CN117242111A

CN117242111A - Hydroxymethyl-organo-phosphine oxide alkoxylates, process for their production, flame-retardant polymers and their use

Info

Publication number: CN117242111A
Application number: CN202280030775.6A
Authority: CN
Inventors: O·霍恩斯坦; A·克鲁克肯伯格; W·施伦特; M·西肯; M·伯格; F·霍夫曼
Original assignee: Clariant International Ltd
Current assignee: Clariant International Ltd
Priority date: 2021-05-11
Filing date: 2022-05-04
Publication date: 2023-12-15
Also published as: EP4337709A1; WO2022238196A1

Abstract

Disclosed are mixtures comprising at least two phosphine oxides of formula (I):wherein R is ¹ Is a monovalent organic group, R ² 、R ³ 、R ⁴ And R is ⁵ Independently of one another, hydrogen, an alkyl radical having from 1 to 8 carbon atoms or an aryl radical having from 6 to 18 carbon atoms, n and m independently of one another being an integer from 0 to 10. These phosphine oxides can be used to make flame retardant polymers.

Description

Hydroxymethyl-organo-phosphine oxide alkoxylates, process for their production, flame-retardant polymers and their use

The present invention relates to alkoxylates of hydroxymethyl-organic-phosphine oxides, to a process for their preparation and to their use in the manufacture of flame retardant polymers.

Flame retardancy of polymers and polymer foams can be achieved by the addition of various substances. Most of these materials are halogenated, especially brominated, organic compounds. However, regulatory pressures on these materials have grown year by year due to toxic and eco-toxic effects. Thus, there is an urgent need to find alternative non-halogenated flame retardants for polymers.

Among these non-halogenated flame retardants, phosphorus-based flame retardants are one of the most effective substances in terms of flame retardance. These phosphorus-based compounds can be further distinguished by their oxidation state.

The industrially useful flame retardants may be phosphates, phosphonates or phosphinates, all of which contain phosphorus-oxygen-carbon bonds, i.e. ester linkages. These ester linkages are all prone to hydrolysis to some extent, thus leading to deleterious effects during polymer processing such as foam production (because the acid formed by hydrolysis deactivates the catalyst, which is necessary for proper foaming), or to degradation of polymer properties, especially polymer foam properties (with cleavage of covalent bonds, the three-dimensional network is destroyed). In this connection, phosphine oxides are very advantageous in comparison with all other phosphorus substances.

Furthermore, the compatibility of the flame retardant with the polymer-or more precisely-with the polyol system is very important. In one aspect, only sufficiently dispersed compounds allow for uniform distribution of the flame retardant in the polymer, and in another aspect stable dispersion is desired, which can also be stored for minutes to days to months.

From the prior art, phosphine oxide compounds are known to exhibit flame retardancy but to exhibit low compatibility with the polymer system and are therefore not technically feasible in such applications.

The reaction between tris- (chloromethyl) -and bis- (chloromethyl) methylphosphine oxide and vicinal diols is disclosed by G.Bor isov et al, phosphorus and Sulfur,1984, volume 21, pages 59-65. The product is linear or cyclic. As linear products, bis- (ethylene glycol) methylphosphine oxide and bis- (propylene glycol) methylphosphine oxide are disclosed. These compounds are characterized by boiling point, melting point and refractive index. Mixtures of different phosphine oxides and the use of phosphine oxides are not disclosed.

US 3,445,405 discloses flame retardant polyurethane compositions prepared by using the condensation product of at least one alkylene oxide and tris (hydroxymethyl) phosphine oxide in a reaction comprising a polyisocyanate and a polyether polymer. The trifunctional phosphine oxides are disclosed in this document as flame retardants for polyurethanes.

U.S. Pat. No. 5,985,965A discloses flame retardant polyurethanes. Mixtures of these oligomeric phosphates containing hydroxyalkoxy groups. Phosphine oxides are not mentioned therein.

Reactive halogen-free flame retardant polyether polyols are known from CN 10580833 A1. These are prepared from trimethylol phosphorus oxide by addition reaction with propylene oxide/ethylene oxide. The product is a multivalent reactive halogen-free flame retardant polyether that can be used to make flame retardant rigid foams. In this document, trifunctional phosphine oxides are disclosed.

Zhang et al in Journal of Appl ied Polymer Science,135 (5), 1-10 (2018) disclose flame retardant polyurethane foams prepared from compatible blends of soybean oil based polyols and phosphorus containing polyols. The phosphorus-containing polyether polyol is synthesized by polymerization between tris- (hydroxymethyl) phosphine oxide and propylene oxide. The soybean oil-based polyol is synthesized from epoxidized soybean oil by ring-opening reaction with lactic acid. Polyurethane foams are prepared by mixing a soybean oil based polyol with a phosphorus-containing polyether polyol. Several properties of polyurethane foams, such as their density and thermal degradation properties, were investigated.

One major application of flame retardant flexible polyurethane foams is in seat liners or headliners in the automotive industry. However, the technical need is not limited to flame retardancy, but another very important need from the industry (and ultimately from the end customer) is the very low emission of potentially harmful Volatile Organic Substances (VOCs). In general, flame retardants are non-reactive small molecules that have a tendency to migrate and evaporate, i.e., to cause exudation and emission of VOCs. There are two concepts regarding the need to achieve low emissions: by using reactive or polymeric flame retardants or reactive small molecules. The latter has the advantage of generally lower viscosity and thus ease of processing.

In addition, the molecular structure may play a decisive role in foam preparation. In fact, for flexible foams, a low crosslink density is necessary to allow defect free formation of the open cell structure of the foam. The phosphine oxides disclosed in the prior art for polyurethane foam applications have a major disadvantage of being trifunctional (i.e. bearing three hydroxyl groups per molecule) and thus each acting as a cross-linking agent in the polymerization reaction (see for example US 3,445,405A or CN 105801833a or the above-mentioned k.zhang et al article).

U.S. Pat. No. 6,380,273 B1 discloses a process for the preparation of polyurethane foams containing halogen-free flame retardants and having high oxidative heat resistance during foaming. The process is useful for making flexible ester and ether foams and rigid foams and facilitates the preparation of polyurethane foams having low haze values. Furthermore, the process results in a polyurethane foam with flame retardancy and high resistance to ageing, i.e. the polyurethane foam has an effective flame retardancy after a corresponding storage period even at elevated temperatures. The disclosed method of making flame retardant flexible polyurethane foams having low sensitivity to core discoloration involves the use of hydroxyalkyl phosphonates as halogen-free flame retardants and as core discoloration inhibitors.

US2001/0034388 A1 discloses halogen-free, water-blown, flame-retardant rigid polyurethane foams which meet the necessary and defined requirements for flame retardancy, ease of preparation, low smoke density and low smoke toxicity. The polyurethane foams described in this document contain alkoxylated alkyl-phosphonic acids as flame retardants.

US 2004/00777641 A1 discloses flame retardant flexible polyurethane foams with high aging resistance and methods for their preparation. This document describes reduced halogen content, low emission polyurethane foams having improved hydrolytic aging resistance when compared to halogen-free flame retardant polyurethane foams and lower halogen content when compared to prior art polyurethane foams. The flame retardant flexible polyurethane foam disclosed in this document comprises a mixture of hydroxyalkyl phosphonate and chlorinated phosphate.

