WO1980002844A1 - Polymeres acryliques ignifuges - Google Patents

Polymeres acryliques ignifuges Download PDF

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Publication number
WO1980002844A1
WO1980002844A1 PCT/CH1980/000065 CH8000065W WO8002844A1 WO 1980002844 A1 WO1980002844 A1 WO 1980002844A1 CH 8000065 W CH8000065 W CH 8000065W WO 8002844 A1 WO8002844 A1 WO 8002844A1
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WO
WIPO (PCT)
Prior art keywords
component
polyacrylonitrile
flame
hydrogen
alkyl
Prior art date
Application number
PCT/CH1980/000065
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German (de)
English (en)
Inventor
C Mauric
R Wolf
Original Assignee
Sandoz Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sandoz Ag filed Critical Sandoz Ag
Publication of WO1980002844A1 publication Critical patent/WO1980002844A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients

Definitions

  • the present invention relates to flame-retardant polyacrylonitriles, in particular polyacrylonitrile fibers.
  • chloroalkyl polyphosphonates as well as bis-phosphorinanyl oxides for the flame-retardant finishing of polyacrylonitrile compounds.
  • the addition of smaller amounts is desirable for these compounds, which is particularly necessary in fiber production in order to maintain the properties of the polyacrylonitrile.
  • oligomeric polyphosphonates and / or certain bis-phosphoranyl oxides have an increased flame-retardant effect in the presence of halogen-containing compounds in polyacrylonitriles, it being possible at the same time to greatly reduce the amount of added flocculent-reducing agent.
  • the present invention relates to flame-retardant polyacrylonitrile compounds, preferably in fiber form, characterized in that these
  • component (c) a bis (2-oxo-1,3,2-dioxaphosphorinanyl) oxide, a bis (2-thiono1,3,2-dioxaphosphorinanyl) oxide and / or a 2-oxo-1,3, Contain 2-dioxaphosphorinanyl-2'-thiono-1 ', 3', 2'-dioxaphosphorinanyl oxide, or a mixture of components (a), (b) and (c).
  • the halogen-containing organic compound of component (a) is present as an additive and is not copolymerized with the polyacrylonitrile.
  • halogen means fluorine, chlorine, bromine or iodine, preferably chlorine or Brcm.
  • Such compounds are, for example, halogenated phthalic acid derivatives such as, for example, tetrabromophthalic anhydride, tetrabromophthalic acid esters or imides; Bicyclo [2, 2, 1] - heptane-2, 3-dicarboxylic acid derivatives, such as, for example, 5,6-dibromo-2,3-dicarboxylic acid-N-ethylimide-bicyclo [2, 2, 1] -heptane of the formula:
  • Terephthalic acid esters such as bis- [2,3-dibromopropyl] terephthalate; halogenated carbonates such as 2,2-bis-bromophthyl-3-bromopropyl carbonate or tribromophenyl carbonate; Halogenated isocyanurates, such as tris (dibromopropyl) isocyanurate of the formula halogenated diphenyl oxide such as decabromobiphenyl oxide; polymeric brominated compounds such as poly (tribromostyrene), brominated polyphenylene ether; halogenated benzene, toluene, xylene or ethylbenzene, such as, for example, hexabromobenzene, pentabromotoluene, tefetrabromxylene, pentabromethylbenzene, hexakis-bromophthyl-benzene, halogenated cyclic linear or branched,
  • Bisphenols e.g. Tetrabromobisphenol-A, Tetrabr ⁇ rfoisphenol-A-diethoxylate, and halogenated alkylaryl ether.
  • Component (a) an alkyl aryl ether of Formsl
  • B is hydrogen, alkyl (C 1-4 ), Hal or a plague
  • A is the single bond, a straight-chain or branched alkylene (C 1-4 ) radical
  • Such halogenated alkyl aryl ethers are e.g. described in German Offenlegungsschrift 27 31 817.
  • component (a) is 2,2-bis (4- (2 ', 3'-dibromopropoxy) -3,5-dibromophenyl) propane of the formula
  • R 1 is independently hydrogen or alkyl (C 1-4 )
  • R 2 alkyl (C 1 _ 4 ) or
  • R 1 and R 2 together with the common carbon atom cyclohexylidene, D or - (CH 2 ) 3 -
  • R 3 is hydrogen, alkyl (C 1-4 ), CH 2 Cl, CH 2 Br, p 2-100 (as average) Z is hydrogen or a radical of the formulas
  • R 1 and R 2 have the cfoigen meanings and
  • R 4 independently of one another are alkyl (C 1-4 ).
  • Such oligomeric polyphosphonates and their preparation are e.g. in Belgian Patent No. 659,335 and in U.S. Patents No. 3,760,037 and No. 3,836,507.
  • Oligomeric polyphosphonates with the recurring groups are preferred
  • Preferred component (c) are bis-phosphorinanyl oxides of the formula
  • R I independently of one another hydrogen, alkyl (C 1-4 ),
  • R II independently of one another hydrogen, alkyl ( 1-4 ),
  • R I and R II together with the common carbon atom form a cyclohexylidene, cyclohexenylidene or 3,4-dibromoyclohexylidene ring,
  • R III and R V independently of one another are hydrogen or alkyl- (C 1-4 ),
  • R IV independently of one another are hydrogen or methyl, at least one of the substituents R I , R II , R III , R IV and R V of
  • R III , R IV and R V always mean hydrogen.
  • Symmetrical compounds and those in which X is sulfur are preferred.
