JPH0533710B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to amine salts of phosphonic acids and their use to make polyurethanes and polyisocyanurates more flame retardant. Polyurethanes and polyisocyanurates are usually made more flame retardant by adding phosphorus-containing compounds, halogen-containing compounds or mixtures thereof. One commonly used phosphorus-containing compound is dimethylmethylphosphonate (DMMP). However, there are certain problems with the use of DMMP. Firstly, it is a relatively volatile liquid (boiling point 181°C), which means that the substance may be lost by volatilization under some circumstances. Second, DMMP typically
Before the isocyanate is added, it is blended with the polyol used to make polyurethanes and polyisocyanurates, along with catalysts, blowing agents, and other ingredients. The formulations tend to be somewhat unstable if stored for long periods of time before use.
The viscosity of such formulations increases when left;
It will then be observed that the foam properties are variable when mixed with the isocyanate co-reactant. Ethanolamine salts of methylphosphonic acid and their use as additives for hydraulic fluids are disclosed in European Patent Application No. 0012106. It is an object of the present invention to provide a new phosphorus-containing flame retardant that provides a polyol formulation that is low volatility and stable on storage. Therefore, the present invention provides general formula a: [In the formula, R ¹ represents a hydrogen atom, a methyl group, or one negative charge, x and y represent an integer such that the positive and negative charges are the same, and R ² represents a hydrogen atom or a methyl group. R ³ represents an alkyl group having 2 to 4 carbon atoms substituted by 1 to 3 hydroxyl groups which may be substituted by an oxyalkylene chain, and these include more than one hydroxyl group is not attached, R ⁴ and R ⁵ may be the same or different, and
the same group as defined for R ³ or a hydrogen atom,
an alkyl group having 1 to 4 carbon atoms, a phenyl group, a benzyl group, or an alkyl group having 1 to 12 carbon atoms, a hydroxyl group optionally substituted by an oxyalkylene chain, and/or a halogen atom having 1 to 3 carbon atoms; It may therefore represent a phenyl group or a benzyl group substituted on an aromatic ring, or R ⁵ is of the formula: (In the formula, R ⁶ is an alkylene group having 2 to 4 carbon atoms,
Represents a phenylene group, xylylene group or diphenylmethane group, or has the following formula

[Formula] or

[Formula] represents a group represented by the following, and the aromatic ring of the R ⁶ group is an alkyl group having 1 to 12 carbon atoms, a hydroxyl group which may be substituted with an oxyalkylene chain, and/or a halogen having 1 to 3 carbon atoms. may be substituted by an atom and R ⁷ represents a hydrogen atom or a methyl group, or R ⁷ is absent if the nitrogen atom is positively charged; R ⁸ is a hydrogen atom or R ³ represents the same group as defined in , and n represents 1 or 2. ), or
or R ⁴ and R ⁵ may be combined with a nitrogen atom to form a 5- or 6-membered heterocycle, optionally containing one oxygen atom, provided that R ¹ is a hydrogen atom or one negative charge. and when R ₂ represents a hydrogen atom, the condition is attached that at least one of R ³ , R ⁴ and R ⁵ represents something other than a hydrogen atom or a β-hydroxyethyl group. ]
Provided is an amine salt of a phosphonic acid represented by: When the hydroxyl groups in R ³ , R ⁴ and R ⁵ are substituted with oxyalkylene groups, the chain has the following formula:

