FR2866904A1 - PROCESS FOR PRODUCING RETICULATED POLYACRYLATE FIBERS - Google Patents
PROCESS FOR PRODUCING RETICULATED POLYACRYLATE FIBERS Download PDFInfo
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- FR2866904A1 FR2866904A1 FR0401962A FR0401962A FR2866904A1 FR 2866904 A1 FR2866904 A1 FR 2866904A1 FR 0401962 A FR0401962 A FR 0401962A FR 0401962 A FR0401962 A FR 0401962A FR 2866904 A1 FR2866904 A1 FR 2866904A1
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- 239000000835 fiber Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 22
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 238000004448 titration Methods 0.000 claims abstract description 16
- 238000004132 cross linking Methods 0.000 claims abstract description 12
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920002972 Acrylic fiber Polymers 0.000 claims abstract description 9
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
- 230000009970 fire resistant effect Effects 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004246 zinc acetate Substances 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 34
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- 238000004043 dyeing Methods 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 3
- 230000000295 complement effect Effects 0.000 claims description 2
- VBYZSBGMSZOOAP-UHFFFAOYSA-N molecular hydrogen hydrate Chemical compound O.[H][H] VBYZSBGMSZOOAP-UHFFFAOYSA-N 0.000 abstract 1
- 238000009987 spinning Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- -1 antistatic Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012487 rinsing solution Substances 0.000 description 1
- 239000008237 rinsing water Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Classifications
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- 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
Landscapes
- 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
Le procédé concerne la fabrication de fibres non feu de polyacrylate réticulé. 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, notamment d'hydrate d'hydrogène , à une température comprise entre 100° et 120°C, de préférence de l'ordre de 105°C,- une deuxième étape , dite d'hydrolyse , par une solution de soude,- une troisième étape , dite de neutralisation , par une solution acide , notamment acide sulfurique , et ,- une quatrième étape par une solution d'un sel métallique , notamment d'acétate de zinc.Les conditions opératoires sont telles que le titrage des fibres traitées est d'au moins 1,5 fois, de préférence de 1,8 à 2,6 fois , le titrage des fibres de départ.Les fibres non feu de polyacrylate réticulé , obtenues par le procédé,ont une ténacité qui peut être supérieure à 15 cN/tex et un allongement qui peut être supérieur à 30%.The process relates to the manufacture of crosslinked polyacrylate fire-resistant fibers. It 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, in particular hydrogen hydrate, with a temperature of between 100 ° and 120 ° C., preferably of the order of 105 ° C., a second step, referred to as hydrolysis, by a sodium hydroxide solution, and a third step, called neutralization step, by a solution. acid, especially sulfuric acid, and a fourth step with a solution of a metal salt, in particular zinc acetate. The operating conditions are such that the titration of the treated fibers is at least 1.5 times, The crosslinked polyacrylate fibers obtained by the process have a toughness which may be greater than 15 cN / tex and an elongation which may be greater than 1.8 to 2.6 times. at 30%.
Description
PROCEDE DE FABRICATION DE FIBRES DE POLYACRYLATE RETICULEPROCESS FOR PRODUCING RETICULATED POLYACRYLATE FIBERS
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 chemical inertness with respect to a large number of reagents and, on the other hand, an excellent resistance to heat. More specifically, it relates to a process for producing 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-fighting properties 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 prevents 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 FR2.602.429. Such polyacrylate fibers have been used in the production of a fire-resistant textile barrier, in particular by the document 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 proposed polyacrylate fibers are necessarily in the form of padded or needle-punched sheets, of the non-woven type, since their technical characteristics do not allow them to be spun by conventional techniques. 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 manufacture 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, there are reported polyacrylate fibers successfully used 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 as 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 copolymère réticulé d'acide acrylique et d'acrylamide. The object of the present invention is to provide a process for producing polyacrylate fibers which is not based on a crosslinked copolymer of acrylic acid and acrylamide.
2866904 2 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 provide a method of manufacturing 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 a first step, called a crosslinking rinse, with a solution based on hydrazine at a temperature between 100 and 120 C, a second step, called hydrolysis, with a sodium hydroxide solution, a third step, called neutralization step, with an acidic 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 treated fibers 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 mechanical properties and capable of being 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, the shrinkage that occurs especially during the second hydrolysis step and also the weight gain due to the crosslinking during the first step and to fixing the zinc ion during 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.... The acrylic fiber cable which is treated according to the various steps mentioned above is a standard cable, that is to say a cable which has not undergone previous transformations and which is conventionally used for the conventional uses of acrylic fibers, by 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 an embodiment variation, the hydrazine-based solution that is used in the first crosslinking step is a hydrazine hydrate solution and the corresponding step has a duration of the order of three hundred and 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 sodium hydroxide solution which is used in the second hydrolysis step is a 4% sodium hydroxide solution and the corresponding step has a duration of about one hundred and twenty minutes at a 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 which is used in the third neutralization step is a 5% sulfuric acid solution and the corresponding third stage has a duration of the order of thirty minutes at a temperature of 1%. 60 C order.