  • the present invention also relates to the use of a composition comprising a mixture of the above components (a) and (b) or (a) and (c) or (a) and (b) and (c) for the flame-retardant finishing of polyacrylonitrile compounds.
  • polyacrylonitrile is to be understood in the broadest sense, preference being given to halogen-free polymers and, in particular, those which are suitable for fiber formation. This includes homopolymers and copolymers of acrylonitrile with preferably at least 50% acrylonitrile. Such polymers are known per se. If the polymer contains at least 85% acrylonitrile, one speaks generally of "polyacrylonitriles"; if the acrylonitrile content is between 50-85% one speaks of "Modacxyls”.
  • the following requests came as comonomers, for example: unsaturated alcohols such as allylalkchol, M ⁇ thallylakchol, ⁇ -hydroxymethacrylonitrile, allyloxyethanol; Ethers such as, for example, vinyl methyl ether, allyl or vinyl ether of amino alcohols, allyl glycidyl ether; Halides such as vinyldiloride, vinylidene chloride, allyl chloride, amines such as vinylpyridines (2-vinylpyridine, 2-> methyl-5-vinylpyridine), vinylquinolines (2-vinylquinoline), vinylpiperazines, vinylimidazoles, 2-amino-4-vinylsulfonyl anisole, allyldimethylamine; Amides such as acrylamide, N-substituted acrylamides (N-dimethylacrylamide, N-dimethylamine prc ⁇ ylacrylamide, N- (2-hydroxyethyl) acrylamide), acrylic acid
  • Halogen-free polymers preferably polyacrylonitrile with at least 85% polymerized acrylonitrile, are preferred.
  • An essential aspect of the invention is the ratio of the total halogen to phosphorus in the polymer and the total content of halogen per se.
  • the atomic ratio of halogen to phosphorus is preferably 5: 2 to 25: 1, preferably 3: 1 to 20: 1, preferably 5: 1 to 15: 1.
  • the total halogen content in the polymer is preferably 1 to 16, preferably 3 to 15, preferably 4 to 12 and preferably 7-12 percent by weight, based on the total polymer weight. If only components (a) and (b) or (a) and (c) are used, these numbers result in a mixing ratio of component (a) to component (b) of preferably 1: 9 to 19: 1 , preferably 1: 1 to 9: 1 and a mixing ratio of components (a) to component (c) of preferably 1: 1 to 19: 1, preferably 7: 1 to 19: 1.
  • the ratio of the sum of components (b) and (c) to component (a) is preferably 1: 9 to 9: 1, preferably 1: 9 to 1: 1, and the ratio of component (c) to component (b) is preferably 1:19 to 1: 1.
  • the components (a) and (b) or (a) and (b) and (c), preferably (a) and (b), are preferably used.
  • Fiber-forming acrylic polymers are spun from the solution. Two processes were considered for this: the wet spinning process and the dry spinning process. In the wet spinning process, the acrylic polymer dissolved in suitable solvents is stretched out in a precipitation bath, washed and wound on bobbins or aftertreated.
  • Suitable solvents came e.g. Dimethylformamide, dimethylacetamide, ethylene carbonate, Dim ⁇ thylsulfoxid, or salt solutions of zinc chloride or sodium thiocyanate in question.
  • the acrylic polymer solution is heated in a dry spinning process, the temperature depending on the boiling point of the solvent (usually dimethylformamide) and then extruded in a heated spinning shaft. Hot air, nitrogen, steam or combinations thereof were suitable as carriers for the evaporating solvent.
  • the flame retardant compositions are stirred into the acrylic polymer solutions and then the flame retardant fibers are spun from the solution.
  • the flame retardant fibers are spun from the solution.
  • preferably between 5 and 30, preferably 10 to 20 percent by weight of the compositions according to the invention (based on polymer including additives) would be used.
  • the present invention also relates to a process for producing flame-retardant polyacrylonitrile fibers, characterized in that the body (a) together with component (b) and / or component (c) is dissolved or dispersed in a solution of polyacrylonitrile and. then the dissolved polyacrylonitrile is spun into a fiber
  • the present invention also relates to an agent for the flame-retardant finishing of polyacrylic compounds consisting of the above components (a) and (b) or (a) and (c) or (a) and (b) and (c).
  • Agents are, for example, the mixtures themselves, solutions or emulsions consisting of the polymer and a solvent (for example dimethylformamide), which is, for example, 20-80, preferably 40-60 percent by weight of components (a) and (b), (a) and (c) or (a) and (b) and (c).
  • the invention relates in particular to the compositions of components (a) and (b) and components (a) and (b) and (c), preferably (a) and (b).
  • Table 1 gives examples of the composition according to the invention, the components given in parts simultaneously expressing the ratio of these compounds in the composition.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)
  • Fireproofing Substances (AREA)