In view of the above, there are solutions that can be used to prepare each technical challenge present in flame retardant polymers such as flexible polyurethane foams.

It is an object of the present invention to provide halogen-free flame retardant compounds which can be used to prepare flame retardant polymers having low VOC emissions as well as non-hydrolytic, high compatibility and open cell foam forming properties. The compounds and flame retardant polymers prepared therefrom should have these different properties in one single compound.

It is another object of the present invention to provide a polymer composition having excellent flame retardancy together with very low VOC emissions and hydrolysis resistance when subjected to high temperatures, preferably in a polymer made from monomers having reactive hydroxyl groups, amino groups or epoxy groups. Furthermore, the polymer composition should show excellent extrudability and plasticity in different plastic articles.

These objects are achieved by providing phosphine oxide compounds and by providing the polymer compositions disclosed hereinafter.

The invention relates to phosphine oxides comprising at least two structurally different compounds of formula (I)

Wherein the method comprises the steps of

R ¹ Is a monovalent organic group which is a monovalent organic group,

R ² 、R ³ 、R ⁴ and R is ⁵ Each identical or different and independently of one another hydrogen, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 18 carbon atoms,

n and m are each independently an integer from 0 to 10.

The term "structurally different" shall broadly cover any difference in the formula (I) of phosphine oxides, including the group R in formula (I) ¹ To R ⁵ And/or any differences in the integers m and n.

Preferred are mixtures of structurally different phosphine oxides of the formula (I), wherein R ² Or R is ³ One of them is hydrogen and R ² Or R is ³ The other of (2) is hydrogen, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 18 carbon atoms, and wherein R ⁴ Or R is ⁵ One of them is hydrogen and R ⁴ Or R is ⁵ Is hydrogen, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 18 carbon atoms.

More preferred are mixtures of structurally different phosphine oxides of formula (I) wherein R ² Or R is ³ One of them is hydrogen and R ² Or R is ³ The other of (a) is hydrogen or an alkyl group having 1 to 2 carbon atoms, preferably methyl, and wherein R ⁴ Or R is ⁵ One of them is hydrogen and R ⁴ Or R is ⁵ The other of (a) is hydrogen or an alkyl group having 1 to 2 carbon atoms, preferably methyl.

These preferred phosphine oxide mixtures comprise at least two structurally different compounds of the formulae (Ia) (Ib) and/or (Ic).

Wherein the method comprises the steps of

R ¹ M and n are as defined above,

R ^2a and R is ^3a Each identical or different and independently of the others hydrogen, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 18 carbons, preferably selected from hydrogen and methyl, and

R ^4a And R is ^5a Each identical or different and independently of one another an alkyl group having from 1 to 8 carbon atoms or an aryl group having from 6 to 18 carbon atoms, and is preferably selected from hydrogen and methyl.

In these preferred mixtures, at least two structurally different compounds of formula (Ia), or at least two structurally different compounds of formula (Ib), or at least two structurally different compounds of formula (Ic), or at least two structurally different compounds of formula (Ia) and (Ib), or at least two structurally different compounds of formula (Ia) and (Ic), or at least two structurally different compounds of formula (Ib) and (Ic) may be present.

Very preferred are phosphine oxides, wherein R ² 、R ³ 、R ⁴ And R is ⁵ Independently of one another selected from hydrogen, C ₁ -C ₆ -alkyl and phenyl, more preferably selected from hydrogen and C ₁ -C ₆ -alkyl, and even more preferably selected from hydrogen and C ₁ -C ₃ -alkyl, and most preferably selected from hydrogen and methyl.

Very preferred are mixtures of phosphine oxides comprising structurally different compounds of formula (I), wherein R ¹ Is C ₁ -C ₆ -alkyl, cyclohexyl or phenyl, preferably C ₁ -C ₃ -alkyl and most preferably methyl.

Very preferred are phosphine oxides comprising at least one compound of formula (I I), wherein R ¹ Is C ₁ -C ₆ -alkyl, cyclohexyl or phenyl, preferably C ₁ -C ₃ -alkyl and most preferably methyl.

Still other highly preferred mixtures of phosphine oxides comprise compounds of formula (I) wherein the sum n+m is a number from 1 to 15 and most preferably from 4 to 12.

The term "monovalent organic group" as used herein includes, unless otherwise specified, monovalent organic groups derived from an organic group by removal of one hydrogen atom. The organic group may be a saturated or unsaturated, straight-chain, branched or mono-or polycyclic hydrocarbon or a saturated or unsaturated heterocyclic group having one or more ring heteroatoms such as oxygen, nitrogen or sulfur in addition to the ring carbon atoms.

The term "alkyl" as used herein includes, unless otherwise indicated, saturated monovalent aliphatic hydrocarbon radicals having straight or branched moieties, preferably C ₁ -C ₁₂ Alkyl groups and most preferably C ₁ -C ₆ -an alkyl group. Examples of alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl or hexyl, preferably methyl or ethyl and most preferably methyl.

Unless otherwise indicated, the term "alkylene" as used herein includes saturated divalent aliphatic hydrocarbon groups having a straight or branched moiety, preferably C ₂ -C ₁₂ Alkylene groups and most preferably C ₂ -C ₆ -an alkylene group. Examples of alkylene groups are ethylene, propylene, isopropylene, butylene, isobutylene, t-butylene, pentylene or hexylene, preferably ethylene, propylene, isopropylene or butylene and most preferably ethylene, propylene or isopropylene.

The term "cycloalkyl" as used herein includes cyclic saturated monovalent hydrocarbon groups having 5 to 7 ring carbon atoms, unless otherwise specified. An example of a cycloalkyl group is cyclohexyl.

The term "aryl" as used herein includes, unless otherwise indicated, aromatic groups derived from aromatic hydrocarbons by removal of one hydrogen, such as, but not limited to, phenyl or naphthyl.

The term "aralkyl" as used herein means, unless otherwise specified, an "aryl-alkyl-" group such as, but not limited to, benzyl (C ₆ H ₅ -CH ₂ (-) or methylbenzyl (CH) ₃ -C ₆ H ₄ -CH ₂ -)。

The term "alkyl-aryl" as used herein means, unless otherwise specified, an "alkyl-aryl-" group, such as, but not limited to: methylphenyl (CH) ₃ -C ₆ H ₄ (-) dimethylphenyl ((CH) ₃ ) ₂ -C ₆ H ₃ (-) or isopropylphenyl ((CH) ₃ ) ₂ C-C ₆ H ₄ -)。

R ¹ Is a monovalent organic group. This is preferably selected from alkyl, cycloalkyl, aryl, aralkyl or alkyl-aryl groups, more preferably from C ₁ -C ₆ -alkyl, cyclohexyl or phenyl. Still more preferably R ¹ Is C ₁ -C ₃ Alkyl, most preferablyAnd (5) selecting methyl.

R ¹ Examples of (a) are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclohexyl or phenyl.

R ² 、R ³ 、R ⁴ And R is ⁵ Independently of one another, hydrogen, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 18 carbon atoms,

R ² 、R ³ 、R ⁴ And R is ⁵ Preferably selected from hydrogen, C ₁ -C ₈ -alkyl and phenyl, more preferably selected from hydrogen and C ₁ -C ₆ -alkyl, and even more preferably selected from hydrogen and C ₁ -C ₃ -alkyl, and most preferably selected from hydrogen and methyl.

