DE1065174B - Process for the production of thermosetting, organic, polymeric substances containing phosphorus, nitrogen and halogen - Google Patents

Process for the production of thermosetting, organic, polymeric substances containing phosphorus, nitrogen and halogen

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Publication number
DE1065174B
DE1065174B DENDAT1065174D DE1065174DA DE1065174B DE 1065174 B DE1065174 B DE 1065174B DE NDAT1065174 D DENDAT1065174 D DE NDAT1065174D DE 1065174D A DE1065174D A DE 1065174DA DE 1065174 B DE1065174 B DE 1065174B
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Prior art keywords
organic
reaction
halogen
thermosetting
alkenyl
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DENDAT1065174D
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German (de)
Inventor
La. Carl Hamalainen New Orleans (V. St. A.)
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Solvay Solutions UK Ltd
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Albright and Wilson Ltd
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Publication of DE1065174B publication Critical patent/DE1065174B/en
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    • 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
    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44F—SPECIAL DESIGNS OR PICTURES
    • B44F11/00—Designs imitating artistic work
    • B44F11/02—Imitation of pictures, e.g. oil paintings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C07F9/5407—Acyclic saturated phosphonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/025—Polyphosphazenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/06—Phosphorus linked to carbon only
    • 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
    • D06M13/244—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 sulfur or phosphorus
    • D06M13/282—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 sulfur or phosphorus with compounds containing phosphorus
    • D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives 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
    • D06M13/244—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 sulfur or phosphorus
    • D06M13/282—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 sulfur or phosphorus with compounds containing phosphorus
    • D06M13/288—Phosphonic or phosphonous acids or derivatives 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • D06M15/43—Amino-aldehyde resins modified by phosphorus compounds
    • D06M15/431—Amino-aldehyde resins modified by phosphorus compounds by phosphines or phosphine oxides; by oxides or salts of the phosphonium radical
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/667—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing phosphorus in the main chain
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/667—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing phosphorus in the main chain
    • D06M15/673—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing phosphorus in the main chain containing phosphorus and nitrogen in the main chain

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Textile Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Biochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Paints Or Removers (AREA)
  • Polyethers (AREA)

Description

BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY

DEUTSCHES JmmL· PATENTAMTGERMAN JmmL PATENT OFFICE

kl. 39 c 25/01 kl. 39 c 25/01

INTERNAT. KL. C 08 fINTERNAT. KL. C 08 f

AUSLEGESCHRIFT 1065174EDITORIAL 1065174

A23747IVb/39cA23747IVb / 39c

ANHE LDETAG:ANHE LDETAG:

BEKANNTMACHUNG DER ANMELDUNG UND AUSGABE DER AUSLEGESCHRIFT:NOTICE THE REGISTRATION AND ISSUE OF THE EDITORIAL:

9. NOVEMBER 1955NOVEMBER 9, 1955

10. SEPTEMBER 1959SEPTEMBER 10, 1959

Die Erfindung bezieht sich auf neuartige vernetzte partiell ungesättigte polymere organische Substanzen, die Phosphor, Stickstoff und Halogen enthalten und bei denen das Verhältnis von Halogen zu den ungesättigten Gruppen in einem ziemlich weiten Bereich variiert werden kann. Diese Produkte eignen sich insbesondere als Flammschutzmittel für Textilien.The invention relates to novel crosslinked partially unsaturated polymeric organic substances that Contain phosphorus, nitrogen and halogen and in which the ratio of halogen to the unsaturated Groups can be varied in a fairly wide range. These products are particularly suitable as a flame retardant for textiles.