Dans une variante de réalisation, la solution de sel métallique qui est mise 10 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 in the fourth step is a zinc acetate solution containing 6% zinc by weight based on 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 about 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 crosslinked polyacrylate fiber tow which is obtained according to the process of the invention is pink in color, being a zinc salt solution in 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 performing a complementary dyeing step, in particular from metalliferous dye, this step being interposed 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 of the order of 1.8 to 2.6 times the titration of the starting fibers.
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 tenacity of greater than 15 cN / tex and an elongation greater than 30%, which makes them particularly suitable for being converted into yarns by techniques conventional spinning.
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. With regard to the thermal properties of these fibers, they have on average a thermal conductivity of 45 mW / m C, an average heating value of 4500 Kcal / kg and a mean temperature of auto-flammability (at 100% oxygen ) of 435 C.
2866904 4 La présente invention sera mieux comprise à la lecture de la description qui va être faite d'un exemple de fabrication de fibres nonfeu 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 given of an example of production of nonfeu fibers of crosslinked polyacrylate implementing four steps successively of crosslinking, hydrolysis, neutralization and dyeing action. 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 cable of acrylic fibers 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 which makes it possible to transform this cable of acrylic fibers into cross-linked polyacrylate fire-resistant fibers is carried out in a conventional dyeing unit.
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; it is compressed to obtain a uniformity of the desired density, then the 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 solution of hydrazine hydrate at 10% at a temperature of 20 ° C. The temperature of the solution is brought gradually to 105 ° C. where it is maintained for about three hours. . The solution is then cooled and emptied from the autoclave. After this first crosslinking step, a rinsing with hot water takes place to remove the remaining hydrazine hydrate solution that has not crosslinked. 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 4% sodium hydroxide solution. 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, a hot rinse is performed so as to remove the remainder of sodium hydroxide solution which has not reacted during the hydrolysis step.
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 2866904 5 éliminer le reliquat d'acide sulfurique qui n'aurait pas été utilisé pour la neutralisation. In the third neutralization step, the autoclave is filled with a 5% sulfuric acid solution. This solution is brought to a temperature of 60 C which is maintained for about thirty minutes, before being removed from the autoclave. After this third step, a hot rinse is performed to remove the remaining sulfuric acid which has not been used for the 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 a solution of zinc acetate and acetic acid. The concentration of this solution is determined so that the amount by weight of zinc is of the order of 6% relative to the weight of cable introduced into the autoclave. This solution is brought to a temperature of about 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 that may include finishing compounds, including antistatic, softening.
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, De manière générale, on cherche à ce que, lors de la première étape, la réticulation soit la plus complète possible. The conditions given above are as a non-exhaustive example, to be adapted according to the starting material and the technical characteristics which are sought for the final product. In general, it is sought that, when the first step, 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 treated fiber into a conventional solvent of acrylic fibers under conditions such that the untreated acrylic fibers are totally dissolved and finding that it is the weight loss for the treated fibers. . If this weight loss 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 being 2.2 dtex and the final titration being 4.87 dtex, the weight loss found during the test 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 carbonise without melting, do not shrink, do not emit toxic smoke, are very rich in oxygen and have a remarkable chemical inertia to a large number of reagents.
2866904 6 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. 2866904 6 They are particularly intended for the field of fire protection, for the realization of thermal barriers, protective clothing, 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 may be used as fibers, especially in nonwovens 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 converted into yarns according to conventional spinning techniques, in pure or in a mixture for the production of woven or knitted articles for protection against fire.
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 fibers obtained was 2.29 dtex and had a tenacity of 16.6 cN / tex and an elongation of 37.5% with an initial modulus 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 about 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 / cm3 and their Limit Oxygen Index (L.O.I.) 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 have no shrinkage with boiling water, can undergo thermal shocks up to 300 C and have a very good resistance to both acids and bases, being 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 subjected twenty four hours at a temperature of 200 C.