R ² 、R ³ 、R ⁴ And R is ⁵ As C ₁ -C ₈ Examples of alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl and octyl.

R ⁶ 、R ⁷ And R is ⁸ Independently of one another, hydrogen or a radical of the formula (III) derived from glycidol.

The chain length of the oxyalkylene units in the individual molecules of formula (I) in the mixture is characterized by the integers n and m.

The integers m and n independently of one another have values from 0 to 10, preferably from 1 to 10 and more preferably from 1 to 8 and even more preferably from 2 to 6.

Preferably comprises R having the same groups ¹ To R ⁵ The groups differ in the value of n and/or m, more preferably in the value of (n+m).

In a mixture comprising compounds of formula (I), the sum of n+m of the individual compounds in the mixture is a number from 0 to 20, preferably from 1 to 15 and most preferably from 4 to 12.

In a mixture comprising compounds of formula (I), at least two structurally different compounds must be present. These comprise different compounds of the formula (I), for example the compounds of the formulae (Ia), (Ib) and/or (Ic) mentioned above.

The oxyalkylene moieties in a single compound of a mixture of structurally different compounds of formula (I) may have different chain lengths (=different values of n and/or m or the sum of m+n).

A particularly preferred example is a mixture of structurally different phosphine oxides of the formula (I), wherein R ¹ Is C ₁ -C ₃ -alkyl, R ² 、R ³ 、R ⁴ And R is ⁵ Each hydrogen, and the oxyalkylene moieties in a single compound have different chain lengths (=different values of n and/or m or m+n).

In a further preferred embodiment of the invention, the mixture of phosphine oxides contains at least one compound of the formula (VI) in addition to at least two structurally different compounds of the formula (I)

Wherein the method comprises the steps of

R ² 、R ³ 、R ⁴ 、R ⁵ M and n are as defined above,

R ¹⁴ and R is ¹⁵ Each identical or different and independently of one another hydrogen, an alkyl radical having from 1 to 8 carbon atoms or an aryl radical having from 6 to 18 carbon atoms, and

r and n and m are independently integers from 0 to 10, preferably from 1 to 10.

Very particular preference is given to mixtures of phosphine oxides comprising at least one compound of the formula (VI) in which R is in addition to at least two structurally different compounds of the formula (I) ² Or R is ³ One of them is hydrogen and R ² Or R is ³ The other of (a) is hydrogen, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 18 carbon atoms, and wherein R ⁴ Or R is ⁵ One of them is hydrogen and R ⁴ Or R is ⁵ The other of (2) is hydrogen, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 18 carbon atoms, and wherein R ¹⁴ Or R is ¹⁵ One of them is hydrogen and R ¹⁴ Or R is ¹⁵ The other of (2) is hydrogen, an alkyl group having 1 to 8 carbon atoms or a compound having 6-Aryl groups of 18 carbon atoms.

Even more preferred are mixtures of phosphine oxides comprising at least two structurally different compounds of formula (I) and at least one compound of formula (VI).

The compounds of formula (VI) are analogous to those of formula (I), but the former bear the group-O- (CHR) ¹⁴ –CHR ¹⁵ -O) _r -H is other than the radical R ¹ (=trifunctional compound with three alkylene oxide groups).

Preferably, the difunctional compounds of formula (I) are present in an amount of from 50 to 100, more preferably from 90 to 100 and even more preferably from 90 to 99.5% by weight, with reference to the total amount of the mixture of compounds of formulae (I) and (VI).

Preferably, the content of trifunctional compounds of formula (VI) is 50-0, more preferably 10-0 and even more preferably 10-0.5% by weight, referred to the total amount of the mixture of compounds of formulae (I) and (VI).

Mixtures of structurally different compounds of formula (I) may be prepared by standard reactions known to the skilled person.

The alkylene oxide of formula (I) may be prepared by reacting a bis-hydroxymethyl-phosphine oxide of formula (VI I) with one or more epoxides of formula (VIII)

Wherein R is ¹ 、R ² And R is ³ As defined above.

The amounts of bis-hydroxymethyl-phosphine oxide and epoxide are selected in such a way that the desired number of recurring alkylene oxide units is obtained.

The reaction between the compounds of formulae (VI I) and (VIII) may be initiated by mixing the compounds and by heating these compounds in the presence of a basic compound, such as an alkali metal hydroxide, e.g. sodium hydroxide or potassium hydroxide. The reaction temperature may vary within a wide range, for example between 50 and 200 ℃. During the reaction, the reaction mixture is preferably stirred, for example by using a stirrer.

The reaction may be carried out at atmospheric pressure, preferably at reduced pressure, for example between 1 and 10 ⁵ Pa, preferably 10 to 10 ⁴ The pressure range of Pa.

The reaction can also be carried out in solution using an organic solvent which is inert under the reaction conditions. Examples of solvents are aprotic organic solvents such as dimethyl sulfoxide, dimethylformamide or dimethylacetamide, or aromatic hydrocarbons such as benzene, toluene or xylene.

The phosphine oxide starting materials of the formula (VI I) are known compounds or can be prepared using standard procedures of phosphorus-organic chemistry.

The epoxide starting materials of formula (VIII) are known compounds or can be prepared using standard procedures of organic chemistry.

Examples of preferred epoxide starting materials are ethylene oxide, propylene oxide, styrene oxide or glycidol.

Surprisingly, it has been found that alkoxylated phosphine oxide compounds of formula (I) as defined above can be used to manufacture flame retardant polymers. A single compound of formula (I) or a mixture of structurally different compounds of formula (I) may be used in the manufacture of the polymer.

Surprisingly, the compounds of formula (I) provide excellent flame retardancy when incorporated into polymers, together with very low VOC emissions and hydrolysis resistance when subjected to high temperatures, preferably in polymers prepared from monomers having reactive hydroxyl groups, amino groups or epoxy groups, such as polyesters, polycarbonates, polyamides, polyurethanes and polyureas. Furthermore, polymer compositions comprising flame retardant polymers made from compounds of formula (I) show excellent extrudability and plasticity in different plastic articles.

The invention also relates to flame-retardant polymers comprising structural units of formula (X)

Wherein the method comprises the steps of

R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ N and m are as defined above.

Preferably, the flame retardant polymer comprises different structural units of formula (X), more preferably structural units of formula (Xa), (Xb) and/or (Xc) optionally in combination with structural units of formula (VIa)

Wherein R is ¹ 、R ^2a 、R ^3a 、R ^4a 、R ^5a 、R ² 、R ³ 、R ⁴ 、R ⁵ 、R ¹⁴ 、R ¹⁵ N and m are as defined above.

The amount of structural units of formula (X) in the polymers of the invention can vary within wide limits. In general, the amount of structural units of the formula (X) is from 0.5 to 30mol%, preferably from 0.5 to 20mol% and most preferably from 1 to 10mol%, referred to the total amount of polymer.

The polymers of the invention comprising structural units of the formula (X) can be prepared by standard reactions known to the skilled worker.

Thus, a polymer-forming mixture of polymerizable compounds is subjected to polymerization conditions, wherein the mixture comprises at least one compound of formula (I) and at least one compound copolymerizable with the compound of formula (I).

The polymer of the present invention may be any natural polymer (including modified by chemical treatment) or any synthetic polymer. Polymer blends may also be used. Suitable polymers include thermoplastic polymers, thermoplastic elastomeric polymers, elastomers or duroplastic polymers.

