EP1313779A1 - Method for making acrylonitrile fibres - Google Patents
Method for making acrylonitrile fibresInfo
- Publication number
- EP1313779A1 EP1313779A1 EP01963097A EP01963097A EP1313779A1 EP 1313779 A1 EP1313779 A1 EP 1313779A1 EP 01963097 A EP01963097 A EP 01963097A EP 01963097 A EP01963097 A EP 01963097A EP 1313779 A1 EP1313779 A1 EP 1313779A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acrylonitrile
- alkoxy
- optionally substituted
- halogen
- deab
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/42—Nitriles
- C08F20/44—Acrylonitrile
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—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
- 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
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
Definitions
- the present invention relates to a process for obtaining polymers based on acrylonitrile. More particularly, it relates to a process for manufacturing fibers based on acrylonitrile.
- Acrylonitrile fibers are not only useful as fibers for clothing, but also as a precursor to carbon fibers as well as fabrics for industrial filter media, tent cloth, sailcloth, sewing thread, reinforcing material for cement to replace asbestos, as a filter medium in the form of a membrane or hollow fibers used in the medical field and as a gas-tight film.
- Acrylonitrile-based polymers are understood to be homo and acrylonitrile copolymers, the latter containing at least 70% by weight of acrylonitrile and at least one unsaturated monomer copolymerizable with acrylonitrile, such as (meth) acrylate methyl, ethyl (meth) acrylate, n, iso or t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, acrylic acid, methacrylic acid, itaconic acid , ⁇ -chloro acrylonitrile, 2-hydroxyethylacrylonitrile, hydroxyalkyl (meth) acrylates, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, vinyl bromide, vinyl acetate, vinyl propionate, (meth) acrylamides and their derivatives, sulfonic acid monomers, styrene and allyl alcohols.
- the acrylonitrile copolymers contain at least 85% by weight of acrylonitrile and at least one unsaturated monomer copolymerizable with acrylonitrile.
- This monomer can be hydrophobic or hydrophilic.
- Conventional processes for the industrial manufacture of acrylonitrile-based polymers include the precipitation polymerization process using a redox polymerization catalyst composed of a persulfate and an acid sulfite in an aqueous medium, the polymerization process in homogeneous solution using a solvent such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide, ethylene carbonate and gamma-butyrolactone and the emulsion polymerization process.
- a solvent such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide, ethylene carbonate and gamma-butyrolactone
- thermal activators such as razobisisobutyronitrile (AIBN), ammonium persulfate or benzoyl peroxide can be used in polymerization in homogeneous solution, they are however slow to act at the temperature at which polymers intended for the textile sector are manufactured. These activators therefore require a significant duration of polymerization and are used mainly in batch and semi-continuous processes.
- AIBN razobisisobutyronitrile
- ammonium persulfate or benzoyl peroxide
- TMSN Tetramethyl succinonitrilej [NC-C (CH 3 ) 2 - C (CH 3 ) 2 - CN], a highly toxic product.
- the Applicant has now found that by polymerizing acrylonitrile with minus an unsaturated monomer copolymerizable with acrylonitrile in the presence of an azocarboxylic acid ester, neither the formation of toxic decomposition products mentioned above nor even cyanated compounds is observed.
- the present invention therefore provides a process for the manufacture of polymers based on acrylonitrile, characterized in that one operates in the presence of at least one ester of azocarboxylic acid of formula (I),
- Ri, R2, R3 e R are independently selected from the group consisting of linear or branched alkyls having from 1 to 9 carbon atoms, preferably from 1 to 4 carbon atoms, optionally substituted by one or more substituents selected from hydroxyl, alkoxy Cl to C 6 alkyl, halogen; - cycloalkyl, C 3 to C * ⁇ 2, optionally substituted with one or more substituents selected from alkyl to C 6 alkoxy, C * -C 6 hydroxy and halogen;
- -aralkyles optionally substituted by one or more alkyl groups -C 6 alkoxy C 6, hydroxy, and halogen;
- R "and R ' are identical or different from each other and are selected independently from the group consisting of linear or branched aliphatic radicals in Ci to C 10 , preferably in C * ⁇ to C.
- these azocarboxylic acid esters have a low melting temperature and the predissolution step in a solvent before addition to the polymerization reactor is not necessary.
- the preferred azocarboxylic acid esters are those in which R "and R 'represent methyl or ethyl and in which R **, R 2 , R 3 and R 4 advantageously represent alkyl groups from d to C.
- the ester " particularly preferred azocarboxylic acid is diethyl
- 2, 2'-azobisisobutyrate that is to say, with R *, R 2, R 3 and R 4 is methyl and R 'and R "is ethyl.
- the azocarboxylic acid esters of formula (I) can be prepared by a conventional two-step process comprising a first step of conversion of the azonitrile, by reaction with an alcohol, in the presence of HCl, according to the Pinner reaction, leading hydrochloride of corresponding azoiminoether and a second hydrolysis step in the presence of the hydrochloride thus obtained. They can also be prepared by improved methods as described in documents DE 2 254 572, EP 80 275 and EP 230 586.
- esters can be prepared by reaction of an azonitrile with an alcohol and acid hydrochloric acid in an aromatic solvent, with an HCl / azonitrile molar ratio> 2 when the alcohol is methanol and> 3 when the alcohol is ethanol or a higher alcohol.
- the process for obtaining acrylonitrile-based polymers according to the present invention can be discontinuous, semi-continuous or continuous.
- the polymerization in the presence of at least one azocarboxylic acid ester of formula (I) can be of the emulsion, suspension or bulk type, in aqueous medium or in solution in an organic solvent or a water / solvent mixture. Most often preferred is suspension or solution polymerization in an organic solvent or a water / solvent mixture.