[Formula] or

[Formula] (In the formula, R ² represents the meaning defined above,
and p represents an integer of 1 to 10, preferably 1 to 4. ). When R ³ , R ⁴ or R ⁵ represents a C2-C4 alkyl group substituted by 1 to 3 hydroxyl groups, it is, for example, a 2-hydroxyethyl group, a 2-hydroxy-n-propyl group or a 2-hydroxyethyl group, a 2-hydroxy-n-propyl group or It may also be a trimethylolmethyl group. When R ⁴ or R ⁵ represents C1 -C4 alkyl, it can be, for example, methyl, ethyl, isopropyl, n-butyl or sec-butyl. When R ⁴ or R ⁵ represents a phenyl group or a benzyl group substituted on the aromatic ring by an alkyl group having 1 to 12 carbon atoms, this alkyl group is, for example, a methyl group, an ethyl group, an isopropyl group, n-
Butyl group, tert-butyl group, n-hexyl group, n-
It may be an octyl group, n-nonyl group or octadecyl group. Furthermore, non-limiting examples of R ³ , R ⁴ and R ⁵ are given in the table of amines of formula that can be used for the preparation of salts of formula a. R ¹ is preferably a methyl group. In formula a, R ² is preferably a methyl group, and
R ³ and R ⁴ are preferably hydroxyethyl groups. In formula a, R ¹ and R ² are preferably methyl groups. The amine salt of the present invention is methylphosphonic acid or the following formula: (wherein R ² represents the meaning defined above,
And R ¹⁶ represents a hydrogen atom or a methyl group. ) with an amine of the formula: (wherein R ² , R ⁴ , R ⁵ , Z ¹ , Z ² and Z ³ have the meanings defined above);
It may be prepared by reaction, optionally in an aqueous or organic solvent, and optionally under an inert gas atmosphere, and heating if necessary to form the salt. The amount of methylphosphonic acid or ester of the formula is such that it reacts with one or more amine groups in the amine of the formula to obtain monosalts, di-salts or more salts as desired. be. If methylphosphonic acid or its monomethyl ester is used, salt formation is rapid and mild conditions may be used. The acid and amine may simply be mixed at room temperature to form the salt. If the amine is a viscous liquid or solid, the mixture may be heated at e.g. 100°C to fully react.
It may be heated up to. Aqueous or organic solvents may be used if desired and removed at the end of the reaction. If DMMP is used, more aggressive reaction conditions are required to ensure salt formation.
The DMMP/amine mixture may be heated to 180°C, optionally under an inert gas atmosphere such as nitrogen gas. Heating at 100 to 180°C for several hours is required. If desired, the reaction may be carried out in an organic solvent, such as a hydrocarbon solvent such as toluene or xylene. Methylphosphonic acid and its salts, its esters, and amines used in the present invention are all known compounds. And it is manufactured by a known method. When producing products containing oxyalkylene chains, these can be done either by reacting an amine with an alkylene oxide and subsequently forming a salt, or by reacting an amine to form a salt which is then reacted with an alkylene oxide. The conjugation can be carried out either by causing Etherification can optionally be carried out before or after salt formation.
1 to 10 moles of ethylene oxide and/or propylene oxide may be used per mole of amine or salt. Alkoxylation may be carried out at temperatures from 30 to 200° C. in the presence or absence of a catalyst. Amines of the formula containing an oxyalkylene chain that can be used in the present invention include those of the formula: In the formula, R ² represents a hydrogen atom or a methyl group, and may be the same or different in each molecule,
R ¹¹ is a hydrogen atom, (-CH ₂ -CH ₃ -O-) _q --H or

[Formula], where q represents 1 to 4; R ¹² represents 1 such as a nonyl group;
represents an alkyl group having from 1 to 12 carbon atoms, and each m may be the same or different and represents 1 to 4; Non-limiting examples of amines of the formula that may be used are: H ₂ NCH ₂ CH ₂ OH HN(CH ₂ CH ₂ OH) ₂ N(CH ₂ CH ₂ OH) ₂

