps, interspersed with rinsing: a first step, called crosslinking, with a solution based on hydrazine at a temperature of between 100 ° and 120 ° C., a second step, called hydrolysis, with a sodium hydroxide solution, a third stage, called neutralization stage, with an acid solution and, a fourth step with a solution of a metal salt, in particular zinc, and in that the operating conditions are such that the titration of the treated fibers is at least 1.5 times the titration of the starting fibers. Procédé selon la revendication 1 caractérisé en ce que la température de la première étape est de l'ordre de 105°C.Process according to Claim 1, characterized in that the temperature of the first stage is of the order of 105 ° C. Procédé selon l'une des revendications 1 et 2, caractérisé en ce que la solution à base d'hydrazine est une solution d'hydrate d'hydrazine et la première étape a une durée de l'ordre de trois cent soixante minutes à une température de l'ordre de 105°C.Process according to one of Claims 1 and 2, characterized in that the hydrazine-based solution is a hydrazine hydrate solution and the first stage has a duration of the order of three hundred and sixty minutes at a temperature of the order of 105 ° C. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que la solution de soude est une solution de soude à 4% et la deuxième étape a une durée de l'ordre de cent vingt minutes à une température de l'ordre de 90°C.Process according to one of Claims 1 to 3, characterized in that the soda solution is a 4% sodium hydroxide solution and the second stage has a duration of the order of one hundred and twenty minutes at a temperature of the order of 90 ° C. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la solution acide est une solution d'acide sulfurique à 5% et la troisième étape a une durée de l'ordre de trente minutes à une température de l'ordre de 60°C.Process according to any one of Claims 1 to 4, characterized in that the acid solution is a 5% sulfuric acid solution and the third stage has a duration of the order of thirty minutes at a temperature of about 60 ° C. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que la solution de sel métallique est une solution d'acétate de zinc à 6% de zinc en poids par rapport au poids de fibres.Process according to any one of Claims 1 to 5, characterized in that the metal salt solution is a solution of zinc acetate containing 6% zinc by weight relative to the weight of fibers. Procédé selon la revendication 6, caractérisé en ce que la quatrième étape a une durée de l'ordre de soixante minutes à une température de l'ordre de 100°C. Process according to Claim 6, characterized in that the fourth step has a duration of the order of sixty minutes at a temperature of the order of 100 ° C. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce qu'il comporte une étape complémentaire de teinture, notamment à partir de colorant métallifère, intercalée entre la troisième étape de neutralisation et la quatrième étape.Process according to any one of Claims 1 to 7, characterized in that it comprises a complementary dyeing step, in particular starting from metalliferous dye, interposed between the third neutralization stage and the fourth stage. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que les conditions opératoires sont déterminées en sorte que le titrage des fibres traitées est de l'ordre de 1,8 à 2,6 fois le titrage des fibres de départ.Process according to any one of Claims 1 to 8, characterized in that the operating conditions are determined so that the titration of the treated fibers is of the order of 1.8 to 2.6 times the titration of the starting fibers. Fibres non feu de polyacrylate réticulé, obtenues par le procédé selon l'une quelconque des revendications 1 à 9, ayant une tenacité supérieure à 15 cN/tex et un allongement supérieur à 30%.Cross-linked polyacrylate fire-resistant fibers obtained by the process according to any one of claims 1 to 9 having a toughness greater than 15 cN / tex and an elongation greater than 30%.
EP05370002A 2004-02-26 2005-02-24 Method for manufacturing cross-linked polyacrylonitrile fibers Withdrawn EP1568818A1 (en)

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FR0401962A FR2866904A1 (en) 2004-02-26 2004-02-26 PROCESS FOR PRODUCING RETICULATED POLYACRYLATE FIBERS
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