Erfindungsgemäß stellt man die neuartigen hitzehärtbaren polymeren Substanzen in der Weise her, daß man einen neutralen Polyphosphornitrilalkenylester, dessen Alkenylreste endständig ungesättigt sind, mit mindestens einem Polyhalogenkohlenwasserstoff, der mindestens zwei Brom- und/oder Chloratome am selben Kohlenstoffatom trägt, in Gegenwart eines Reaktionsanlassers, der auf der Entstehung freier Radikale beruht, reagieren läßt.According to the invention, the novel thermosetting polymeric substances are prepared in such a way that a neutral polyphosphoronitrile alkenyl ester, the alkenyl radicals of which are terminally unsaturated, with at least a polyhalohydrocarbon containing at least two bromine and / or chlorine atoms on the same carbon atom carries, in the presence of a reaction initiator, which is based on the formation of free radicals, can react.

Die erhaltenen Polymere sind Polyphosphornitrilesteraddukte, von denen man annimmt, daß die Struktureinheiten im wesentlichen aus Gruppen folgender Formel bestehen:The polymers obtained are polyphosphonitrile ester adducts which are believed to be the structural units essentially consist of groups of the following formula:

R'
ιR '
ι R'R ' I
-RC =I.
-RC = — RC- C(R')2
I j - RC- C (R ') 2
I j I I
X CXY2 II
X CXY 2 = C(R'),,= C (R ') ,, R' R'
ι ιR 'R'
ι ι I I
RC —CRII
RC —CR

X(R').C C(RO2CXY2 X (R '). CC (RO 2 CXY 2

CXY2 CXY 2

XCH2 CH2CXY2 Verfahren zur Herstellung hitzehärtbarer,XCH 2 CH 2 CXY 2 Process for the production of thermosetting,

organischer, Phosphor, Stickstofforganic, phosphorus, nitrogen

und Halogen enthaltenderand halogen containing

polymerer Substanzenpolymeric substances

Anmelder:Applicant:

Albright & Wilson Limited,Albright & Wilson Limited,

Birmingham, WarwickshireBirmingham, Warwickshire

(Großbritannien)(Great Britain)

Vertreter: Dr.-Ing. F. Wuesthoff und Dipl.-Ing. G. Puls, Patentanwälte, München 9, Schweigerstr. 2Representative: Dr.-Ing. F. Wuesthoff and Dipl.-Ing. G. pulse, Patent Attorneys, Munich 9, Schweigerstr. 2

Beanspruchte Priorität: V. St. v. Amerika vom 9. November 1954Claimed priority: V. St. v. America 9 November 1954

OQ
-N = P-OQ
-N = P-

OQ JOQ J

worin Q variabel ist und folgende Gruppen umfaßt:where Q is variable and comprises the following groups:

wobei R ein Alkylenrest, R' ein Wasserstoffatom oder ein Alkylrest, X ein Brom- oder Chloratom und Y ein Brom-, Chlor- oder Wasserstoffatom ist. Wenn z. B. der Alkenylalkohol Allylalkohol ist, dann istwhere R is an alkylene radical, R 'is a hydrogen atom or an alkyl radical, X is a bromine or chlorine atom and Y is a bromine, Is chlorine or hydrogen atom. If z. B. the alkenyl alcohol is allyl alcohol, then is

Q gleich — CH2CH = CH2,
-CH2CH-CH2 und -CH2CH-CHCH2 Q equals - CH 2 CH = CH 2 ,
-CH 2 CH-CH 2 and -CH 2 CH-CHCH 2

Diese Addukte stellt man mit Hilfe eines Polyhalogenmethans der Formel CX2Y2 her, wobei X Biom oder Carl Hamalainen, New Orleans, La. (V. St. A.), ist als Erfinder genannt wordenThese adducts are produced with the aid of a polyhalomethane of the formula CX 2 Y 2 , where X Biom or Carl Hamalainen, New Orleans, La. (V. St. A.), has been named as the inventor

Chlor und Y Brom, Chlor oder Wasserstoff ist. Beispiele solcher Polyhalogenmethane umfassen Verbindungen der Formel CBr4, CBr3Cl, CBr2Cl2, CBrCl3, CBr8H, CBr2H2, CCl4, CCl3H und CCl2H2.Chlorine and Y is bromine, chlorine or hydrogen. Examples of such polyhalomethanes include compounds of the formula CBr 4 , CBr 3 Cl, CBr 2 Cl 2 , CBrCl 3 , CBr 8 H, CBr 2 H 2 , CCl 4 , CCl 3 H and CCl 2 H 2 .