2866904 72866904 7
Claims (10)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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FR0401962A FR2866904A1 (en) | 2004-02-26 | 2004-02-26 | PROCESS FOR PRODUCING RETICULATED POLYACRYLATE FIBERS |
EP05370002A EP1568818A1 (en) | 2004-02-26 | 2005-02-24 | Method for manufacturing cross-linked polyacrylonitrile fibers |
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FR0401962A FR2866904A1 (en) | 2004-02-26 | 2004-02-26 | PROCESS FOR PRODUCING RETICULATED POLYACRYLATE FIBERS |
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FR0401962A Withdrawn FR2866904A1 (en) | 2004-02-26 | 2004-02-26 | PROCESS FOR PRODUCING RETICULATED POLYACRYLATE FIBERS |
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Cited By (1)
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WO2023195951A1 (en) * | 2022-04-04 | 2023-10-12 | Aksa Akrilik Kimya Sanayii Anonim Sirketi | Improved polyacrylate fiber production process and their use |
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ITMI20070807A1 (en) * | 2007-04-19 | 2008-10-20 | Montefibre Spa | PROCEDURE FOR THE PRODUCTION OF FIREPROOF AND LOW EMISSION FIBER POLYAMILATE FIBERS UNIFORMLY TINTED AND ACRYLIC FIBERS SO OBTAINED |
JP5056358B2 (en) * | 2007-11-02 | 2012-10-24 | 日本エクスラン工業株式会社 | Dyeable cross-linked acrylate fiber, method for producing the same, and dyed cross-linked acrylate fiber obtained by dyeing the fiber |
WO2023219590A1 (en) * | 2022-05-11 | 2023-11-16 | Aksa Akrilik Kimya Sanayii Anonim Sirketi | Fire proof and flame retardant polyacrylate fiber and production method thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2719461A1 (en) * | 1977-04-30 | 1978-11-02 | Bayer Ag | Halogen-free flame-retardant acrylonitrile! polymers - prepd. by treatment with hydrazine and metal salt solns. |
GB2346569A (en) * | 1998-12-30 | 2000-08-16 | Univ Montfort | Method for the production of fibrous catalysts |
JP2001146678A (en) * | 1999-11-24 | 2001-05-29 | Toho Rayon Co Ltd | Moisture-absorbing and releasing fiber, its production and mix-spun fiber |
JP2001159073A (en) * | 1999-11-29 | 2001-06-12 | Toho Rayon Co Ltd | Antimicrobial acrylic moisture-absorbing or releasing fiber, method for producing the same, and blended yarn |
EP1277877A1 (en) * | 2000-09-18 | 2003-01-22 | Sakaren Co., Ltd | Method of treating textile product containing highly crosslinked acrylic polymer fiber before dyeing, method of dyeing the textile product, textile product treated before dyeing, and textile product |
-
2004
- 2004-02-26 FR FR0401962A patent/FR2866904A1/en not_active Withdrawn
-
2005
- 2005-02-24 EP EP05370002A patent/EP1568818A1/en not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2719461A1 (en) * | 1977-04-30 | 1978-11-02 | Bayer Ag | Halogen-free flame-retardant acrylonitrile! polymers - prepd. by treatment with hydrazine and metal salt solns. |
GB2346569A (en) * | 1998-12-30 | 2000-08-16 | Univ Montfort | Method for the production of fibrous catalysts |
JP2001146678A (en) * | 1999-11-24 | 2001-05-29 | Toho Rayon Co Ltd | Moisture-absorbing and releasing fiber, its production and mix-spun fiber |
JP2001159073A (en) * | 1999-11-29 | 2001-06-12 | Toho Rayon Co Ltd | Antimicrobial acrylic moisture-absorbing or releasing fiber, method for producing the same, and blended yarn |
EP1277877A1 (en) * | 2000-09-18 | 2003-01-22 | Sakaren Co., Ltd | Method of treating textile product containing highly crosslinked acrylic polymer fiber before dyeing, method of dyeing the textile product, textile product treated before dyeing, and textile product |
Non-Patent Citations (2)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 2000, no. 22 9 March 2001 (2001-03-09) * |
PATENT ABSTRACTS OF JAPAN vol. 2000, no. 23 10 February 2001 (2001-02-10) * |
Cited By (1)
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---|---|---|---|---|
WO2023195951A1 (en) * | 2022-04-04 | 2023-10-12 | Aksa Akrilik Kimya Sanayii Anonim Sirketi | Improved polyacrylate fiber production process and their use |
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