【formula】

[Formula] CH ₃ N (CH ₂ CH ₂ OH) ₂

[Formula] H ₂ N-C (CH ₂ OH) ₂ (CH ₃ ) ₂ NCH ₂ CH ₂ OH CH ₃ NHCH ₂ CH ₂ OH Propylan A260 (Diamond
ethylene diamine/alkylene oxide condensation products, such as those sold under the trademark Shamrock); Treatment with alkylene oxides such as those sold under the trademark Tanol R650X or Tanol R350X (Texaco) as described in U.S. Pat. No. 3,297,597; phenol/formaldehyde/diethanolamine Mannitz base, (In the formula, R ² represents the meaning defined above.)
and the following formula: and the following formula: It is a mixture of these oligomer compounds represented by: The amine salts of this invention may be used alone or in conjunction with other flame retardants such as those listed below to impart flame retardancy to rigid or flexible polyurethanes or polyisocyanurates. Polyurethanes and polyisocyanurates are made by reacting polyols with polyisocyanates in the presence of blowing agents and catalysts if foams are desired. The amount of polyisocyanate is varied to produce the desired product. The present invention provides 1 to 6, preferably 1 to 6
Applicable to the entire range of polymers with an isocyanate index of 4.5. Further embodiments of the present invention provide formulas a and/or b: [In the formula, R ¹ represents a hydrogen atom, a methyl group, or one negative charge, x and y represent an integer such that the positive and negative charges are the same, and R ² represents a hydrogen atom or a methyl group. R ³ represents an alkyl group having 2 to 4 carbon atoms substituted by 1 to 3 hydroxyl groups which may be substituted by an oxyalkylene chain, and these include more than one hydroxyl group is not attached, R ⁴ and R ⁵ may be the same or different, and
the same group as defined for R ³ or a hydrogen atom,
an alkyl group having 1 to 4 carbon atoms, a phenyl group, a benzyl group, or an alkyl group having 1 to 12 carbon atoms, a hydroxyl group optionally substituted by an oxyalkylene chain, and/or a halogen atom having 1 to 3 carbon atoms; It may therefore represent a phenyl or benzyl group substituted on an aromatic ring, or R ⁵ is of the formula: (In the formula, R ⁶ is an alkylene group having 2 to 4 carbon atoms,
Represents a phenylene group, xylylene group or diphenylmethane group, or has the following formula