Thermoplastic polymers are preferred. The thermoplastic polymer may be selected from the following: polyamides, polycarbonates, polyesters, polyvinyl esters, polyvinyl alcohols, polyurethanes and polyureas. Preferred thermoplastic polymers are prepared from monomers having functional groups that are reactive with hydroxyl groups. These are preferably selected from the following: polyamides, polycarbonates, polyesters, polyvinyl alcohols, polyurethanes and polyureas.

Another preferred class of polymers are rigid plastic polymers. More preferably, these are selected from the following: polyurethanes, epoxy resins, phenolic resins, melamine resins, and unsaturated polyester resins.

Yet another preferred class of polymers are thermoplastic elastomeric polymers. These constitute different types and are known to the skilled person.

Examples of thermoplastic elastomeric polymers include thermoplastic and elastomeric polyurethanes (TPE-U), thermoplastic and elastomeric polyesters (TPE-E), and thermoplastic and elastomeric polyamides (TPE-A).

The thermoplastic elastomeric polymers may be derived from different combinations of monomers. Typically, these blocks contain so-called hard segments and soft segments. The soft segments are typically derived from polyalkoxy glycol ethers in TPE-U and TPE-E and from amino-terminated polyalkoxy glycol ethers in TPE-A. The hard segments are typically derived from short chain diols or diamines in TPE-U, TPE-A and TPE-E. The thermoplastic elastomeric polymer is also derived from aliphatic, cycloaliphatic and/or aromatic dicarboxylic acids or diisocyanates as a supplement to the diol or diamine.

Furthermore, mixtures of two or more polymers may be used, in particular thermoplastic materials and/or thermosetting materials.

Examples of polymers are:

hydrocarbon resins, including hydrogenated versions thereof (e.g., tackifier resins) and mixtures of polyalkylene and starch.

The polymers are derived from alpha-, beta-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, butyl acrylate impact modified polymethyl methacrylates, polyacrylamides and polyacrylonitriles, and copolymers of the mentioned monomers with each other or with other unsaturated monomers, such as acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.

The polymers are derived from unsaturated alcohols and amines, or from their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate or polyvinyl maleate, polyvinyl butyral, polyallylphthalate, polyallylmelamine; and copolymers thereof with olefins.

Homopolymers and copolymers of cyclic ethers, for example polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.

Polyacetals such as polyoxymethylene, and those polyoxymethylene which contain comonomers such as ethylene oxide; polyacetal modified with thermoplastic polyurethane, acrylate or MBS.

Polyphenylene oxides and sulfides and mixtures thereof with styrene polymers or polyamides.

Polyurethanes derived from polyethers, polyesters or polybutadienes having two terminal hydroxyl groups and aliphatic or aromatic polyisocyanates, and precursors thereof.

Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example nylon 2/12, nylon 4/6, nylon 6, K122, zytel 7301, durethan B29, nylon 6/6Zytel 101, durethan A30, durethan AKV, durethan AM, ultramid A3, nylon 6/9. Nylon 6/9, nylon 6/10, nylon 6/12, nylon 6/66, nylon 7 nylon 7, nylon 8, nylon 9, nylon 10 nylon 10,9, nylon 10, nylon 11, nylon 12, grillamid L20, aromatic polyamides derived from meta-xylene, diamine and adipic acid; polyamides prepared from hexamethylenediamine and m-and/or terephthalic acid (poly-m-xylylenediamine, poly-p-xylylenediamine) and optionally elastomers as modifiers, for example poly-p-xylylenediamine-2, 4-trimethylhexamethylenediamine or poly-m-xylylenediamine. Block copolymers of the foregoing polyamides with polyolefins, olefin copolymers, ionomers, or chemically bonded or grafted elastomers; or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. In addition, EPDM-or ABS-modified polyamides or copolyamides; and polyamides that are polycondensed during processing ("RIM polyamide systems").

Polyureas, polyimides, polyamide-imides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.

Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1, 4-dimethylolcyclohexyl terephthalate, polyhydroxybenzoates and block polyether esters derived from polyethers having hydroxyl end groups; polyesters modified with polycarbonates or MBS.

Polycarbonates, polyester carbonates, polysulfones, polyether sulfones and polyether ketones.

The rigid plastic or thermosetting polymer or resin is preferably a polyurethane resin, an epoxy resin, a phenolic resin, a melamine-formaldehyde resin, a urea-formaldehyde resin and/or an unsaturated polyester.

The thermosetting resin is preferably a polyurethane resin, an epoxy resin or an unsaturated polyester resin.

The thermosetting polymers are preferably used in electrical switching components, components in automotive construction, electrical engineering, electronics, printed circuit boards, prepregs, potting materials for electronics, boat and rotor blade construction, outdoor GFRP applications, household and hygiene applications, engineering materials and other products.

Other polymers of the invention are rigid plastic polymers derived from aldehydes and phenols, urea or melamine, such as phenolic resins, urea-formaldehyde resins and melamine-formaldehyde resins.

Other polymers of the invention comprise crosslinkable acrylic resins derived from substituted acrylates, for example from epoxy acrylates, urethane acrylates or polyester acrylates.

Still other preferred polymers of the invention are epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, such as bisphenol a diglycidyl ether, the products of bisphenol F diglycidyl ether, which can be crosslinked with or without accelerators by means of conventional hardeners such as anhydrides or amines.

Still other preferred thermosets are polymers from the following classes: cyanate esters, cyanate ester/bismaleimide copolymers, bismaleimide/triazine epoxy blends, and butadiene polymers.

The epoxy resin is preferably a polyepoxide compound. The epoxy resin is preferably derived from the following: polyglycidyl-formaldehyde resins, polyglycidyl-urea-formaldehyde resins, polyglycidyl-melamine-formaldehyde resins and bisphenol resins.

Preferred epoxy resins are diglycidyl esters of bisphenol A, diglycidyl esters of bisphenol F, polyglycidyl esters of phenolic resins and cresol-formaldehyde resins, polyglycidyl esters of phthalic acid, isophthalic acid and terephthalic acid, and trimellitic acid, N-glycidyl compounds of aromatic amines and heterocyclic nitrogen bases, and di-and polyglycidyl compounds of polyhydric aliphatic alcohols.

Suitable hardeners are aliphatic, cycloaliphatic, aromatic and heterocyclic amines or polyamines, such as ethylenediamine, diethylenetriamine, triethylenetetramine, propane-1, 3-diamine, hexamethylenediamine, aminoethylpiperazine, isophoronediamine, polyamide-amine, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfone, aniline-formaldehyde resins, 2, 4-trimethylhexane-1, 6-diamine, m-xylylenediamine, bis (4-aminocyclohexyl) methane, 2-bis (4-aminocyclohexyl) propane, 3-aminomethyl-3, 5-trimethylcyclohexylamine (isophoronediamine), polyamide-amine, cyanoguanidine and dicyandiamide, and the same polyacids or anhydrides thereof, such as phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride, and phenols such as phenol-novolac resins, cresol-novolac resins, dicyclopentadiene-phenol adduct resins, phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins, bisphenol-modified phenol aralkyl resins, phenol-trimethylol methane resins, tetraphenol ethane resins, naphthol-novolac resins, naphthol-phenol cocondensate resins, naphthol-cresol cocondensate resins, bisphenol-modified phenol resins, and aminotriazine-modified phenol resins. All hardeners can be used alone or in combination with one another.