Im allgemeinen eignen sich solche endständig ungesättigten neutralen Ester aus Alkenylalkoholen und Phosphornitrilhalogeniden, die eine durch freie Radikale induzierte Polymerisation eingehen können. Man kann sie nach der in J. Am. Chem. Soc. 71,2251 (1949) beschriebenen Methode aus Polyphosphormtrilchlorid und Alkohol herstellen, indem man z. B. einen endständig ungesättigten Alkenylalkohol oder dessen Alkoholat mit einem Phosphornitrilhalogenid unter Abscheidung von Halogenwasserstoff oder dem Salz eines Halogenwasserstoffes kondensiert, bis die Halogenatome des Phosphornitrilhalogenids durch Alkenoxyreste ersetzt worden sind. Geeignete Verfahren zur Herstellung dieser Ester unter Verwendung eines endständig gesättigten Alkenylalkohols oder seines Alcoholates sind auch in den USA.-Patentschriften 2 192 921, 2 214 769 oder 2 586 312 beschrieben. Einen neutralen Ester eines Alkenylalkohols kann man auf seine Fähigkeit, einer durch freie Radikale induzierten Polymerisation sich zu unterziehen, z. B. dadurch prüfen, daß man den Ester in Gegenwart freier Radikale, z. B. solcher, die von einem Peroxyd bei seiner Zersetzungstemperatur gebildet werden, unterwirft undIn general, those terminally unsaturated neutral esters of alkenyl alcohols and phosphonitrile halides are suitable, which can enter into a polymerization induced by free radicals. One can they according to the in J. Am. Chem. Soc. 71, 2251 (1949) Method from Polyphosphormtrilchlorid and alcohol produce by z. B. a terminally unsaturated one Alkenyl alcohol or its alcoholate with a phosphonitrile halide with the separation of hydrogen halide or the salt of a hydrogen halide condenses until the halogen atoms of the phosphonitrile halide have been replaced by alkenoxy radicals. Suitable processes for the preparation of these esters under The use of a terminally saturated alkenyl alcohol or its alcoholate is also described in the USA patents 2 192 921, 2 214 769 or 2 586 312. You can use a neutral ester of an alkenyl alcohol its ability to undergo free radical induced polymerization, e.g. B. thereby consider that the ester can be used in the presence of free radicals, e.g. B. those produced by a peroxide at its decomposition temperature be formed, subjected and

dabei seine Viskosität prüft.. W.enn die Viskosität des Esters zunimmt, kann er in dem erfindungsgemäßen Verfahren verwendet werden.checks its viscosity. If the viscosity of the Ester increases, it can be used in the process of the invention.

Neutrale Ester endständig ungesättigter Alkcnylalkoholc, bei denen der Alkcnylrest 2 bis 6 Kohlcnstoffatomc enthält, zieht man im allgemeinen vor, insbesondere Allylester, bei denen der Alkenylrest die Formel -CH2CR1 = CH2 aufweist, wobei R1 Wasserstoff, Halogen oder ein Alkylrest-' sein kann. Beispiele geeigneter Alkcnylgruppcn sind: Vinyl, Allyl, Propenyl, Methallyl, 4-Pentcnyl und 2,4-Pentadienyl. Im allgemeinen zieht man für das erfindungsgemäße Verfahren Ester aus Alkcnylalkoholen und niedrigen, d. h. in organischen Lösungsmitteln., löslichen Phosphornitrilchloridcn vor, wie z. ß. von Trimcrcn, Tctrameicn oder von Gemischen, bei denen diese Oligomeren vorherrschen, insbesondere sind solche Ester geeignet, die aus Phosphornitrilhalogcniden, die viskose Flüssigkeiten darstellen und ein Molekulargewicht in der Größenordnung von 700, d. h. von 600 bis 800, aufweisen, erhalten wurden. Diese oligomeren Ester kann man auch durch thermische Polymerisation der präformierten Ester aus monomeren Phosphornitrilhalogcnidcn darstellen.Neutral esters of terminally unsaturated alkynyl alcohols in which the alkynyl radical contains 2 to 6 carbon atoms are generally preferred, in particular allyl esters in which the alkenyl radical has the formula -CH 2 CR 1 = CH 2 , where R 1 is hydrogen, halogen or an alkyl radical -' can be. Examples of suitable alkyl groups are: vinyl, allyl, propenyl, methallyl, 4-pentynyl and 2,4-pentadienyl. In general, for the process according to the invention, esters of alkynyl alcohols and low, ie, in organic solvents, soluble phosphonitrile chloride, such as, for. ß. of trimers, trams or mixtures in which these oligomers predominate, particularly those esters are suitable which have been obtained from phosphonitrile halides, which are viscous liquids and have a molecular weight of the order of magnitude of 700, ie from 600 to 800. These oligomeric esters can also be prepared from monomeric phosphonitrile halides by thermal polymerization of the preformed esters.