Abstract

Compositions ignifugees a base de polyacrylonitriles, se presentant de preference sous forme fibrillaire, et qui contiennent: (a) au moins un compose organique, non-halogene et ne formant pas fibre, presentant dans sa molecule au moins six atomes de carbone, ne contenant pas de phosphore et ne copolymerisant pas avec le polyacrylonitrile, (b) un polyphosphonate halogene oligomere ou (c) un oxyde bis-(2-oxo-1,3,2-dioxaphosphorinanyle), un oxyde bis- (2-thiono-1,3,2-dioxaphosphorinanyle) et/ou un oxyde (2-oxo-1,3,2-dioxaphosphorinanyle)-(2'-thiono-1',3',2'-dioxaphosphorinanyle), ou un melange de composants (a), (b) et (c).
PCT/CH1980/000065 1979-06-19 1980-06-02 Polymeres acryliques ignifuges WO1980002844A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH571179 1979-06-19
CH5711/79 1979-06-19
CH1059979 1979-11-29

Publications (1)

Publication Number Publication Date
WO1980002844A1 true WO1980002844A1 (fr) 1980-12-24

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ID=25698252

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CH1980/000065 WO1980002844A1 (fr) 1979-06-19 1980-06-02 Polymeres acryliques ignifuges

Country Status (5)

Country Link
DE (1) DE3022061A1 (fr)
FR (1) FR2459263A1 (fr)
GB (1) GB2053235B (fr)
IT (1) IT8048992A0 (fr)
WO (1) WO1980002844A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH667275A5 (de) * 1985-03-22 1988-09-30 Sandoz Ag Flammgehemmte methylmethacrylatpolymer- und -copolymermassen.
US8466096B2 (en) 2007-04-26 2013-06-18 Afton Chemical Corporation 1,3,2-dioxaphosphorinane, 2-sulfide derivatives for use as anti-wear additives in lubricant compositions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3645964A (en) * 1969-07-16 1972-02-29 Michigan Chem Corp Fire retardant acrylonitrile polymer compositions
FR2280640A1 (fr) * 1974-07-30 1976-02-27 Sandoz Sa Ignifugation de matieres organiques polymeres au moyen de derives du dioxaphosphorinane
JPS5260843A (en) * 1975-11-14 1977-05-19 Mitsubishi Rayon Co Ltd Resin compositions with improved flowability
DE2731817A1 (de) * 1976-07-23 1978-01-26 Sandoz Ag Flammhemmend wirkende zusammensetzung

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3645964A (en) * 1969-07-16 1972-02-29 Michigan Chem Corp Fire retardant acrylonitrile polymer compositions
FR2280640A1 (fr) * 1974-07-30 1976-02-27 Sandoz Sa Ignifugation de matieres organiques polymeres au moyen de derives du dioxaphosphorinane
JPS5260843A (en) * 1975-11-14 1977-05-19 Mitsubishi Rayon Co Ltd Resin compositions with improved flowability
DE2731817A1 (de) * 1976-07-23 1978-01-26 Sandoz Ag Flammhemmend wirkende zusammensetzung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Patent Abstracts of Japan, Vol. 2, no. 117 (29 September 1978), Page 2202c-77; & JP-A-52 060 843 (Mitsubishi Rayon) 19-05-1977 *

Also Published As

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IT8048992A0 (it) 1980-06-17
GB2053235A (en) 1981-02-04
GB2053235B (en) 1983-04-13
FR2459263A1 (fr) 1981-01-09
DE3022061A1 (de) 1981-01-08

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