Suitable catalysts or accelerators for crosslinking in the polymerization are tertiary amines, benzyldimethylamine, N-alkylpyridines, imidazoles, 1-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, lewis acids, metal salts of organic acids and amine complex salts.

Other preferred polymers of the invention are crosslinked polymers derived from aldehydes on the one hand and phenols, ureas or melamines on the other hand, such as phenolic resins, urea-formaldehyde resins and melamine-formaldehyde resins. The polymer preferably comprises a crosslinkable acrylic resin derived from a substituted acrylic ester, for example from an epoxy acrylate, a urethane acrylate or a polyester acrylate.

Highly preferred polymers of the invention are polyurethanes and polyureas. Most preferred is polyurethane.

Polyurethanes are polymers composed of organic units linked by urethane linkages while polyureas contain carbon-amide linkages. Polyurethanes and polyureas can be thermosetting polymers that do not melt when heated; thermoplastic polyurethanes and polyureas are also useful.

Polyurethanes are often formed by reacting di-or triisocyanates with polyols. Both the isocyanate and the polyol used to prepare the polyurethane contain an average of two or more functional groups per molecule. Diols and diisocyanates result in linear polyurethanes, and crosslinked polyurethanes can be prepared, for example, by converting a triisocyanate diisocyanate mixture with a triol-diol mixture. The properties of the polyurethanes can vary within wide limits. Depending on the degree of crosslinking and/or the isocyanate or OH component used, thermoset, thermoplastic or elastomer materials are obtained. Polyurethane foam is of paramount importance as a soft or hard foam. However, polyurethanes are also used as molding compounds for molding, as casting resins (isocyanate resins), as (textile) elastic fibers, polyurethane coatings and as polyurethane adhesives.

The properties of polyurethane resins are greatly affected by the type of isocyanate and polyol used in their manufacture. The long soft segments contributed by the polyol result in flexible, elastic and/or thermoplastic polyurethanes. Higher amounts of crosslinking monomer give tough or rigid polyurethanes. Short chains with many crosslinks produce hard thermoset polyurethanes. The crosslinked polyurethane comprises a three-dimensional network and has a very high molecular weight. Rigid plastic polyurethanes do not soften or melt when they are heated; they are thermosetting polymers.

Polyols are compounds having an average of two or more hydroxyl groups per molecule. Polyol chain length and functionality contribute significantly to polyurethane properties. Polyols used to prepare rigid or thermoset polyurethanes have molecular weights of several hundred, while polyols used to prepare flexible or thermoplastic polyurethanes have molecular weights of several thousand.

The thermoset polyurethane is preferably derived from a polyol, preferably an aliphatic polyol having a low molecular weight with two, three or four hydroxyl groups, such as from ethylene glycol, propylene glycol, trimethylol propane or pentaerythritol, and from aliphatic or aromatic polyisocyanates and their precursors.

The starting materials for the preparation of the polyurethanes are, for example, aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic polyisocyanates (see, for example, W.Siefken, jus tus Liebigs Annalen der Chemie,562, pages 75 to 136), for example of the formula Q (NCO) _r Wherein r=2 to 4, preferably 2 to 3, and Q is an aliphatic hydrocarbon group having 2 to 18 carbon atoms, preferably 6 to 10 carbon atoms, a cycloaliphatic hydrocarbon group having 4 to 15 carbon atoms, preferably 5 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, preferably 6 to 13 carbon atoms, or an araliphatic hydrocarbon group having 8 to 15 carbon atoms, preferably 8 to 13 carbon atoms. Suitable polyisocyanates are aromatic, cycloaliphatic and/or aliphatic polyisocyanates having at least two isocyanate groups and mixtures thereof. Aromatic polyisocyanates such as tolylene diisocyanate, methylenediphenyl diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, tris (4-isocyanatophenyl) methane and poly (Methylene-polyphenylene diisocyanate; alicyclic polyisocyanates such as methylene diphenyl diisocyanate, tolylene diisocyanate; aliphatic polyisocyanates and hexamethylene diisocyanate, isophorone diisocyanate, dimeric (dimethyl) diisocyanate, 1-methylenebis (4-isocyanatocyclohexane-4, 4' -diisocyanatodicyclohexylmethane isomer mixtures, 1, 4-cyclohexyldiisocyanate, desmodur products (Bayer) and lysine diisocyanate and mixtures thereof.

Polyisocyanates which are readily available industrially and are derived from toluene 2, 4-and/or 2, 6-diisocyanate or from diphenylmethane 4,4 '-and/or 2,4' -diisocyanate are generally particularly preferred.

Suitable polyisocyanates are modified products obtained by reaction of polyisocyanates with polyols, urea, carbodiimide and/or biuret.

Other starting materials for preparing the polyurethanes or polyureas of the present invention are compounds having at least two hydrogen atoms which are capable of reacting with isocyanates and having a molecular weight of from 400 to 10,000 ("polyol components"). These are compounds having amino groups, thio groups or carboxyl groups, and preferably having hydroxyl groups, in particular 2 to 8 hydroxyl groups, and in particular those having a molecular weight of 1000 to 6000, preferably 2000 to 6000, and are generally binary to eight-membered, preferably binary to six-membered polyethers or polyesters, or polycarbonates or polyesteramides, as are known per se for the preparation of homogeneous or cellular polyurethanes, and as described, for example, in DE-A28 32253.

Preferred polyester polyols are obtained by polycondensation of polyols such as ethylene glycol, diethylene glycol, propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, methylpentanediol, 1, 6-hexanediol, trimethylolpropane, glycerol, pentaerythritol, diglycerol, glucose and/or sorbitol with dibasic acids such as oxalic acid, malonic acid, succinic acid, tartaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid and/or terephthalic acid. These polyester polyols may be used alone or in combination.

Other starting materials which may be used are compounds having at least two hydrogen atoms which are capable of reacting with isocyanates and having a low molecular weight, for example from 30 to 500. Again, in this case, these are compounds having hydroxyl groups and/or amino groups and/or thio groups and/or carboxyl groups, preferably compounds having hydroxyl groups and/or amino groups and acting as chain extenders or crosslinkers. These compounds generally have from 2 to 8, preferably from 2 to 4, hydrogen atoms which are capable of reacting with isocyanates.

Still other preferred thermosetting polymers of the present invention are unsaturated polyester resins (UP resins) derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyols and vinyl compounds as crosslinking agents.

The UP resin is cured by free radical polymerization using an initiator (e.g., peroxide) and an accelerator.

The unsaturated polyesters may contain ester groups as linking elements in the polymer chain.

Preferred unsaturated dicarboxylic acids and derivatives for the preparation of unsaturated polyesters are maleic acid, maleic anhydride and fumaric acid, itaconic acid, citraconic acid and mesaconic acid. These may be blended with up to 200 mole% (based on the unsaturated acid component) of at least one aliphatic saturated or cycloaliphatic dicarboxylic acid.

Preferred saturated dicarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, dihydrophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylene tetrahydrophthalic acid, adipic acid, succinic acid, sebacic acid, glutaric acid, methylglutaric acid, pimelic acid.

Preferred polyhydric, especially dihydric, optionally unsaturated alcohols are conventional alkane diols and oxaalkane diols having acyclic or cyclic groups.