Die vorzugsweise verwendeten Polyhalogenkohlenwasscrstoffc haben die folgenden FormelnThe polyhalohydrocarbons preferably used have the following formulas

X
Λ. X
Λ.

X YX Y

IjIj

oder Y — C — C — Yor Y - C - C - Y

XYXY

wobei X Brom und Y Brom, Chlor oder Wasserstoff ist. Zu den geeigneten Polyhalogcnkohlcnwasscrstoffengehören z. B. Bromoform, Kohlcnstofftetrabromid, Tribromtrichloräthan und die Dibromdichloräthane. Insbesondere werden Polyhalogenmcthanc der Formel CX2Y2 vorgezogen. where X is bromine and Y is bromine, chlorine or hydrogen. Suitable polyhalohydrocarbons include e.g. B. Bromoform, Kohlcnstofftetrabromid, Tribromtrichloräthan and the Dibromodichloräthane. In particular, polyhalogenics of the formula CX 2 Y 2 are preferred.

Bei dem crfindungsgcrnäßcn Verfahren reagieren die in Reaktion tretenden funktionellen Gruppen der beiden Ausgangsstoffe in folgender Weise miteinander:In the process of discovery, the in Reaction occurring functional groups of the two starting materials with each other in the following way:

-CX2 H C = C--CX 2 HC = C-

— C —C —- C - C -

I I — ex χI I - ex χ

wobei X ein Brom- oder Chloratom ist.where X is a bromine or chlorine atom.

Geeignete Rcaktionsanlasser, die auf der Bildung freier Radikale beruhen, sind im wesentlichen alle Verbindungen, die unter dem Einfluß von Wärme, Licht oder fester Elementarteilchen, die im Lauf der Reaktion entstehen, freie Radikale bilden. Beispiele für geeignete Rcaktionsanlasser, die auf der Bildung freier Radikale beruhen, umfassen Pcroxyde, wie z. B. Dibenzoylperoxyd, Ditcrtiärbutylpcroxyd und Wasserstoffperoxyd, Alkalipcrsulfate, Hydroperoxydderivate, wie z. B. Benzoylhydropcroxyd, Cumolhydropcroxyd, Azoverbindungen, wie z. B. 2,2-Diazodiisobutyronitril, und Ketone, die man in Verbindung mit aktinischcm Licht verwendet. Ein Anlassen durch Pcroxyde wird bevorzugt, da die wasserlöslichen Pcroxyde sich dort eignen, wo die Reaktion in einem wäßrigen Medium durchgeführt wird.Suitable reaction starters based on the formation of free radicals are essentially all compounds those under the influence of heat, light or solid elementary particles that occur in the course of the reaction arise, form free radicals. Examples of suitable reaction starters based on the formation of free radicals based include Pcroxides, such as. B. dibenzoyl peroxide, di-butyl hydroxide and hydrogen peroxide, Alkali sulfates, hydroperoxide derivatives, such as. B. Benzoylhydropcroxide, Cumolhydropcroxyd, azo compounds, such as. B. 2,2-diazodiisobutyronitrile, and ketones, which one used in conjunction with actinic light. Tempering with Pcroxyde is preferred because the water-soluble Pcroxides are suitable where the reaction is carried out in an aqueous medium.