[Formula] or

[Formula] represents a group represented by the following, and the aromatic ring of the R ⁶ group is an alkyl group having 1 to 12 carbon atoms, a hydroxyl group which may be substituted with an oxyalkylene chain, and/or a halogen having 1 to 3 carbon atoms. may be substituted by an atom and R ⁷ represents a hydrogen atom or a methyl group, or R ⁷ is absent if the nitrogen atom is positively charged; R ⁸ is a hydrogen atom or R ³ represents the same group as defined in , and n represents 1 or 2. ), or
or R ⁴ and R ⁵ may be combined with a nitrogen atom to form a 5- or 6-membered heterocycle, optionally containing one oxygen atom] mixed inside. Concerning polyurethane or polyisocyanurate. When using an amine salt derived from a polyol, it may be used alone as the sole polyol component to react with a polyisocyanate to produce a polyurethane or polyisocyanurate. In many cases where such high levels of flame retardants are not required, the salt may be incorporated into the polyurethane or polyisocyanurate by adding it to the reaction mixture used to make the polyurethane or polyisocyanurate. Alternatively, the amine salt of the invention may be added to the hydroxyl group-containing reactant (polyester or polyether polyol) before reacting with the polyisocyanate. When using amines containing hydroxyl groups, they commonly react with isocyanates as well as polyols. The viscosity of the polyolamine salt mixture does not appreciably change upon storage at room temperature, and constant foaming conditions are achieved that do not vary with storage time. Alternatively, the prepolymer is prepared by reacting an amine salt of formula a with a polyisocyanate to give a product with either isocyanate or hydroxy end groups, and the polymer is then converted into a polyol or polyisocyanate. It is produced by further reaction with The amount of the amine salt flame retardant of the present invention that can be incorporated into the polyurethane or polyisocyanurate will depend on the degree of flame retardancy required. In those cases where polyols are also used, typical amounts of amine salt flame retardant may be from 1 to 200 parts by weight, preferably from 3 to 100 parts by weight, per 100 parts by weight of polyol. Amine salts may be mixed with other flame retardant compounds. These may be, for example, halogen atom-containing compounds such as aliphatic and aromatic bromine compounds, oxyalkylated phosphates, chloroalkyl phosphates, phosphonates or triaryl phosphates. Examples of suitable compounds are pentabromo-diphenyl ether, dibromocresyl glycidyl ether, tetrabromobisphenol A, dibromonepentyl glycol, diols prepared by reaction of tetrabromo-phthalic anhydride with ethylene oxide and/or propylene oxide, Tris (chloroethyl) phosphate,
Tris(monochloropropyl) phosphate, diethyl bis-(hydroxyethyl)-aminoethyl phosphonate, and mixtures of isopropylated or tertiary-butylated phenyl phosphates, tricresyl phosphate, as described in GB 1146173. ate, tricylyl phosphate and cresyl diphenyl phosphate. The ratio of hydroxyamine salt to other flame retardants may be from 5:95 to 95:5. The polyurethane and polyisocyanurate compositions may also contain unreacted amine-reacted methylphosphonic acid and its monomethyl or dimethyl esters, but preferably no acidic additives are present in the formulation. The isocyanates and polyols used in producing the polyurethanes and polyisocyanurates may be any of those known in practice. Isocyanates typically include toluene diisocyanate, methylene diphenyl diisocyanate, high molecular weight methylene diphenyl diisocyanate, hydrogenated methylene diphenyl diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and polyisocyanate prepolymers containing two or more unreacted isocyanate groups. It is a liquid such as. As is conventional, the toluene diisocyanate used in the present invention includes isomers of 2,4- and 2,4-toluene diisocyanate. The concentrations of these isomers are not critical. For rigid foams, polyols can be combined with polyhydroxy compounds such as glycerol, sutucarose, sorbitol, trimethylolpropane, pentaerythritol, triethanolamine, or with amines such as ethylenediamine, polyaromatic amines, or aromatic Mannitz bases. It may also be a polyfunctional active hydrogen compound derived from reaction with propylene oxide and/or ethylene oxide. Generally, for the production of flexible polyurethane foams the polyols are polyoxyethylene/oxypropylene diol, polyoxyethylene/oxypropylene triol, castor oil and