Preferred unsaturated monomers copolymerizable with the monomers for preparing the unsaturated polyesters preferably bear vinyl, vinylidene or allyl groups, such as preferably styrene, and e.g. cyclo-alkylated or alkenylated styrenes, wherein the alkyl groups may contain 1 to 4 carbon atoms, such as vinyltoluene, divinylbenzene, alpha-methylstyrene, t-butylstyrene; vinyl esters of carboxylic acids having 2 to 6 carbon atoms, preferably vinyl acetate, vinyl propionate, vinyl benzoate; vinyl pyridine, vinyl naphthalene, vinyl cyclohexane, acrylic acid and methacrylic acid and/or their esters (preferably vinyl, allyl and methallyl esters) having 1 to 4 carbon atoms in the alcohol component, their amides and nitriles, maleic anhydride, maleic acid monoesters and diesters having 1 to 4 carbon atoms in the alcohol component, maleic acid monoamides and diamides or cyclic imides, for example butyl acrylate, methyl methacrylate, acrylonitrile, N-methylmaleimide or N-cyclohexylmaleimide; allyl compounds such as allylbenzene and allyl esters such as allyl acetate, diallyl phthalate, diallyl isophthalate, diallyl fumarate, allyl carbonate, diallyl phthalate, diallyl carbonate, triallyl phosphate and triallyl cyanurate.

The preferred vinyl compound for crosslinking is styrene.

Preferred unsaturated polyesters may also have ester groups in the side chains, such as polyacrylates and polymethacrylates.

Preferred hardener systems for unsaturated polyesters are peroxides and accelerators.

Preferred accelerators are metal coinitiators and aromatic amines and/or UV light and photosensitizers, for example benzoin ethers and azo catalysts such as azoisobutyronitrile, mercaptans such as lauryl mercaptan, bis (2-ethylhexyl) sulfide and bis (2-mercaptoethyl) sulfide.

In one method of preparing a flame retardant copolymer, a polymer derived from at least one C ₄ -C ₈ At least one ethylenically unsaturated dicarboxylic anhydride of a dicarboxylic acid, at least one vinylaromatic compound and at least one polyol and then reacting with a flame retardant of formula (I) and/or (I I).

The invention also relates to polymer compositions comprising the flame retardant polymer of the invention as component a) and optionally additives as component b).

The amount of component b) can vary within wide limits. Typical amounts of component(s) b) are from 0 to 60% by weight, preferably from 1 to 50% by weight and more preferably from 5 to 30% by weight, referred to the total amount of the flame retardant polymer composition.

Examples of additives b) are antioxidants, blowing agents, further flame retardants, light stabilizers, heat stabilizers, impact modifiers, processing aids, glidants, processing aids, nucleating and clarifying agents, antistatic agents, lubricants such as calcium stearate and zinc stearate, viscosity and impact modifiers, compatibilizers and dispersants, dyes or pigments, drip retardants, additives for laser marking, hydrolysis stabilizers, chain extenders, softeners and/or plasticizers, fillers and/or reinforcing agents.

The flame retardant polymer composition according to the invention preferably contains an additional filler as component b). These are preferably selected from metal hydroxides and/or metal oxides, preferably alkaline earth metals such as magnesium hydroxide, aluminum hydroxide, silicates, preferably phyllosilicates, such as bentonite, kaolin, muscovite, pyrophyllite, white iron ore and talc or other minerals such as wollastonite, silica such as quartz, mica, feldspar and titanium dioxide, alkaline earth metal silicates and alkali metal silicates, carbonates, preferably calcium carbonate and talc, clays, mica, silica, calcium sulfate, barium sulfate, pyrite, glass beads, glass particles, wood flour, cellulose powder, carbon black, graphite and chalk.

The flame retardant polymer composition according to the invention preferably contains a reinforcing agent as component b), more preferably reinforcing fibers. These are preferably selected from glass fibers, carbon fibers, aramid fibers, potassium titanate whiskers, glass fibers being preferred. The incorporation of the reinforcing agent into the molding composition can be carried out in the form of recycled strands (rovings) or in the form of cut strands (short glass fibers). In order to improve the compatibility with the polymer matrix, the reinforcing fibers used may be provided with a coating and an adhesion promoter. Commonly used glass fibers typically have diameters in the range of 6 to 20 microns.

These additives b) may impart other desirable properties to the polymer compositions of the present invention. In particular, the mechanical stability can be increased by reinforcing with fibres, preferably with glass fibres.

The flame retardant polymer composition of the invention is preferably prepared by providing component a) and optionally b), for example by mixing or by incorporation into a masterbatch, and by incorporating component a) and optionally b) into a polymer or polymer mixture.

Component a) and optionally b) may be incorporated into the polymer composition by premixing all components as powders and/or pellets in a mixer and then homogenizing them in the polymer melt in a compounding device, such as a twin screw extruder. The melt is usually drawn off as strands, cooled and granulated. The components a) and optionally b) can also be introduced directly separately into the compounding device by means of a metering system. It is also possible to mix components a) and optionally b) into the finished polymer particles or powder and to process the mixture directly, for example on an injection molding machine, to form parts.

The method for producing flame-retardant polymer compositions is characterized in that component a) and optionally b) are incorporated into polymer pellets at elevated temperature in a compounding assembly and homogenized. The resulting homogenized polymer melt is then formed into strands, cooled, and dispensed. The resulting pellets are dried, for example, in a convection oven at 90 ℃.

It is likewise possible to mix components a) and optionally b) with the prepared polymer pellets/powder and to process the mixture directly, for example on a film blowing line or a fiber spinning line.

Preferably, the compounding device is selected from a single screw extruder, a multizone screw or a twin screw extruder.

The flame retardant polymer composition according to the invention is suitable for the preparation of molded parts, such as films, sheets, threads and fibers, for example by injection molding, extrusion, blow molding or compression molding.

The invention also relates to shaped parts produced from a composition comprising component a) and optionally b).

The resulting shaped part preferably has a rectangular shape with a regular or irregular base, or has a cube, mat or prismatic shape.

The polymer composition according to the invention is particularly suitable for the production of foams, preferably polyurethane foams.

The invention furthermore relates to the use of compounds of formula (I) and/or (I I) as defined above as monomers in the manufacture of flame retardant polymers.

Furthermore, the present invention relates to the use of the polymer composition comprising components a) and optionally b) for the manufacture of high resilience foam seats, rigid foam insulation boards, microcellular foam seals and mats, durable elastomeric wheels and tires, automotive suspension bushings, electrical potting materials, high performance adhesives, surface coatings and sealants, synthetic fibers, carpet liners, hard plastic parts and hoses.

Finally, the invention relates to the use of the polymer composition comprising components a) and optionally b) for the manufacture of electrical switching parts, parts in automotive structures, electrical engineering or electronics, printed circuit boards, prepregs, potting materials for electronic parts, boat and rotor blade structures, outdoor GFRP applications, household and hygiene applications and engineering materials.

Examples

Method/test + standard

Compatibility with Standard polyol

The flame retardant was dispersed in the polyols at different ratios using a mechanical stirrer. The dispersion was stored at 23℃for 48h. Thereafter, homogeneity of the dispersion was visually evaluated.