Die Reaktion zwischen den Alkcnylphosphornitrilestcrn und dem Polyhalogcnkohlenwasserstoff kann man unter sehr unterschiedlichen Bedingungen und in sehr unterschiedlichen Reaktionsverfahren durchführen. Man kann ein inertes flüssiges Verdünnungsmittel verwenden, was im allgemeinen vorgezogen wird. Im wesentlichen ist jede Flüssigkeit, die gegenüber den Reaktionsteilnehmern inert ist und dennoch ein geeignetes Lösungs- oder Dispersionsmittel für diese und für den auf der Bildung freier Radikale beruhenden Anlasser darstellt, geeignet,The reaction between the alkylphosphonitrile esters and the polyhalohydrocarbon can be used under very different conditions and in very different ways perform different reaction processes. An inert liquid diluent can be used, which is generally preferred. Essentially any liquid is exposed to the reactants is inert and yet a suitable solvent or dispersant for this and for the one on which it is formed free radical starter is suitable,

z. B. Wasser, Kohlenwasserstoffe, wie Pcntanc, Hexane, Benzol und Toluol, Äther, wie Diäthyl- oder Diphenyläthei sowie Dioxan und Ketone, wie Aceton und Methyläthylketon u. dgl.z. B. water, hydrocarbons such as Pcntanc, hexanes, benzene and toluene, ethers such as diethyl or diphenyl ethers as well as dioxane and ketones such as acetone and methyl ethyl ketone and the like.

Die Reaktion kann man in geeigneter Weise bei Ubcr- oder Unterdruck und bei jeder Temperatur unterhalb der Zersetzungstemperatur der Reaktionsteilnehmer und des Reaktionsmediums durchführen, vorausgesetzt, daß das letztere flüssig ist. Im allgemeinen kann man, wenn man einen peroxydischen Reaktionsanlasser verwendet, die Reaktion unter Atmosphärendruck und bei etwa 70 bis 90° C durchführen.The reaction can be carried out in a suitable manner under vacuum or pressure and at any temperature below the Perform decomposition temperature of the reactants and the reaction medium, provided that the the latter is liquid. In general, when using a peroxidic reaction starter, one can use the Carry out the reaction under atmospheric pressure and at about 70 to 90 ° C.

Das Verhältnis der in den neuartigen Polycsteraddukten noch enthaltenen ungesättigten Gruppen kann man abändern, indem man die Reaktionszeit und/oder das Verhältnis des verwendeten Polyhalogenkohlenwasscrstoffes variiert, wobei eine längere Reaktionszeit im allgemeinen einen geringeren Anteil an ungesättigten Gruppen in dem Addukt ergibt. Bei den Polyesteraddukten liegt das Verhältnis von Halogen zu Phosphor vorzugsweise zwischen 2 : 1 und 6:1, insbesondere .venn man die Addukte als Mittel zum Flammfestmachen verwendet. Bei im wesentlichen vollständiger Durchführung der Reaktion ist die Verwendung von etwa 1J3 bis 4/3 Mol Polyhalogenkohlenwasserstoff je Mol Phosphornitrilester besonders vorteilhaft.The ratio of the unsaturated groups still present in the novel polymer adducts can be changed by varying the reaction time and / or the ratio of the polyhalohydrocarbon used, a longer reaction time generally resulting in a lower proportion of unsaturated groups in the adduct. In the case of the polyester adducts, the ratio of halogen to phosphorus is preferably between 2: 1 and 6: 1, in particular when the adducts are used as flame-proofing agents. At substantially complete implementation of the reaction, the use of about 1 J 3 to 4/3 moles per mole polyhalohydrocarbon is Phosphornitrilester particularly advantageous.

Da das neue polymere Polyester-Addukt vorzugsweise in wäßriger Emulsion zum Flammfestimprägniercn von Textilien verwendet wird, kann bei einer bevorzugten Durchführungsform des Vcifahrens das Addukt in situ gleich als Emulsion hergestellt werden. Hierbei wird zuerst eine wäßrige Emulsion, enthaltend den Phosphor.-nitrilester, den Polyhalogenwasserstoff, ein wasserlösliches Peroxyd und ein Emulgiermittel, zubereitet, die dann auf die Temperatur erhitzt wird, bei der das Peroxyd freie Radikale bildet, bis das erwünschte Polymere entsteht. Im allgemeinen zieht man wäßrige Emulsionen mit einem verhältnismäßig hohen Gehalt an organischen Stoffen zur Verwendung als flammfest machendes Mittel vor, weshalb man die erwünschten Addukte vorzugsweise in einer konzentrierten wäßrigen Emulsion herstellt. Der ρ,,-Wert der Emulsion beträgt vorzugsweise 5 bis 8 und kann eingestellt werden, indem man genügend wasserlösliche schwache Base zugibt. Geeignete Basen sind unter anderem: anorganische Basen, wie z. B. Alkalibikarbonatc, und organische Basen, wie z. B. Pyridin, Dimethylanilin und Triäthanolamin. Im allgemeinen genügt die Verwendung von etwa 5 bis 10 Teilen Alkalibikarbonat je 100 Teile Phosphornitrilester.Since the new polymeric polyester adduct is preferably used in an aqueous emulsion for the flame-proof impregnation of Textiles is used, in a preferred embodiment of the process, the adduct can be used in situ can be produced as an emulsion. First, an aqueous emulsion containing the phosphorus nitrile ester, the polyhalogen, a water-soluble peroxide and an emulsifier, prepared the then heated to the temperature at which the peroxide forms free radicals until the desired Polymers are created. In general, aqueous emulsions with a relatively high content are attracted organic substances for use as a flame retardant, which is why the desired Preferably produces adducts in a concentrated aqueous emulsion. The ρ ,, value of the emulsion is preferably 5 to 8 and can be adjusted by adding enough water-soluble weak base. Suitable bases include: inorganic bases, such as. B. Alkalibikarbonatc, and organic Bases such as B. pyridine, dimethylaniline and triethanolamine. In general, it is sufficient to use about 5 to 10 parts of alkali bicarbonate per 100 parts of phosphonitrile ester.

Man kann bei dieser Durchführungsform des Verfahrens im wesentlichen jedes übliche Emulgiermittel verwenden. Geeignete Mittel sind unter anderem Polyvinylalkohol, Alkoholsulfate, Dioktylnatriumsulfosuccinat, Isopropylnaphthalinnatriumsulfonat, Ammoniumolcat, Carboxymcthylcellulose und Harzseifen, wobei man Polyvinylalkohol mittlerer Viskosität vorzieht. Geeignete Mengenverhältnisse smd 1 Teil Polyvinylalkohol, 50 Teile organischer Reaktionstcilnehmer und 100 Teile Wasser.
Der Anteil des peroxydischen Polymerisationskatalysators kann wie bei üblichen Emulsions-Polymerisationen weitgehend verändert werden. Vorzugsweise verwendet man etwa 0,01 bis 0,03 Mole Katalysator je Mol Phosphat-Reaktionstcilnehmer. Essentially any conventional emulsifying agent can be used in this embodiment of the process. Suitable agents include polyvinyl alcohol, alcohol sulfates, dioctyl sodium sulfosuccinate, isopropyl naphthalene sodium sulfonate, ammonium olate, carboxymethyl cellulose and resin soaps, polyvinyl alcohol of medium viscosity being preferred. Suitable proportions are 1 part of polyvinyl alcohol, 50 parts of organic reactants and 100 parts of water.
The proportion of the peroxide polymerization catalyst can be changed to a large extent, as in the case of customary emulsion polymerizations. It is preferred to use from about 0.01 to 0.03 moles of catalyst per mole of phosphate reactant.

Wie schon erwähnt, sind die erfindungsgemäßen flüssigen oder festen halogenalkylierten Alkenyl-Phosphor-As already mentioned, the liquid or solid haloalkylated alkenyl phosphorus according to the invention are

nitrilpolyester-Addukte hitzehärtbare Polymere, die gegen Verbrennen relativ beständig sind. Man kann sie in üblicher Weise wie hitzehärtbare Polymere anwenden, z. B. als geformte Kunstharzgegenstände, wie Knöpfe, Behälter und elektrische Isolatoren, und als Überzüge, wie z. B. Anstriche und Lacke. Die neuartigen Addukte eignen sich insbesondere zur Verminderung der Entflammbarkeit entflammbarer Textilien, wobei man sie auf der Faser aushärten kann. Sie können einfach aus organischen Lösungen oder wäßrigen Dispersionen aufgebracht werden, und man kann sie zur Behandlung von Textilstoffen in Gestalt von Fasern, Schnitzeln, Garnen, Fäden und Geweben verwenden. Insbesondere bei Verfahren zur Behandlung wertvoller Textilien können sie, gemeinsam mit anderen polymeren Stoffen, angewendet werden, um organischen Textilien eine besondere Beständigkeit gegen Verbrennen zu verleihen.nitrile polyester adducts thermosetting polymers that are relatively resistant to burning. They can be used in the usual way as thermosetting polymers, e.g. As molded synthetic resin articles such as buttons, containers and electrical insulators, and as coatings such as e.g. B. Paints and varnishes. The novel adducts are particularly suitable for reducing the flammability of flammable textiles, whereby they can be cured on the fiber. They can easily be applied from organic solutions or aqueous dispersions, and they can be used to treat fabrics in the form of fibers, chips, yarns, threads and fabrics. In particular in processes for treating valuable textiles, they can be used together with other polymeric substances to give organic textiles a particular resistance to burning.

Die folgenden Beispiele sollen die Erfindung weiter erläutern; alle Teile und Prozentangaben sind gewichtsmäßig. The following examples are intended to explain the invention further; all parts and percentages are by weight.

Die neutralen Ester aus Alkenylalkoholen und Phosphornitrilhalogeniden, die in den Beispielen verwendet wurden, waren Alkylester, die durch Reaktion von 116 Teilen im wesentlichen trimerer Phosphornitrilchloride mit 162 Teilen Natriumallylalkoholat, gelöst in Benzol, dargestellt wurden. Die sich ergebenden Ester waren viskose Flüssigkeiten mit einem Molekulargewicht von 720 bis 770.The neutral esters of alkenyl alcohols and phosphonitrile halides, used in the examples were alkyl esters obtained by reacting 116 parts of essentially trimeric phosphorus nitrile chlorides with 162 parts of sodium allyl alcoholate, dissolved in Benzene. The resulting esters were viscous liquids having a molecular weight from 720 to 770.

Beispiel 1example 1

Eine Emulsion, die etwa 16 Teile Allylphosphornitrilester, 15 Teile Bromoform (Molarverhältnis von Bromoform zu Ester beträgt 0,6: 1), 1,5 Teile Natriumbicarbonat und 0,6 Teile Polyvinylalkohol als Emulgiermittel in 70 Teilen Wasser enthält, wird auf etwa 80° C erhitzt, dann werden etwa 0,6 Teile Kaliumpersulfat zugegeben und die Emulsion etwa 1 Stunde lang bei 80 bis 86° C gehalten, wobei eine stabile Emulsion entsteht, die ein Phosphor, Stickstoff und Halogen enthaltendes Polymeres enthält und sich zur Imprägnierung von Textilien eignete. In situ kann es dann bei 140° C ausgehärtet werden.An emulsion containing about 16 parts of allyl phosphonitrile ester, 15 parts of bromoform (molar ratio of bromoform to ester is 0.6: 1), 1.5 parts of sodium bicarbonate and contains 0.6 parts of polyvinyl alcohol as an emulsifier in 70 parts of water, is heated to about 80 ° C, then about 0.6 parts of potassium persulfate are added and the emulsion is added for about 1 hour at 80 to 86 ° C held, whereby a stable emulsion is formed, the polymer containing phosphorus, nitrogen and halogen contains and is suitable for the impregnation of textiles. It can then be cured in situ at 140 ° C.

Beispiel 2Example 2

Eine Emulsion mit einem Gehalt von etwa 29 Teilen Allylester, 18 Teilen Bromoform (Molarverhältnis von Bromoform zu Ester betrug 0,4:1), 4,6 Teilen Natriumbicarbonat und 0,9 Teilen Polyvinylalkohol als Emulgiermittel in 107 Teilen Wasser wird auf etwa 80° C erhitzt, dann ungefähr 0,9 Teile Kaliumpersulfat zugegeben und das Ganze etwa 1 Stunde lang bei etwa 80 bis 86° C gehalten, wobei eine stabile Emulsion des Polymeren ίο entsteht.An emulsion containing about 29 parts of allyl ester, 18 parts of bromoform (molar ratio of Bromoform to ester was 0.4: 1), 4.6 parts sodium bicarbonate and 0.9 parts of polyvinyl alcohol as an emulsifier in 107 parts of water is heated to about 80 ° C, then about 0.9 parts of potassium persulfate are added and this is done for about 1 hour at about 80 to 86 ° C held, creating a stable emulsion of the polymer ίο.

Claims (5)

Patentansprüche:Patent claims: 1. Verfahren zur Herstellung hitzehärtbarer, organischer, Phosphor, Stickstoff und Halogen enthaltender, polymerer Substanzen, dadurch gekennzeichnet, daß man neutrale Polyphosphornitrilalkenylester mit endständig ungesättigten Alkenylresten mit einem Polyhalogenkohlenwasserstoff, der mindestens zwei Halogenatome, wie Brom und/oder Chlor, am gleichen Kohlenstoffatom enthält, in Gegenwart eines freie Radikale bildenden Katalysators zur Reaktion bringt.1. Process for the production of thermosetting, organic, phosphorus, nitrogen and halogen containing, polymeric substances, characterized in that neutral polyphosphoronitrile alkenyl esters are used terminally unsaturated alkenyl radicals with a polyhalohydrocarbon of at least two Contains halogen atoms, such as bromine and / or chlorine, on the same carbon atom, in the presence of a free one Bringing radical-forming catalyst to reaction. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Polyhalogenkohlenwasserstoff ein Polyhalogenmethan, vorzugsweise Bromoform, verwendet.2. The method according to claim 1, characterized in that the polyhalohydrocarbon is used a polyhalomethane, preferably bromoform, is used. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man einen Polyphosphornitrilalkenylester verwendet, dessen Alkenylreste 2 bis 6 Kohlenstoffatome, vorzugsweise 3 Kohlenstoffatome, aufweist.3. The method according to claim 1 or 2, characterized in that there is a polyphosphoronitrile alkenyl ester used, the alkenyl radicals of which have 2 to 6 carbon atoms, preferably 3 carbon atoms, having. 4. Verfahren nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß man als Katalysator ein Peroxyd verwendet.4. The method according to claim 1 to 3, characterized in that the catalyst is a peroxide used. 5. Verfahren nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß man die Reaktion in wäßriger Emulsion stattfinden läßt.5. The method according to claim 1 to 4, characterized in that the reaction is carried out in aqueous Let emulsion take place. In Betracht gezogene Druckschriften:Considered publications: Journal of the American Chemical Society 71, S. 2251 (1949).Journal of the American Chemical Society 71, p. 2251 (1949).
DENDAT1065174D 1954-11-09 Process for the production of thermosetting, organic, polymeric substances containing phosphorus, nitrogen and halogen Pending DE1065174B (en)

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