Polyether polyols such as methyl glucoside polyether polyols having an average molecular weight in the range of 6500. Other polyols that may be used in place of the polyether polyols are aliphatic difunctional carboxylic acids such as adipic acid, sebacic acid and difunctional carboxylic acids such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butylene glycol and butanetriol. or a polyester polyol such as a reaction product with a trifunctional hydroxy compound. Additionally, polyols such as glycerol, hexanetriol, butanetriol, trimethylolpropane, trimethylolethane, and pentaerythritol may be used in the polymerization reaction with the polyol to maintain the desired stoichiometrically balanced ratio of isocyanate groups to hydroxyl groups. May be included. When producing foamed polyurethanes and polyisocyanurates, e.g. sodium hydroxide, sodium acetate, tertiary amines, or trimethylamine, triethylenediamine, N-methylmorpholine, N,N-dimethylcyclohexylamine and N,N-dimethylamino Any conventional base catalyst can be used, such as tertiary amine producing materials such as ethethanol. Hydrocarbon tin alkyl carboxylates, metal compounds such as dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate and tin octoate, and 2,4,6-tris(N,N-dimethylamino-methyl)phenol, 1, 3,5-tris(N,N-dimethyl-
Other compounds that promote trimerization of isocyanates such as 3-aminopropyl)-S-hexahydrotriazine, potassium octoate, potassium acetate, and DABCO
TMR ) and POLYCAT43
Catalysts, such as those sold under the trademark , are also applicable. Many other catalysts may be substituted for those described above, if desired. The amount of catalyst used is approximately 0.05% by weight relative to the total weight of the polyol used.
It may range from about 5% by weight or more. Mixtures of the above and/or other catalysts may also be used. The blended polyol-polyisocyanate mixture must be added or made in situ with a suitable blowing agent or blowing agent system to provide an open cell or closed cell structure. Suitable blowing agents include liquid but relatively volatile halogenated hydrocarbons such as dichlorodifluoromethane, trichlorofluoromethane and methylene chloride. These are about 5% to about 50% by weight of the polyol.
is added as a liquid to one or more components of the polyol-polyisocyanate mixture and substantially volatilized in the liquid mixture to form closed cell cells. Subsequently, the mixture is cured to its final closed cell form. Halogenated hydrocarbons are particularly desirable as blowing agents when special insulating properties are derived, but other blowing agents, such as carbon dioxide generated by adding water to polyols or by adding isocyanates at the same time, are Especially available for open cell forms. It should also be noted that the formation of foam may still be carried out together with the use of blowing agents and the addition of water to the polyol. Emulsifiers and/or surfactants may be incorporated into the mixture to achieve a relatively uniform distribution of the various components of the liquid system and the resulting foam formation. These materials are physical in effect and are not necessary, especially if dense foams are desired. Any of the hundreds of conventional surfactants can be used in amounts up to 4% based on the weight of the polyol used. Suitable surfactants are polydimethylsiloxane and polydimethylsiloxane polyalkylene copolymers and the like known to those skilled in the art. It is also within the scope of this invention to use other materials in the composition if desired to achieve a particular end result. Such materials are included without limitation in the Modern Plastics Encyclopedia.
(Modern Plastics Encyclopedia.) Volume 58, Number 10A, pages 170-187, adhesion promoters, antioxidants, antistatic agents, antimicrobial agents,
Contains colorants, heat stabilizers, light stabilizers, pigments, plasticizers, preservatives, UV stabilizers, and fillers. The invention will be explained in more detail by the following examples. In the examples, "parts" means parts by weight. Example 1 2245.6 parts of p-nonylphenol/formaldehyde/diethanolamine Mannitz base [Tanol Earl 650] reacted with 49.6 parts of dimethylmethylphosphonate and propylene oxide
It is sold under the trademark Thanol R650 _x . ] is heated to 120°C with stirring under a nitrogen atmosphere. Stirring is continued for 4 hours at 120°C, then the reaction mixture is transferred to a rotary evaporator and volatiles are removed by heating at 90°C for 2 hours at a pressure of 133 Pa. The residue consists of 266 parts of viscous liquid. The ³¹ P nuclear magnetic resonance chemical shift of the product is 23.8 ppm downfield, characteristic of a phosphonic acid/amine salt. Example 2 By a method similar to that described in Example 1,
81.8 parts dimethylmethylphosphonate and 202.6 parts Thanol R650 _x
) to produce 256 parts of a viscous liquid product ( ³¹ P
chemical shift = 23.5 ppm downfield). Example 3 By a method similar to that described in Example 1,