The following criteria (see table of "Properties XY") apply, where the more "x" the better

Grade	5％FR	10％FR	30％FR
				-	Two phases	Two phases	Two phases
x	Clarification/turbidity	Cloudiness	Two phases
				xx	Clarifying	Clarifying	Cloudiness
xxx	Clarifying	Clarifying	Clarifying

Hydrolytic stability test of flame retardant substances

A10% by weight solution of each compound in water was stirred at 100℃for 2 hours. Then pass through ³¹ The solution was analyzed by P NMR and titrated to see if a change in spectrum or acid number occurred.

Hydrolytic stability test of polyol compositions for PUR manufacture

The hydrolytic stability was determined by measuring the evolution of the acid number of the polyol-FR-water blend over time at elevated temperature. For this purpose, 90g of polyol, 9g of FR (10% (w/w)) and 4,5g of water (5% (w/w)) were homogenized by stirring at 1500rpm for 2 min. The samples were then stored at 40 ℃ and the acid number was determined after a given period of time. The samples were homogenized by stirring at 1500rpm for 2min prior to analysis. For reference, development of acid value of a polyol-water blend to which no FR was added was performed.

Raw materials and sources

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Synthesis example

Example 1: production of BMPO-PO having 1 equivalent PO

BMPO-PO was prepared by the reaction between BMPO and propylene oxide. In the process, 234g of propylene oxide, 500g of BMPO (90% purity) and 5.5g of potassium hydroxide were charged into a 3000mL glass reactor equipped with a magnetic bar. The glass reactor was heated in a constant temperature oil bath at 150℃for 48h. Unreacted PO and small molecules were removed under reduced pressure at 100deg.C to obtain a yellowish transparent liquid. The mixture contained 30% (n=0, m=0), 40% (n=1, m=0), 15% (n=1, m=1), 5% higher oligomers and 10% phosphorus-free diol.

Example 2: production of BMPO-PO having 2 equivalent PO

BMPO-PO was prepared by the reaction between BMPO and propylene oxide. In the process, 470g of propylene oxide, 500g of BMPO (90% purity) and 5.5g of potassium hydroxide were charged into a 3000mL glass reactor equipped with a magnetic bar. The glass reactor was heated in a constant temperature oil bath at 150℃for 48h. Unreacted PO and small molecules were removed under reduced pressure at 100deg.C to obtain a yellowish transparent liquid. The mixture contained 10% (n=0, m=0), 25% (n=1, m=0), 40% (n=1, m=1), 10% (n=2, m=1), 5% higher oligomers and 10% phosphorus-free diol.

Example 3: production of BMPO-PO having 3 equivalent PO

BMPO-PO was prepared by the reaction between BMPO and propylene oxide. In the process, 700g propylene oxide, 500g BMPO (90% purity) and 5.5g potassium hydroxide were charged into a 3000mL glass reactor equipped with a magnetic bar. The glass reactor was heated in a constant temperature oil bath at 150℃for 48h. Unreacted PO and small molecules were removed under reduced pressure at 100deg.C to obtain a yellowish transparent liquid. The mixture contained 10% (n=1, m=0), 40% (n=1, m=1), 30% (n=2, m=1), 10% higher oligomers and 10% phosphorus-free diol.

Example 6: production of BMPO-EO with 3 equivalent EO

BMPO-EO is prepared by the reaction between BMPO and ethylene oxide. In the process, 213g of ethylene oxide, 100g of BMPO (90% purity) and 0.5g of potassium hydroxide were charged into a 1000mL glass reactor equipped with a magnetic bar. The glass reactor was heated in a constant temperature oil bath at 150℃for 6h. Unreacted ethylene oxide and small molecules were removed under reduced pressure at 100 ℃ to obtain a yellowish transparent liquid. The mixture contained 10% (n=1, m=0), 40% (n=1, m=1), 30% (n=2, m=1), 10% higher oligomers and 10% phosphorus-free diol.

Properties of the flame retardant of the invention compared to the reference Material

Details of the selected syntheses (equivalents of alkylene oxide) and elements (phosphorus) of the examples of the invention are disclosed together with their miscibility in polyether-type (Arcol 1104) and polyester-type (Desmophen 60WB 01) polyols in table 1. One trend to be explained is that as the equivalents of PO employed in their synthesis are higher, the better the miscibility of BMPO-PO, i.e. BMPO-PO (item 3) is completely miscible even at 30% concentrations in the polyester polyol, whereas less PO results in non-uniformity at these high concentrations. EO produced an alkoxylation product of BMPO with less miscibility than PO using the same synthesis parameters (item 6 vs item 3). BMPO-PO (item 3) also performed better in those miscibility experiments in polyester-type polyols than the reference materials (Ref-1 to Ref-3). Of the polyether polyols, ref-1 and Ref-2 show the best miscibility of all selected examples.

Application examples

Hydrolytic stability of pure flame retardant materials

TABLE 2 hydrolytic stability of pure flame retardant materials in boiling water

In Table 2, the hydrolytic stability of BMPO-PO is shown compared to the commercially available reference materials Exolit OP 550 and Exolit OP 560. As expected, the propoxylated phosphine oxide showed no tendency to hydrolyze even after 4h of exposure to boiling water, whereas the reference material showed a significant increase in acid number after the same treatment. The effect of the latter can be attributed to the oxidation state of the phosphoric acid type (OP 550) or phosphonic acid type (OP 560) of the respective reference materials. The alkoxylated acids, i.e. phosphoric acid/phosphonic acid esters, have a much higher tendency to hydrolyze than the phosphine oxide-alkoxylates. Furthermore, the former releases free acid upon hydrolysis, while the latter releases hydroxymethyl moieties with much lower acidity.

Hydrolytic stability of flame retardant materials in polyol/water mixtures

Table 3 hydrolysis stability test: development of acid number of a mixture of polyol with 10% (m/m) of flame retardant and 5% (m/m) of water during storage at 40 ℃.

Table 3 shows the same trend as in table 2-only in a more application-no significant contribution of the increase in acid number compared to the neat polyol for item 3, indicating a similarly high hydrolytic stability of FR 1 during storage as the polyol. After 28 days of storage, the acid number of the neat polyol was 0.1 and was found to be as low as 1104 (polyether polyol) 0.5-those numbers when FR1 was added indicate no to negligible hydrolysis of FR. In contrast, exolit OP 550 shows after 11 days>40, which can be explained by hydrolysis of FR. />The same experiment in 60WB01 (polyester polyol) showed similar results. The acid numbers of the pure polyol and the FR 1-added system are shown to be identicalAn acid number of 1.9 indicates that FR 1-hydrolysis does not contribute to an increase in acid number. Exolit OP 550 showed a rapid increase in acid number (94.7 after 28 days) under the same conditions, indicating rapid hydrolysis of this material.

Polyurethane flexible foam formulation and application test results

TABLE 4 having a weight of 30kg/m ³ Polyurethane formulation with flame retardant for flexible foam of bulk density.

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* TCPP = tris (1-chloro-2-propyl) phosphate

Use in PUR foams

Table 5 application test results for flexible polyurethane foam.

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Table 5 shows that all formulations except Ref. FM-3 can be processed into stable flexible foams, where the trifunctional polyol TMPO-PO results in significant crosslinking and thus foam collapse. Collapse is, of course, the worst case for foam production. Uncollapsed formulations cannot be found in such polyether-type systems and thus show difficulties in using TMPO-PO.