- the solvent can be any solvent used for an acrylonitrile-based polymer, such as dimethylformamide, dimethylacetamide, dimethylsulphoxide, ethylene carbonate, isopropanol and gamma-butyrolactone.
- concentration of monomer (s) in the reaction medium can vary between 10 and 70% by weight.
- a surfactant or dispersant may be present.
- These agents are generally water-soluble polymers such as water-soluble celluloses, polyvinyl pirrolidone, polyacrylamide, polyoxyethylene, polycarboxylic acids, poly sulfonic acids and polyvinyl alcohol. They are used in an amount of 0.1 to 3% by weight relative to the monomer (s).
- the monomer concentration represents between 15 and 60% by weight of the reaction mixture consisting of monomer (s), water and optionally surfactant or dispersing agent.
- azocarboxylic acid ester (s) used is preferably between 0.01 and 6% by weight relative to the monomer (s).
- a transfer agent such as mercaptans can also be used to adjust the molecular weights of the polymers.
- the polymers thus obtained can be spun into a fibrous material by conventional wet spinning, dry jet wet spinning or dry spinning techniques.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Toxicology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Artificial Filaments (AREA)
- Polymerization Catalysts (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0011016A FR2813319A1 (en) | 2000-08-29 | 2000-08-29 | PROCESS FOR PRODUCING ACRYLONITRILE FIBERS |
FR0011016 | 2000-08-29 | ||
PCT/FR2001/002611 WO2002018462A1 (en) | 2000-08-29 | 2001-08-14 | Method for making acrylonitrile fibres |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1313779A1 true EP1313779A1 (en) | 2003-05-28 |
Family
ID=8853783
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01963097A Withdrawn EP1313779A1 (en) | 2000-08-29 | 2001-08-14 | Method for making acrylonitrile fibres |
Country Status (7)
Country | Link |
---|---|
US (1) | US20040068069A1 (en) |
EP (1) | EP1313779A1 (en) |
JP (1) | JP2004507592A (en) |
AU (1) | AU2001284139A1 (en) |
CA (1) | CA2420769A1 (en) |
FR (1) | FR2813319A1 (en) |
WO (1) | WO2002018462A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009145051A1 (en) * | 2008-05-30 | 2009-12-03 | 三菱レイヨン株式会社 | Acrylonitrile copolymer and method for manufacturing the same, and acrylonitrile copolymer solution and polyacrylonitrile precursor fiber for carbon fiber and method for manufacturing the same |
FR2935148B1 (en) * | 2008-08-25 | 2010-08-27 | Arkema France | PROCESS FOR PRODUCING CARBON FIBERS |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2471959A (en) * | 1948-01-15 | 1949-05-31 | Du Pont | Polymerizations employing azo compounds as catalysts |
NL79400C (en) * | 1951-01-19 | |||
BE509761A (en) * | 1951-03-06 | |||
BE535867A (en) * | 1954-02-19 | |||
US3697492A (en) * | 1969-06-16 | 1972-10-10 | Celanese Corp | Acrylonitrile polymerization |
JPS59191704A (en) * | 1983-04-13 | 1984-10-30 | Japan Exlan Co Ltd | Production of high-molecular weight acrylonitrile polymer |
JPS62256807A (en) * | 1986-04-30 | 1987-11-09 | Mitsubishi Rayon Co Ltd | Production of acrylonitrile polymer |
JP2581541B2 (en) * | 1986-05-30 | 1997-02-12 | 和光純薬工業 株式会社 | Polymerization method of vinyl acetate |
JP2710665B2 (en) * | 1989-05-17 | 1998-02-10 | 株式会社日本触媒 | Method for producing short fibrous (meth) acrylonitrile-based polymer |
JP3408279B2 (en) * | 1993-04-09 | 2003-05-19 | 三菱化学株式会社 | Method for producing high nitrile copolymer |
FR2788517B1 (en) * | 1999-01-15 | 2001-03-16 | Atochem Elf Sa | PROCESS FOR THE PREPARATION OF AZOIMINOETHERS AND ESTERS OF AZOCARBOXYLIC ACIDS, AND NOVEL MIXED ESTERS OF AZOCARBOXYLIC ACIDS |
JP3570618B2 (en) * | 1999-10-06 | 2004-09-29 | 日東紡績株式会社 | Method for producing allylamine-based copolymer |
-
2000
- 2000-08-29 FR FR0011016A patent/FR2813319A1/en active Pending
-
2001
- 2001-08-14 WO PCT/FR2001/002611 patent/WO2002018462A1/en not_active Application Discontinuation
- 2001-08-14 CA CA002420769A patent/CA2420769A1/en not_active Abandoned
- 2001-08-14 AU AU2001284139A patent/AU2001284139A1/en not_active Abandoned
- 2001-08-14 EP EP01963097A patent/EP1313779A1/en not_active Withdrawn
- 2001-08-14 JP JP2002523975A patent/JP2004507592A/en active Pending
-
2003
- 2003-02-28 US US10/375,052 patent/US20040068069A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of WO0218462A1 * |
Also Published As
Publication number | Publication date |
---|---|
FR2813319A1 (en) | 2002-03-01 |
JP2004507592A (en) | 2004-03-11 |
US20040068069A1 (en) | 2004-04-08 |
WO2002018462A1 (en) | 2002-03-07 |
CA2420769A1 (en) | 2002-03-07 |
AU2001284139A1 (en) | 2002-03-13 |
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Legal Events
Date | Code | Title | Description |
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
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17P | Request for examination filed |
Effective date: 20030210 |
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AK | Designated contracting states |
Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK RO SI |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: TEMBOU N'ZUDIE, DENIS Inventor name: COLOMBIE, DAMIEN Inventor name: CERF, MARTINE |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: ARKEMA |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20060202 |