24.8 parts of dimethylmethylphosphonate and 106.0 parts of phenol/formaldehyde/diethanolamine Mannitz base (sold under the trademark Thanol R350 _x ) reacted with propylene oxide. ] to obtain 128.5 parts of a viscous liquid product ( ³¹ P chemical shift = 24.2 ppm downfield). Example 4 By a method similar to that described in Example 1,
49.6 parts dimethylmethylphosphonate and 106.0 parts Thanol
R350 _x ) to obtain 155.2 parts of a viscous liquid product ( ³¹ P chemical shift = 24.4 ppm downfield). Example 5 By a method similar to that described in Example 1,
62.0 parts of dimethylmethylphosphonate and 74.5 parts of triethanolamine are reacted exothermically.
132.2 parts of viscous liquid product ( ³¹ P chemical shift =
21.4ppm low field). Elemental analysis of the product: C=38.8%, H=9.7%, N=5.2%, P=11.1
%. The calculated values for C ₉ H ₂ DNO ₆ P are: C = 39.6%, H = 8.8%, N = 5.1%, P = 11.4
%. The product is essentially an amine/phosphonate salt. Example 6 By a method similar to that described in Example 1,
12.4 parts of dimethylmethylphosphonate and 10.5 parts of diethanolamine were reacted exothermically to produce 22.3 parts of a viscous liquid product ( ^31P chemical shift = 22.0 ppm
low magnetic field). The elemental analysis values of the product are: C = 36.0%, H = 9.4%, N = 6.0%, P = 13.3
%. The calculated values of C ₇ H ₂₀ NO ₅ P are: C=36.7%, H=8.7%, N=6.1%, P=13.5
%. The product is essentially an amine/phosphonate salt. Example 7 By a method similar to that described in Example 1,
31.0 parts dimethylmethylphosphonate and 67.5 parts ethylenediamine/alkylene oxide condensate (sold under the trademark Propylan A260). ] to obtain 96.1 parts of a viscous product ( ³¹ P chemical shift = 21.5 ppm downfield). Example 8 11.0 parts of methylphosphonic acid monomethyl ester and 61.4 parts of Thanol R650 _x are heated to 80° C. with stirring. Stirring is continued for 1.5 hours at 80°C. The reaction mixture is then transferred to a rotary evaporator and any volatile materials are removed by heating at 80° C. for 1 hour at a pressure of 133 Pa. The residual product is 68 parts viscous liquid ( ³¹ P chemical shift = 24.9 ppm downfield)
Consisting of Example 9 By a method similar to that described in Example 8,
22.0 parts of methyl phosphonic acid monomethyl ester and 61.4 parts of Thanol R650 _x are reacted to produce 80.2 parts of a viscous liquid product ( ³¹ P chemical shift = 25.2 ppm downfield)
get. Example 10 By a method similar to that described in Example 8,
22.0 parts methylphosphonic acid monomethyl ester and
51.0 by reacting 29.8 parts of triethanolamine
One part of a viscous product is obtained. ³¹ P chemical shift=
19.6ppm low field. Example 11 19.2 parts of methylphosphonic acid and 122.8 parts of Thanol _{R650 x are} heated to 100° C. with stirring. Stirring is continued for 30 minutes at 100°C. The reaction mixture is transferred to a rotary evaporator and any volatile materials are removed by heating at 80° C. for 1 hour at a pressure of 133 Pa. The residual product consists of 141.6 parts of a very viscous liquid ( ^31P chemical shift = 22.0 ppm downfield). Example 12 By a method similar to that described in Example 11,
19.2 parts of methylphosphonic acid and 59.6 parts of triethanolamine are reacted to yield 76.7 parts of a viscous liquid product ( ³¹ P chemical shift = 20.5 ppm downfield). Examples 13-24 The following examples illustrate flame retardant rigid foam polyurethane compositions that may be prepared from polyols and polymerizable diphenylmethane diisocyanates in accordance with the present invention. The following foam formulations are utilized to demonstrate the effectiveness of flame retardants. Reactant concentration (parts) Thanol R650x1 Water as directed 0.2 Silicone surfactant 2 Trichlorofluoromethane
40 (foam density 30±1Kg/ ^m3 ) Flame retardant Suprasec DMD2 as directed
Amount that gives an index of 1.05 1 is aromatic polyol, 2 is polymerizable diphenylmethane diisocyanate. The above ingredients are mixed together in a high speed stirrer (2000 rpm) for 10 seconds, with the isocyanate added at the end, and immediately poured into cardboard molds. The ensuing exothermic reaction spontaneously forms a foam. The length of time after the addition of the isocyanate until the mixture has formed a creamy consistency is referred to as the cream time. The time required for the foam to reach its maximum volume is referred to as the generation time. The time until the foam is no longer sticky is referred to as the non-stick time. After reaching the tack-free time, the foam is aged for 3 days at ambient temperature. After 3 days of storage, specimens were cut from the foam and subjected to the Limiting Oxygen Index Test and
DIN4102B2 Vertical Burn test
Do this. The results are shown in the table below, and for comparison, the same foam material is produced without flame retardant. Example
No cracking, distortion, or burning was observed in the foams obtained from No. 13 and No. 24.