Compared to Ref.FM-1 (TCPP) and FM-2 (BMPO-EO), 4 parts in FM-1 (BMPO-PO) was sufficient to reach a rating of "SE" in the FMVSS 302 test. The reason for the poor flame retardant properties of BMPO-EO-compared to its propoxylated analogues-is the low compatibility of the material with the polyol in which the material is dispersed. Delamination results in uneven distribution of the flame retardant in the final foam sample. Thus, some samples performed well while others failed completely (burned), resulting in an overall poor rating for B.

FM-1 has better air permeability and can achieve lower compression set values than Ref. FM-2. Both properties are advantageous for the latter application.

Both emission indicators "fogging" and "VOC" show successful covalent incorporation of BMPO-PO into polyurethane matrix, resulting in values below the critical value for automotive applications. The effect of "non-reactive" flame retardants can be seen in ref. Fm-1, where TCPP results in very high haze and VOC values, which is not acceptable for such automotive applications.

Claims

1. Phosphine oxides comprising a mixture of at least two structurally different compounds of formula (I)

Wherein the method comprises the steps of

R ¹ Is C ₁ -C ₆ -an alkyl group, a cyclohexyl group or a phenyl group,

n and m are each independently an integer from 0 to 10.

2. Phosphine oxides of formula (I) according to claim 1, wherein R ² Or R is ³ One of which is hydrogen and R ² Or R is ³ The other of (a) is hydrogen, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 18 carbon atoms, and wherein R ⁴ Or R is ⁵ One of which is hydrogen and R ⁴ Or R is ⁵ Is hydrogen, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 18 carbon atoms.

3. Phosphine oxides of formula (I) according to claim 2, wherein R ² Or R is ³ One of which is hydrogen and R ² Or R is ³ The other of (a) is hydrogen or an alkyl group having 1 to 2 carbon atoms, preferably methyl, and wherein R ⁴ Or R is ⁵ One of which is hydrogen and R ⁴ Or R is ⁵ The other of (a) is hydrogen or an alkyl group having 1 to 2 carbon atoms, preferably methyl.

4. A phosphine oxide according to at least one of claims 1 to 3, wherein R ² 、R ³ 、R ⁴ And R is ⁵ Independently of one another selected from hydrogen, C ₁ -C ₆ -alkyl and phenyl, more preferably selected from hydrogen and C ₁ -C ₆ -alkyl, and even more preferably selected from hydrogen and C ₁ -C ₃ -alkyl, and most preferably selected from hydrogen and methyl.

5. The phosphine oxide of at least one of claims 1 to 4, wherein R ¹ Is C ₁ -C ₃ -alkyl, and preferably methyl.

6. Phosphine oxide according to at least one of claims 1 to 5, wherein the sum of n+m of each of the phosphine oxides of formula (I) contained in the mixture is a number from 1 to 15, and most preferably a number from 4 to 12.

7. Phosphine oxide according to at least one of the claims 1 to 6, wherein the mixture comprises at least one compound of formula (VI) in addition to at least two structurally different compounds of formula (I)

Wherein the method comprises the steps of

R ¹⁴ And R is ¹⁵ Independently of one another, hydrogen, an alkyl radical having from 1 to 8 carbon atoms or an aryl radical having from 6 to 18 carbon atoms, and

r and n and m are independently integers from 0 to 10, preferably from 1 to 10.

8. The phosphine oxide of formula (I) according to claim 7, wherein R ² Or R is ³ One of which is hydrogen and R ² Or R is ³ The other of (a) is hydrogen, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 18 carbon atoms, and wherein R ⁴ Or R is ⁵ One of them is hydrogen and R ⁴ Or R is ⁵ The other of (a) is hydrogen, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 18 carbon atoms, and wherein R ¹⁴ Or R is ¹⁵ One of which is hydrogen and R ¹⁴ Or R is ¹⁵ Is hydrogen, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 18 carbon atoms.

9. Phosphine oxide according to at least one of the claims 1 to 8, wherein the alkylene oxide moieties in a single compound of a mixture of structurally different compounds of formula (I) have different values of n and/or m or the sum of m+n.

10. A flame retardant polymer comprising structural units of formula (X):

wherein the method comprises the steps of

R ¹ Is C ₁ -C ₆ -an alkyl group, a cyclohexyl group or a phenyl group,

n and m are each independently an integer from 0 to 10.

11. The flame retardant polymer according to claim 10, wherein the polymer comprises different structural units of formula (X).

12. The flame retardant polymer according to claim 11, wherein the polymer comprises at least two structural units of the formulae (Xa), (Xb) and/or (Xc), optionally in combination with structural units of the formula (VIa)

Wherein the method comprises the steps of

R ^2a And R is ^3a Independently of one another, hydrogen, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 18 carbons,

R ^4a and R is ^5a Independently of one another, an alkyl radical having from 1 to 8 carbon atoms or an aryl radical having from 6 to 18 carbon atoms, and

R ¹⁴ and R is ¹⁵ Independently of one another, hydrogen, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 18 carbon atoms.

13. Flame retardant polymer according to at least one of claims 10 to 12, wherein the amount of structural units of formula (X) in the polymer is 0.5-30mol%, preferably 0.5-20mol% and most preferably 1-10mol%, referred to the total amount of polymer.

14. Flame retardant polymer according to at least one of claims 10 to 13, wherein the polymer is a thermoplastic polymer, preferably selected from the following: polyamides, polycarbonates, polyesters, polyvinyl esters, polyvinyl alcohols, polyurethanes and polyureas.

15. Flame retardant polymer according to at least one of claims 10 to 13, wherein the polymer is a rigid plastic resin, preferably selected from polyurethane resins, epoxy resins, phenolic resins, melamine-formaldehyde resins, urea-formaldehyde resins and/or unsaturated polyesters.

16. The flame retardant polymer according to at least one of claims 10 to 15, wherein the polymer is a polyurethane.

17. A composition comprising

a) Flame retardant polymer according to at least one of claims 10 to 16, and optionally

b) At least one auxiliary agent.

18. The composition of claim 17, wherein the additive is selected from antioxidants, blowing agents, additional flame retardants, light stabilizers, heat stabilizers, impact modifiers, processing aids, glidants, processing aids, nucleating and clarifying agents, antistatic agents, lubricants such as calcium stearate and zinc stearate, viscosity and impact modifiers, compatibilizers and dispersants, dyes or pigments, anti-drip agents, additives for laser marking, hydrolytic stabilizers, chain extenders, softeners and/or plasticizers, fillers and/or reinforcing agents.

19. Shaped part prepared from a composition according to at least one of claims 17 to 18.

20. The use of a compound of formula (I) as claimed in claim 1 as a monomer in the manufacture of flame retardant polymers.

21. Use of the polymer composition according to at least one of claims 17 to 18 for the manufacture of high resilience foam seats, rigid foam insulation boards, microcellular foam seals and mats, durable elastomeric wheels and tires, automotive suspension bushings, electrical potting materials, high performance adhesives, surface coatings and sealants, synthetic fibers, carpet liners, hard plastic parts and hoses.

22. Use of the polymer composition according to at least one of claims 17 to 18 for the manufacture of electrical switching components, components in automotive structures, electrical engineering or electronics, printed circuit boards, prepregs, potting materials for electronic components, boat and rotor blade structures, outdoor GFRP applications, household and hygiene applications and engineering materials.