【table】

TABLE Examples 25 and 26 The following examples illustrate flame retardant, flexible foam polyurethane compositions that may be prepared from polyols and toluene diisocyanate in accordance with the present invention. The following foam formulations were utilized to demonstrate the effectiveness of flame retardants. Reactant concentration (parts) Propylan B383 100 Silicone surfactant 1 Water 4 (foam density 28 + 1 Kg/m ² ) Stannous octoate 0.3 Propamine A 0.4 Flame retardant Toluene diisocyanate as directed Index 1.08 The above ingredients are mixed in a high-speed manual stirrer (2000 rpm).
Mix together for 10 seconds at room temperature and pour into cardboard molds as quickly as possible. The ensuing exothermic reaction spontaneously forms a foam. After the foam was cured for 7 days at ambient temperature, it was found to have the physical properties shown in the table below. For comparison, a foam is produced from the same reactants in the same manner, maintaining the isocyanate index at 1.08, but without the use of flame retardants. After storage for 3 days, specimens are cut from the foam and the specimens are subjected to a BS4735 horizontal burn test. The results are shown in the table below.

Table: Examples 27 and 28 The storage stability of polyol formulations containing the products of the invention is detailed below. Two formulations are produced and their viscosities are measured after production and after 39 days. Regarding the viscosity, there was a very slight difference on the one hand and no difference on the other hand.

【table】

Claims (1)

[Claims] 1 General formula a: [In the formula, R ¹ represents a hydrogen atom, a methyl group, or one negative charge, x and y represent an integer such that the positive and negative charges are the same, and R ² represents a hydrogen atom or a methyl group. R ³ represents an alkyl group having 2 to 4 carbon atoms substituted by 1 to 3 hydroxyl groups which may be substituted by an oxyalkylene chain, and these include more than one hydroxyl group is not attached, R ⁴ and R ⁵ may be the same or different, and
the same group as defined for R ³ or a hydrogen atom,
an alkyl group having 1 to 4 carbon atoms, a phenyl group, a benzyl group or an alkyl group having 1 to 12 carbon atoms, a hydroxyl group which may be substituted by an oxyalkylene chain, and or a halogen atom having 1 to 3 atoms; may represent a phenyl group or a benzyl group substituted on an aromatic ring, or R ⁵ may be of the formula: (In the formula, R ⁶ is an alkylene group having 2 to 4 carbon atoms,
It represents a phenylene group, a xylylene group, a diphenylmethane group, or a group represented by the following formula [Formula] or [Formula], and the aromatic ring of R ⁶ group is an alkyl group having 1 to 12 carbon atoms, oxyalkylene a hydroxyl group which may be substituted by the chain, and/or which may be substituted by 1 to 3 halogen atoms, and R ⁷ represents a hydrogen atom or a methyl group, or if the nitrogen atom is positively charged R ⁷ is absent; R ⁸ represents a hydrogen atom or the same group as defined for R ³ and n represents 1 or 2. ), or
or R ⁴ and R ⁵ may be combined with a nitrogen atom to form a 5- or 6-membered heterocycle, optionally containing one oxygen atom, provided that R ¹ is a hydrogen atom or one negative When R 2 represents a charge and R ₂ represents a hydrogen atom, the condition is attached that at least one of R ³ , R ⁴ and R ⁵ represents something other than a hydrogen atom or a β-hydroxyethyl group. ] An amine salt of phosphonic acid represented by 2. The amine salt according to claim 1, wherein R ¹ represents a methyl group. 3. The amine salt according to claim 1, wherein in formula a, R ² represents a methyl group, and R ³ and R ⁴ represent a hydroxyethyl group. 4. The amine salt according to claim 1, wherein R ¹ and R ² represent a methyl group. 5 When the hydroxyl group in R ³ , R ⁴ and R ⁵ is substituted with an oxyalkylene chain, the chain has the following formula: [Formula] or [Formula] (wherein R ² represents a hydrogen atom or a methyl group) ,
And p represents an integer from 1 to 10. ) The amine salt according to claim 1, characterized in that it has the following. 6 Methylphosphonic acid or the following formula: (In the formula, R ² represents a hydrogen atom or a methyl group, and R ¹⁰ represents a hydrogen atom or a methyl group.) The ester represented by the following formula: [In the formula, R ³ represents an alkyl group having 2 to 4 carbon atoms substituted with 1 to 3 hydroxyl groups which may be substituted with an oxyalkylene chain, and these include any one carbon atom. does not have more than one hydroxyl group attached to it, R ⁴ and R ⁵ may be the same or different, and
the same group as defined for R ³ or a hydrogen atom,
an alkyl group having 1 to 4 carbon atoms, a phenyl group, a benzyl group or an alkyl group having 1 to 12 carbon atoms, a hydroxyl group which may be substituted by an oxyalkylene chain, and or a halogen atom having 1 to 3 atoms; may represent a phenyl group or a benzyl group substituted on an aromatic ring, or R ⁵ may be of the formula: (In the formula, R ⁶ is an alkylene group having 2 to 4 carbon atoms,
It represents a phenylene group, a xylylene group, a diphenylmethane group, or a group represented by the following formula [Formula] or [Formula], and the aromatic ring of R ⁶ group is an alkyl group having 1 to 12 carbon atoms, oxyalkylene a hydroxyl group which may be substituted by the chain, and/or which may be substituted by 1 to 3 halogen atoms, and R ⁷ represents a hydrogen atom or a methyl group, or if the nitrogen atom is positively charged R ⁷ is absent; R ⁸ represents a hydrogen atom or the same group as defined for R ³ and n represents 1 or 2. ), or
Alternatively, R ⁴ and R ⁵ may be combined with the nitrogen atom to form a 5- or 6-membered heterocycle, optionally containing one oxygen atom. ] Preparation of amine salts of phosphonic acids, comprising reacting with amines of the formula, optionally in an aqueous or organic solvent, optionally under an inert gas atmosphere, and heating if necessary to form the salt. Method. 7. A process according to claim 6, characterized in that the compound represented by the formula is dimethylmethylphosphonate, and the reaction is carried out by heating at a temperature of up to 200°C. 8 General formula a: [In the formula, R ¹ represents a hydrogen atom, a methyl group, or one negative charge, x and y represent an integer such that the positive and negative charges are the same, and R ² represents a hydrogen atom or a methyl group. R ³ represents an alkyl group having 2 to 4 carbon atoms substituted by 1 to 3 hydroxyl groups which may be substituted by an oxyalkylene chain, and these include more than one hydroxyl group is not attached, R ⁴ and R ⁵ may be the same or different, and
the same group as defined for R ³ or a hydrogen atom,
an alkyl group having 1 to 4 carbon atoms, a phenyl group, a benzyl group or an alkyl group having 1 to 12 carbon atoms, a hydroxyl group which may be substituted by an oxyalkylene chain, and or a halogen atom having 1 to 3 atoms; may represent a phenyl group or a benzyl group substituted on an aromatic ring, or R ⁵ may be of the formula: (In the formula, R ⁶ is an alkylene group having 2 to 4 carbon atoms,
It represents a phenylene group, a xylylene group, a diphenylmethane group, or a group represented by the following formula [Formula] or [Formula], and the aromatic ring of R ⁶ group is an alkyl group having 1 to 12 carbon atoms, oxyalkylene a hydroxyl group which may be substituted by the chain, and/or which may be substituted by 1 to 3 halogen atoms, and R ⁷ represents a hydrogen atom or a methyl group, or if the nitrogen atom is positively charged R ⁷ is absent; R ⁸ represents a hydrogen atom or the same group as defined for R ³ and n represents 1 or 2. ), or
or R ⁴ and R ⁵ may be combined with a nitrogen atom to form a 5- or 6-membered heterocycle, optionally containing one oxygen atom, provided that R ¹ is a hydrogen atom or one negative When R 2 represents a charge and R ₂ represents a hydrogen atom, the condition is attached that at least one of R ³ , R ⁴ and R ⁵ represents something other than a hydrogen atom or a β-hydroxyethyl group. ] A flame retardant for polyurethane and polyisocyanurate consisting of an amine salt of phosphonic acid represented by: