Phosphorus containing flame retardants

Phosphorus-containing flame retardant {PHOSPHORUS CONTAINING FLAME RETARDANTS}

This application claims priority to U.S. Patent Application Serial No. 14/592,472, filed January 8, 2015, and U.S. Patent Application Serial No. 14/337,500, filed July 22, 2014.

<u>technical field</u>

Certain phosphonates, or mixtures of such salts, heated to temperatures in excess of 200° C. produce thermally stable, highly efficient flame retardant materials well suited for use as flame retardant additives in polymers. Various methods are provided for making a flame retardant material from more than one phosphonic acid salt, each method capable of producing a different flame retardant material with the same mixture of starting phosphonic acids.

Polymers such as polyolefins, polyesters, polycarbonates, polyamides, polyurethanes, epoxy resins, and other thermoplastic or thermoset polymeric resins are often prepared by incorporating therein phosphorus-containing compounds, halogen-containing compounds, or mixtures thereof. make it more flame retardant. For example, US Pat. No. 3,689,602 discloses halogenated phosphoric acid esters as flame retardant additives for plastics.

Some polymers are processed at high temperatures, for example 200°C, 220°C, 250°C or higher, and many known flame retardants are not suitable under these conditions because they are too volatile, not sufficiently thermally stable, and process for reasons such as having an adverse effect on Certain organophosphorus flame retardant compounds, such as some phosphoric acid esters, may also exhibit plasticizing effects, which may adversely affect the mechanical properties of the polymer to which they are added. In addition, some phosphate-like compounds are relatively unstable to hydrolysis, which can lead to the unwanted formation of various phosphate compounds.

Salts of phosphorus containing acids are known flame retardant additives, especially for thermoplastic polymers. U.S. Patent 3,894,986 discloses flame retardant thermoplastic polyesters containing alkali salts of phosphonic acids, such as mono sodium salts of ethane-phosphonic acids or sodium salts of mono-methyl esters of alkane-phosphonic acids. U.S. Pat. No. 4,972,011 discloses aluminum salts of alkylphosphonic acids or mono-alkyl esters of alkane-phosphonic acids, ie salts of compounds of formula la, wherein R is, for example, unsubstituted or substituted with one or more halo or hydroxy groups. methyl, ethyl, propyl or isopropyl, etc.; R' is hydrogen, methyl, ethyl, propyl, or isopropyl.

[Formula Ia]

<img file="KR102403004B1_D0001.tif" />

DE 3833977 discloses metal salts of compounds of the formula Ia prepared by reacting dimethylmethylphosphinate with a metal oxide or hydroxide in water at high pressure and at a temperature of from 120° C. to 200° C.; The reaction carried out in an aqueous solution under high pressure at a temperature of up to 190° C. in an autoclave is exemplified. Adducts of these salts with amines such as ethylene diamine and melamine, and the use of these adducts as flame retardants in thermoplastics are also disclosed.

A salt of a phosphinic acid, i.e. a compound of formula II wherein R₁ and R₂is alkyl or carbon-based aromatic) are also known flame retardant additives for thermoplastic polymers.

[Formula II]

<img file="KR102403004B1_D0002.tif" />

Salts are known wherein M is selected from Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Li, Na, K or a protonated nitrogen base. For example, US Pat. Nos. 5,780,534 and 6,013,707 disclose that calcium phosphinate and aluminum phosphinate of formula II are particularly effective for polyesters, such as dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, n-propyl calcium and aluminum salts of methylphosphinic acid, n-propylethylphosphinic acid, di-n-propylphosphinic acid, diisopropylphosphinic acid or diphenylphosphinic acid.

As is common to many flame retardant systems, the performance of phosphorus containing acid derivatives can be enhanced by the presence of other flame retardants, synergists and adjuvants. U.S. Pat. No. 6,472,448 discloses a flame retardant, rigid polyurethane foam in which a combination of an oxalkylated alkylphosphonic acid and an ammonium polyphosphate is present as a flame retardant.

U.S. Pat. No. 6,365,071 discloses synergistic flame retardant formulations for thermoplastic polymers, such as engineering plastics, in particular for polyesters, which flame retardant formulations are A) a phosphinate of formula II above, for example aluminum dimethylphosphinate. , aluminum methylethylphosphinate, and aluminum methylpropylphosphinate and B) nitrogen compounds such as allantoin, i.e. (2,5-dioxo-4-imidazolidinyl) urea, benzoguanamine, glycoluril, i.e. tetrahydroimidazo[4,5-d]imidazole-2,5-dione, urea cyanurate, melamine cyanurate and melamine phosphate.

U.S. Pat. No. 6,255,371 discloses a flame retardant formulation comprising: A) a phosphinate of formula II above, for example diethyl phosphinate, wherein M is calcium, magnesium, aluminum and/or zinc, and B) condensation or reaction products of melamine, such as melamine polyphosphate, melam polyphosphate and melem polyphosphate.

U.S. Pat. No. 6,547,992 discloses a flame retardant formulation for a thermoplastic polymer comprising a phosphinate and minor amounts of inorganic and/or mineral compounds that do not contain nitrogen. WO 2012/045414 discloses a flame-retardant composition, wherein the flame-retardant composition is A) a phosphinic acid salt of formula II, wherein M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce , Bi, Li, Na, K or a protonated nitrogen base); B) metal salts of phosphorous acid; and other optional ingredients.

The phosphinates mentioned above, for example in US Pat. Nos. 6,365,071 and 6,255,371, are said to be thermally stable and do not degrade the polymer during processing nor affect the manufacturing process of the plastic composition. These phosphinates are nonvolatile under the conditions customary in the manufacture and processing of thermoplastic polymers. However, these materials are not necessarily suitable for use in all polymer systems and may cause problems in processing or may lack the flame retardant effectiveness required for certain polymers. There is still a need for flame retardants with improved processability for use in the preparation of flame retardant polymer compositions having higher efficacy with lower additive concentrations and having highly desirable physical properties.

Phosphonates, ie salts that are metal salts of compounds according to formula Ia, are also reported to be thermally stable, but this is of course a relative point of view. As disclosed in US 2007/0029532, the degradation of such phosphonates is well known at the temperatures encountered during the processing of polyesters and polyamides, which damage the polymers in such processes.

U.S. Pat. No. 5,053,148 discloses heat-resistant foams obtained by heating a metal phosphonate or metal phosphonate precursor to a temperature of greater than 200° C., which is useful, for example, as an electrical insulation and/or heat-insulating material. It is also disclosed that this reaction is used to foam or render other substrates porous. Such substrates include, for example, thermoplastic polymers or plastics, such as aromatic polyesters, polyethers, polysulfides, polyamides, polycarbonates, polyimides, polysiloxanes or polyphosphazenes, metal phosphonates and/or It can be introduced into the foaming operation as a mixture with its precursor.

While US Pat. No. 5,053,148 may suggest that a porous polyamide can be produced by heating a mixture of a metal phosphonate and a polyamide according to a "foaming process," nothing in US Pat. It does not counter or deny the disclosure of US 2007/0029532 that the decomposition of Except to suggest that porous foams can be produced by heating metal phosphonates and polymers such as polyamides, there is no mention in US Pat.

<p>The difficulties in thermal processing of certain thermoplastic resins in the presence of metal salts of alkylphosphonic acids, and the poor physical properties of the polymer compositions thus obtained, have been confirmed by experiments. However, the product obtained by heating certain alkylphosphonic acid metal salts, such as aluminum salts, calcium salts, zinc salts, etc., at a temperature above 200°C is thermally stable at a temperature above 400°C, resulting in the obtained polymer composition It has now been discovered that it can be thermally incorporated onto a thermoplastic polymer resin without adversely affecting its physical properties. In some cases, mixtures of these products, or products produced by heat treatment of mixtures of phosphonates, are used. It has also been found that polymer compositions comprising the flame retardants of the present invention, such as thermosetting or thermoplastic compositions, exhibit excellent flame retardant activity, either alone or in combination with other flame retardants, synergists or adjuvants.</p>

<p>Compounds of formula (I):</p><p>[Formula I]</p><p><img file="KR102403004B1_D0003.tif" /></p><p>(wherein y is a number from 1 to 7, for example from 1 to 4, M is a metal cation having a formal charge of (+)y, p is a number from 1 to 7, for example from 1 to 4, R is, for example, alkyl, aryl, alkylaryl or arylalkyl) at a temperature greater than 200°C, for example from 220°C to 250°C or higher, for example from 200°C, 220°C or 250°C to It undergoes a reaction when heated at a temperature of 400° C. to form different species that are typically thermally stable to temperatures above 400° C. and are well suited for use as flame retardant additives in polymers. These reaction products have improved flame retardant properties compared to the compounds of formula (I) and are more easily processed into polymer resins such as polyamides without adversely affecting the physical properties of the resins. Although the mechanism of action is uncertain at the present time, when the material of the present invention is used with a phosphinate, i.e. a compound of formula II, excellent and surprising results in a manner suggesting the possibility that the two materials may have different and complementary activities is obtained</p><p>The present invention relates to a flame retardant comprising a product obtained by heat treatment of a compound of formula (I), a process for the preparation of a flame retardant, a synergistic blend of a flame retardant with another flame retardant or flame retardant synergist, for example a blend of a flame retardant of the invention with a phosphinic acid salt , and a flame retardant or synergistic blend of the present invention.</p><p>Also provided is a process for preparing a flame retardant polymer, the process comprising the steps of heating a compound of formula (I) under conditions that chemically convert the compound into a thermally stable flame retardant material of the invention as described above, followed by the steps of: incorporating the produced thermally stable flame retardant into a polymer resin, for example, by melt processing the polymer and the flame retardant at high temperatures. Certain embodiments provide a method in which a thermally stable flame retardant prepared by heating a compound of formula (I) is added to a polymer resin together with a phosphinic acid salt of formula (II) and/or other synergists.</p><p>In a particular embodiment of the invention, the flame retardant material comprises a mixture of compounds obtained from heat treatment of more than one compound of formula (I) having different values for R and/or M. Such mixtures can be prepared in a variety of ways, resulting in mixtures having different compositions and product forms, even when derived from the same combination of compounds of formula (I). For example, certain embodiments of the present invention provide flame retardancy obtained by treating one or more phosphonic acid compounds with one or more metal compounds to form an intermediate salt complex, followed by heating the intermediate salt complex as above. mixture; a flame retardant mixture obtained by combining two or more metal phosphonates of formula (I) to form an intimate salt mixture, followed by heating the salt mixture as above; and separately heating at least two individual metal phosphonates of formula (I) to form at least two individual flame retardant materials, which are then blended together by suitable techniques.</p>

<p>Polymeric compositions comprising the flame retardants of the present invention, such as thermosetting or thermoplastic compositions, have been found to exhibit excellent flame retardant activity, either alone or in combination with other flame retardants, synergists or adjuvants.</p>

One embodiment of the present invention is a flame retardant polymer composition, the flame retardant polymer composition comprising:

a) thermosetting or thermoplastic polymers, for example thermoplastic polymers;

b) one or more than one phosphonic acid salt, ie a compound of formula (I), at a temperature of at least 200° C., for example at least 220° C., generally at least 250° C., for example between 250° C. and 400° C. or between 260° C. and 360° C. A flame-retardant material obtained by heating at a temperature of ° C., wherein the flame-retardant material is 1% to 50% by weight, based on the total weight of the flame-retardant composition:

[Formula I]

<img file="KR102403004B1_D0004.tif" />

(wherein R is an alkyl, aryl, alkylaryl or arylalkyl group, p is a number from 1 to 7, such as from 1 to 4, such as 1, 2, 3 or 4, M is a metal, y is M^(+)yis a number from 1 to 7, such as 1 to 4, such as 1, 2, 3 or 4, often 2 or 3, such that (+)y is a metal cation representing the charge formally assigned to the metal cation ),

and

c) optional additional flame retardants or flame retardant synergists.

For example, in formula (I), y = 1 M^(+)yis a mono-cation, such as Li⁺, Na⁺ or K⁺represents M, where y is 2^(+)yis a di-cation, such as Mg⁺⁺, Ca⁺⁺ or Zn⁺⁺ etc., where y is 3 M^(+)yis a tri-cation, such as Al⁺⁺⁺ etc. As is customary for organometallic species, these formulas are ideal, the starting materials being complex salts or salts in which a certain atomic valence is shared, such as a salt in which a single oxygen anion is shared between two metal cations, etc. may include Usually, the starting salts are charge balanced, i.e., in compounds of formula (I) where p = y, M^(+)ygo Na⁺When , p is 1 and M is Al⁺⁺⁺When , p is 3, etc.

While not wishing to be bound by theory, spectroscopic data and other analyzes have shown that heat treatment of compounds of formula (I) within the temperature treatment ranges of the present invention includes compounds and complex dehydration products thereof generally believed to be represented by empirical formula (IV). It suggests that it creates a material that:

[Formula IV]

<img file="KR102403004B1_D0005.tif" />

wherein R and M are as defined for formula I, q is a number from 1 to 7, such as 1, 2 or 3, and r is from 0 to 5, such as 0, 1 or 2, often 0 or a number of 1, y is a number from 1 to 7, for example from 1 to 4, n is 1 or 2, with the proviso that 2(q) + r = n(y). Typically, heat treatment of a compound of formula (I) according to the present invention produces a material comprising more than one compound, wherein at least one compound is generally represented by the empirical formula (IV), and complex dehydration products thereof. As is customary for organometallic species, formula IV is ideal, and the product may include polymer salts, complex salts, salts in which certain valences are shared, and the like.

For example, when M is aluminum, i.e., when a compound of formula (I), wherein M is Al, is heated according to the invention, elemental analysis shows that q is 1, r is 1, n is 1 and y is 3 suggesting the formation of a product with empirical formula IV.

The flame-retardant material obtained according to the invention is more thermally stable than the starting phosphonates of formula (I), exhibits greater flame-retardant activity, and has improved processability in various polymer resins.

Often, a single compound of formula (I) is heated to produce the flame retardant material of the present invention. In another embodiment, more than one compound of formula (I) is heated to produce the flame retardant material of the present invention, i.e. different R groups and/or different metal cations M^(+)yA mixture of compounds of formula (I), including compounds having

When formed from a compound of formula (I) in which one R group and one metal are present, a mixture of compounds comprising at least one compound of formula (IV) is usually formed, wherein said mixture and said compound or compound of formula (IV) They contain one R group and one metal. In some embodiments of the present invention, the flame retardant material comprises a mixture of compounds in which more than one R group and/or more than one metal is present, which comprises more than one R group and/or more than one metal. Mixtures of compounds of formula IV exist. Flame retardants of the present invention comprising compounds containing more than one R group and/or more than one metal can be formed in a variety of ways.

The first method may be termed the intermediate salt complex method, in which one or more phosphonic acid compounds are treated with one or more suitable metal compounds to provide an intermediate salt complex corresponding to formula I, wherein R and/or It contains multiple values for M. Often, the metal, or at least one of the metals, used to form the intermediate salt complex will be a bidentate or polydentate metal, and more than one intermediate complex may be formed. This salt complex is then heat-treated as described above,

a) at least one compound corresponding to formula IV having more than one R group and/or more than one M group, and/or

b) mixtures of compounds corresponding to formula IV

wherein the mixture yields a flame retardant material comprising compounds having different R groups and/or different M groups.

Alternatively, the second method may be termed the salt admixture method, in which two or more metal phosphonate salts of formula (I) are combined to form a salt comprising salts having different values for R and/or M form a mixture. Then, this mixture is subjected to the heat treatment described above,

a) at least one compound corresponding to formula IV having more than one R group and/or more than one M group, and/or

b) mixtures of compounds corresponding to formula IV

wherein the mixture yields a flame retardant material comprising compounds having different R groups and/or different M groups.

A third method for obtaining flame retardant materials of the invention comprising compounds of formula IV having multiple values for R and/or M is, as described above, different by having different values for R and/or M. heating two or more separate metal phosphonates of formula (I) separately to separately obtain two or more flame retardant materials of the present invention, and then mixing these flame retardant materials together to form a blended flame retardant composition do.

The exact composition of the mixture obtained by the preceding three processes, namely the intermediate salt complex method, the salt admixture method, and the blending of the flame-retardant materials obtained separately will generally be different, starting from the same phosphonic acid compound and metal. Even when you do Accordingly, differences in physical properties, stability, compatibility and performance are generally encountered for products of different methods.

The polymer of the flame retardant composition of the present invention may be any polymer known in the art, such as polyolefin homopolymers and copolymers, rubbers, polyesters, epoxy resins, polyurethanes, polyalkylene terephthalates, polysulfones, polyimides, polyphenylene ethers, styrenic polymers and copolymers, polycarbonates, acrylic polymers, polyamides, polyacetals, epoxy resins and biodegradable polymers. mixtures of different polymers, such as polyphenylene ether/styrenic resin blends, polyvinyl chloride/ABS or other impact modified polymers such as ABS with methacrylonitrile and α-methylstyrene, and polyester/ABS or polycarp Bonate/ABS and polyester plus some other impact modifiers may also be used. Such polymers are either commercially available or prepared by means well known in the art.

The flame retardants of the present invention are particularly useful for thermoplastic polymers processed and/or used at high temperatures, for example styrenic polymers including HIPS, polyolefins, polyesters, polycarbonates, polyamides, polyurethanes, polyphenylene ethers, etc. do.

For example, the polymer may be a polyester-series resin, a styrenic resin, a polyamide-series resin, a polycarbonate-series resin, a polyphenylene oxide-series resin, a vinyl-series resin, an olefin-based resin, an acrylic resin, It may be an epoxy resin, or a polyurethane. The polymer may be a thermoplastic or thermoset resin and may be reinforced, for example glass reinforced. There may be more than one polymeric resin. In certain embodiments, the polymer is an engineering polymer, for example a thermoplastic or reinforced thermoplastic polymer, for example a glass-reinforced thermoplastic polymer, such as optionally glass-filled polyesters, epoxy resins or polyamides, for example glass-filled polyesters such as glass-filled polyalkylene terephthalates, or glass-filled polyamides.

Polyester-series resins include, for example, homopolyesters and copolyesters obtained by polycondensation of a dicarboxylic acid component and a diol component, and polycondensation of a hydroxycarboxylic acid or lactone component, e.g. for example aromatic saturated polyester-series resins such as polybutylene terephthalate or polyethylene terephthalate.

Polyamide-series resins include polyamides derived from diamines and dicarboxylic acids; polyamides obtained from aminocarboxylic acids, if necessary in combination with diamines and/or dicarboxylic acids; and polyamides derived from lactams, if necessary in combination with diamines and/or dicarboxylic acids. Polyamides also include copolyamides derived from at least two different types of polyamide constituents. Examples of polyamide-series resins include aliphatic polyamides such as nylon 46, nylon 6, nylon 66, nylon 610, nylon 612, nylon 11 and nylon 12, aromatic dicarboxylic acids such as terephthalic acid and/or isophthalic acid; Polyamides obtained from aliphatic diamines, for example hexamethylenediamine or nonamethylenediamine, and both aromatic and aliphatic dicarboxylic acids, for example both terephthalic acid and adipic acid, and aliphatic diamines, for example hexamethylenediamine polyamides obtained from, and others. These polyamides may be used alone or in combination.

Polyamides with a melting point of at least 280° C. are used extensively to produce molding compositions, which have excellent dimensional stability at high temperatures and very good flame-retardant properties, for example molded articles for the electrical and electronic industry enables the creation of Molding compositions of this type are required, for example, in the electronics industry for producing components that are mounted on printed circuit boards according to the so-called surface mounting technology, SMT. In these applications, these components must withstand temperatures of up to 270° C. for short periods of time without dimensional changes.

Such high temperature polyamides include certain polyamides produced from alkyl amines and acids, such as nylon 4,6, also termed polyamide 4,6, although many high temperature polyamides are aromatic and semiaromatic polyamides, i.e. containing aromatic groups. are homopolymers, copolymers, terpolymers, or higher order polymers derived from monomers. A single aromatic or semiaromatic polyamide may be used, or a blend of aromatic and/or semiaromatic polyamides is used. It is also possible to blend the foregoing polyamides and polyamide blends with other polymers including aliphatic polyamides.

Examples of these high temperature aromatic or semiaromatic polyamides include nylon 4T, poly(m-xylylene adipamide) (polyamide MXD,6), poly(dodecamethylene terephthalamide) (polyamide 12,T), poly( decamethylene terephthalamide) (polyamide 10,T), poly(nonamethylene terephthalamide) (polyamide 9,T), hexamethylene adipamide/hexamethylene terephthalamide copolyamide (polyamide 6,T/6, 6), hexamethylene terephthalamide/2-methylpentamethylene terephthalamide copolyamide (polyamide 6,T/D,T); hexamethylene adipamide/hexamethylene terephthalamide/hexamethylene isophthalamide copolyamide (polyamide 6,6/6,T/6,I); poly(caprolactam-hexamethylene terephthalamide) (polyamide 6/6,T); hexamethylene terephthalamide/hexamethylene isophthalamide (6,T/6,I) copolymer and the like.

Accordingly, certain specific embodiments of the present invention include polyamides that melt at high temperatures, for example at 280°C or higher, 300°C, or higher, and in some embodiments 320°C or higher, for example 280°C to 340°C, such as Compositions comprising polyamide 4,6 and the aromatic and semiaromatic polyamides described above, articles comprising the high temperature polyamide and the flame retardant material of the present invention, methods of making the compositions and methods of shaping the articles.

Flame retardants (b) exhibit excellent activity in polymer systems, either alone as flame retardants or in combination with other flame retardants, synergists or adjuvants. The concentration of the flame retardants of the present invention in the polymer composition will, of course, depend on the exact chemical composition of the flame retardants, polymers and other ingredients found in the final polymer composition. For example, when used as the sole flame retardant component of a polymer formulation, the flame retardant of the present invention may be present in a concentration of from 1% to 50% by weight of the total weight of the final composition, for example from 1% to 30% by weight. . Typically, when used as the sole flame retardant, the materials of the present invention will be present in at least 2%, such as at least 3%, at least 5%, at least 10%, at least 15%, at least 20% or at least 25%. In many embodiments, the flame retardant of the present invention is present in an amount of up to 45%, while in other embodiments the amount of the flame retardant of the present invention is no more than 40% of the polymer composition, for example no more than 35%. Obviously, when used in combination with other flame retardants or flame retardant synergists, the material of the present invention should require less.

Any known compounding technique may be used to prepare the flame retardant polymer composition of the present invention, for example, the flame retardant may be introduced into the molten polymer by blending, extrusion, fiber or film formation, and the like. In some cases, the flame retardant is incorporated into the polymer upon formation or curing of the polymer, for example the flame retardant of the present invention may be added to the polyurethane prepolymer prior to crosslinking, or it may be added to the polyamine or alkyl-polycarboxylic acid prior to polyamide formation. It can be added to the carboxyl compound or to the epoxy mixture prior to curing.

Another embodiment of the present invention relates to flame retardant materials and synergistic blends of flame retardant materials with other ingredients. The flame retardant of the present invention comprises more than one as defined above at a temperature of 200°C or higher, for example 220°C or higher, generally 250°C or higher, for example 250°C to 400°C or 260°C to 360°C. Obtained by heating the phosphonate of formula (I). As described above, a material produced by heating a compound of formula (I) at the listed temperatures is generally believed to be a compound or mixture of one or more such compounds, which is believed to be represented by the empirical formula (IV):

[Formula IV]

<img file="KR102403004B1_D0006.tif" />.

The phosphonates of formula (I) are known and various methods of their preparation have been described in the art. For example, US 2006/0138391 states that R is hydrogen, C_1-18alkyl, C_5-6cycloalkyl, C_2-6alkenyl, C_6-10aryl, or C_7-11aralkyl, such alkyl, alkenyl, aryl, or aralkyl being unsubstituted or halogen, hydroxyl, amino, C_1-4 Alkylamino, di-C_1-4Alkylamino, C_1-4Alkoxy, carboxy or C_2-5may be substituted with alkoxycarbonyl; M is, for example, group IA, IB, IIA, IIB, IIIA, IVA, VA or VII of the periodic table, for example Li, K, Na, Mg, Ca, Ba, Zn, Ge, B, Al, Cu, Disclosed are compounds of formula (I), which may be selected from Fe, Sn or Sb and the like. It is noted in US 2006/0138391 that none of the compounds corresponding to formula (I) were hybridized into polymer resins at high temperatures or heated above 200°C. The only salts actually exemplified in US 2006/0138391 are the aluminum salts of methyl methylphosphonic acid, i.e. the salts of the compounds of formula la above wherein R and R' are methyl, i.e.

<img file="KR102403004B1_D0007.tif" />

to be.

The starting material for the flame retardant of the present invention, ie the compound of formula (I), may for convenience be selected from the salts disclosed in US 2006/0138391 and elsewhere in the art. Compounds of formula (I) useful in the present invention may also contain other R groups not found in US 2006/0138391, such as aryl substituted with alkyl, and compounds of formula (I) comprising metal cations not specifically mentioned therein. It may be useful as a starting material.

In some embodiments of the present invention, the salt of formula I is wherein R is C_1-12 alkyl, C_6-10 aryl, C₇_-18 Alkylaryl, or C_7-18 Includes compounds which are arylalkyl groups, wherein the groups are further substituted as described in US 2006/0138391, but often R is unsubstituted C_1-12 alkyl, C_6-10 aryl, C_7-18 Alkylaryl, or C_7-18 arylalkyl. For example, R is substituted or unsubstituted, usually unsubstituted C_1-6 alkyl, C₆ aryl, C_7-10 Alkylaryl, or C_7-₁₂ arylalkyl, for example C_1-4 alkyl, C₆ aryl, C_7-19 Alkylaryl, or C_7-10 arylalkyl.

In the most general embodiment of the invention, M^(+)ycan be almost any metal cation, but M is generally Li, K, Na, Mg, Ca, Ba, Zn, Zr, Ge, B, Al, Si, Ti, Cu, Fe, Sn or Sb, e.g. for Li, K, Na, Mg, Ca, Ba, Zn, Zr, B, Al, Si, Ti, Sn or Sb, in many embodiments M is Li, K, Na, Mg, Ca, Ba, Zn, Zr, B, Al, Sn or Sb, and in certain embodiments M is Al, Zn or Ca. Excellent results are achieved, for example, when M is Al or Ca.

R as alkyl is a straight or branched chain alkyl group having the specified number of carbon atoms, for example unbranched alky, such as methyl, ethyl, propyl, butyl, pentyl, hexyl heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and unbranched alkyls such as isopropyl, iso-butyl, sec-butyl, t-butyl, ethyl hexyl, t-octyl, and the like. For example, R as alkyl is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-buty, t-butyl, often R is methyl, ethyl, propyl or isopropyl, eg methyl.

Typically, when R is aryl, it is phenyl or naphthyl, for example phenyl. Examples of R as alkylaryl include phenyl substituted with one or more alkyl groups, for example, a group selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-buty, t-butyl, and the like. Examples of R as arylalkyl include, for example, benzyl, phenethyl, styryl, cumyl, phenpropyl, and the like.

In one embodiment, R is methyl, ethyl, propyl, isopropyl, phenyl or benzyl, for example methyl or phenyl.

In certain embodiments, for example, the starting material is a compound of formula I, wherein R is methyl, ethyl, propyl, isopropyl, benzyl or phenyl, M is Al, Zn or Ca, and p is 2 or 3. In one particular embodiment, R is methyl, ethyl, propyl, isopropyl, or phenyl, p=3, and M is Al; In another specific embodiment R is methyl, ethyl, propyl, isopropyl, or phenyl, p=2, and M is Zn or Ca, eg Ca.

In certain embodiments, at least one R is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-buty, t-butyl and phenyl, and at least one M is selected from Al, Zn and Ca . In certain embodiments, each R is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-buty, t-butyl and phenyl, and each M is selected from Al, Zn and Ca.

The time taken to convert the phosphonate of formula (I) to the flame retardant of the present invention will vary depending on a variety of factors, including, for example, the chemical structure of the starting phosphonate, reaction temperature, and other reaction conditions. do. For example, higher temperatures can lead to faster reaction times. It is believed that water is produced during the reaction and the presence of a water absorbent or vacuum will also reduce the reaction time. The design of the reaction vessel, the presence of other materials during heating, etc. may also affect the reaction time.

Good conversions are often obtained, for example, by heating the phosphonate of formula I at a temperature of at least 200° C., 220° C., 250° C. or higher for a time of up to 20 hours, typically less than 12 hours. In certain circumstances, this time may be extremely short, for example at a higher temperature in the reaction vessel or environment that makes heat transfer to the starting material highly efficient, for example between 250°C and 400°C or above 400°C. The use of temperature can significantly reduce reaction times, for example to less than or less than 0.2 hours, 0.1 hours, or 0.01 hours, with complete reaction times measured in seconds or less are possible.

In general, full conversion to the flame retardant of the present invention is achieved by reacting the starting phosphonate at a temperature of 200°C to 400°C for 0.01 h or 0.2 h to 20 h, often 0.1 h or 0.2 h to 12 h, or 1 h to 8 h. It is obtained by heating, but as described above, the time for full conversion will depend on the temperature. For example, heating of a phosphonate of formula I from 250° C. to 400° C. will require heating for less than 12 hours, for example from 1 hour to 8 hours. Excellent results are obtained when the starting phosphonate is heated at 260° C. to 340° C. for 1 hour to 6 hours, for example 2 hours to 6 hours.

For example, tris-[methylphosphonic acid] aluminum salt, i.e., a water-soluble solid compound of formula III wherein R is methyl, is heated at a temperature of 250° C. to 320° C. for 2 hours to 6 hours to form a solid material, which solid The material, in contrast to the starting material, is insoluble in water and is stable at temperatures above 400°C. However, higher reaction temperatures may be used, as shown in the examples, heating at 280° C. for 4 hours yields excellent results.

[Formula III]

<img file="KR102403004B1_D0008.tif" />

Likewise, even when heating tris-[ethylphosphonic acid] aluminum salt, i.e., a compound of formula III, wherein R is ethyl, or tris-[phenylphosphonic acid] aluminum salt, i.e., a compound of formula III wherein R is phenyl , a similar ethyl and phenyl containing flame retardant material is produced.

As described above, even when starting from a single compound of formula (I) in which one R group and one metal are present, a mixture of compounds comprising at least one compound of formula (IV) is usually formed, wherein said mixture and the compound or compounds of formula (IV) include its one R group and its one metal. In certain embodiments of the present invention, the flame retardant material comprises a mixture of compounds in which more than one R group and/or more than one metal is present, which comprises more than one R group and/or more than one metal. Mixtures of compounds of formula IV exist. Flame retardants of the present invention comprising compounds containing more than one R group and/or more than one metal can be formed in a variety of ways.

According to the intermediate salt complex method, treatment of one or more phosphonic acid compounds with one or more suitable metal compounds, for example in a single vessel, provides an intermediate salt complex corresponding to formula (I), wherein the complex is in R and/or M contains multiple values for Often, the metal, or at least one of the metals, used to form the intermediate salt complex will be a bidentate or polydentate metal, and more than one intermediate complex may be formed. This salt complex is then heat-treated as described above,

a) at least one compound corresponding to formula IV having more than one R group and/or more than one M group, and/or

b) mixtures of compounds corresponding to formula IV present

wherein the mixture yields a flame retardant material comprising compounds having different R groups and/or different M groups.

For example, according to the intermediate salt complex method, a single solution or suspension of at least two different phosphonic acids of formula (lb):

[Formula Ib]

<img file="KR102403004B1_D0009.tif" />

(wherein R is as defined for formula I above), for example methyl phosphonic acid and ethyl phosphonic acid or methyl and phenyl phosphonic acid in a solvent such as an organic solvent, water, or a mixture of an organic solvent and water treatment with a suitable metal compound, such as calcium carbonate, aluminum triethoxide, etc., to form an intermediate mixture of salts and salt complexes, which is heated upon isolation and drying to form the flame retardant of the present invention.

Of course, suitable intermediates may also be formed by treating a single phosphonic acid of formula Ib with two or more metal compounds, or by mixing two or more phosphonic acids with two or more metal compounds.

In the salt admixture process, two or more different phosphonic acids of formula (lb) are treated individually with a metal compound to first form the individual portions of salts of formula (la), then the salts already formed separately are combined to form a mixture, e.g. in solution A mixture of salts is formed, which is then isolated by standard methods such as distillation of a solvent and then heated to form the flame retardant of the present invention. Other methods of isolation can be used, such as concentrating the solution and filtering the suspended salts, trituration of the salts, or physically mixing the isolated salts, although greater consistency is achieved by removing the solvent from the solution via distillation. (consistency) will be predicted.

As above, by separately treating a single phosphonic acid of formula Ib with two or more metal compounds, or by separately treating separate mixtures of two or more phosphonic acids of formula Ib with two or more metal compounds, etc. Although suitable salt mixtures can also be formed, such systems can result in a very high degree of complexity.

A person skilled in the art knows that salts from the intermediate salt complex process and an intermediate mixture of salt complexes, which are then heated according to the invention, are produced according to the salt admixture process, in particular when one or more bidentate or polydentate metals are used, followed by heating. It will be readily understood that this will often be different from the mixture of salts used. In addition, neither of these two methods of producing a flame retardant from a starting material comprising one or more R groups or metals prior to exposure to high temperatures of the present invention provide different individual formulas by having different values for R and/or M After heating the metal phosphonates of I separately, blending the resulting compositions is likely to produce a product that is not readily obtained.

Thus, the various approaches for making the flame retardant materials of the present invention provide one great flexibility in synthesizing a wide variety of mixtures with different physical properties, stability, miscibility and/or flame retardant performance.

In general, the selected phosphonic acid metal salt or mixture of salts used as the starting material is heated in the absence of other materials. However, although these salts can be heated, for example, in the presence of an inert carrier, another flame retardant, or other potential additive, etc., the presence of added water is usually avoided, as water is removed from the starting material during the reaction. because it is considered to be For example, the starting material may be mixed with other flame retardant materials, polymer stabilizers, or other known polymer additives prior to heating above 200. Thermal transformation of the salt can also occur in the presence of small amounts of polymer as an inert carrier, but care must be taken to avoid situations in which the transformation of the starting salt is impeded by the presence of other materials. For example, a polymer or other material may melt under the reaction temperature and coat the salt, or even react with the salt to produce undesirable results.

Accordingly, in many embodiments the compound or compounds of formula (I) are subjected to heat treatment in the absence of other components. If a polymer or other inert carrier is present during the reaction, it is usually in an amount less than the amount of the phosphonic acid metal salt, for example less than 50% by weight or less than 25% by weight of the phosphonic acid metal salt and the mixture of the polymer. It is present in an amount of less than 10% by weight, for example less than 5% by weight or from 0% to 2% by weight. Since salts of formula (I) are believed to liberate water upon reaction, heating the salts above 200°C in the presence of materials that are unstable in the presence of water at elevated temperatures, including polymers that may undergo hydrolysis, should be avoided. it is recommended

According to the present invention, the phosphonic acid metal salt or salts of formula (I) is thermally converted into a different, more thermally stable flame retardant material before it is incorporated into the bulk of the polymer it is intended to protect. In contrast to the salts of formula (I), also known as flame retardants, the flame retardants of the present invention are stable at processing temperatures above 200° C., for example polymers such as polyesters and polyamides containing linkages susceptible to reaction and cleavage. does not undergo a reaction that may have a negative effect on For example, polyalkylene phthalates, polyamides, and many other condensation polymers are processed at high temperatures. At high temperatures, the salts of formula (I) apparently undergo a reaction that liberates water, which can lead to hydrolysis at the ester or amide linkages, leading to chain scission and loss of molecular weight and desired physical properties.

The flame retardants of the present invention may be used in combination with a variety of other flame retardants, synergists or flame retardant adjuvants as known in the art. For example, the flame retardant of the present invention may be formulated with one or more materials selected from:

carbon black, graphite, carbon nanotubes, silicon; polyphenylene ether (PPE), phosphine oxide and polyphosphine oxide such as benzyl phosphine oxide, poly benzyl phosphine oxide and the like;

melamine, melamine derivatives and condensation products, melamine salts such as, without limitation, melamine cyanurate, melamine borate, melamine phosphate, melamine metal phosphate and the like;

inorganic compounds such as clays, metal salts such as hydroxides, oxides, oxide hydrates, borates, carbonates, sulfates, phosphates, phosphites, hypophosphites, silicates, mixed metal salts and the like, such as talc and other magnesium silicates; Calcium silicate, aluminosilicate, aluminosilicate (DRAGONITE) as hollow tube, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, HALLOYSITE or boron phosphate, calcium molybdate, exfoliated vermiculite, zinc stannate, hydroxy Zinc stannate, zinc sulfide and zinc borate, zinc molybdate (KEMGARD 911A/B), zinc phosphate (KEMGARD 981), magnesium oxide or magnesium hydroxide, aluminum oxide, aluminum hydroxide (Byeom), aluminum trihydrate, silica, tin oxide , antimony (III and V) oxide and antimony oxide hydrate, titanium oxide, and zinc oxide or zinc oxide hydrate, zirconium oxide and/or zirconium hydroxide and the like.

Unless otherwise specified, in the context of this application, the term "phosphate" when used as a component in a "phosphate salt", such as metal phosphate, melamine phosphate, melamine metal phosphate, etc. Hydrogen phosphate, dihydrogen phosphate, pyrophosphate, polyphosphate, or phosphoric acid condensation product refers to an anion or polyanion.

Likewise, unless otherwise specified, in the context of this application, the term "phosphite" when used as a component in a "phosphite salt", such as metal phosphite, etc., refers to phosphite or hydrogen phosphite. phosphite).

The flame retardants of the present invention also include other flame retardants, such as halogenated flame retardants, alkyl or aryl phosphine oxide flame retardants, alkyl or aryl phosphate flame retardants, alkyl or aryl phosphonates, alkyl or aryl phosphinates, and salts of alkyl or aryl phosphinic acids. It can be formulated with One particular embodiment provides a synergistic mixture of a flame retardant of the present invention with a phosphinic acid salt of formula II, for example aluminum tris(dialkylphosphinate).

Accordingly, in many embodiments, a flame retardant polymer composition according to the present invention comprises a polymer (a), a flame retardant (b), and (c) one or more additional flame retardants, and/or one or more synergists or flame retardant adjuvants. include as

For example, in some embodiments, the flame retardant polymer composition comprises one or more additional flame retardants, such as halogenated flame retardants, phosphine oxide flame retardants, alkyl or aryl phosphonates, or salts of alkyl or aryl phosphinates, such as aluminum tris(dialkylphosphinate) such as aluminum tris(diethylphosphinate).

In some embodiments, the flame retardant polymer composition comprises one or more synergists or flame retardant adjuvants such as melamine, melamine derivatives and condensation products, melamine salts, phosphine oxides and polyphosphine oxides, metal salts such as hydroxides, oxides, oxides. hydrates, borates, phosphates, phosphites, silicates and the like, for example aluminum hydrogenphosphite, melem or melamine metal phosphates, for example melamine metal phosphates wherein the metal comprises aluminum, magnesium or zinc. In certain embodiments, one or more additional flame retardants, synergists or flame retardant adjuvants include aluminum tris(dialkylphosphinate), aluminum hydrogenphosphite, methylene-diphenylphosphine oxide-substituted polyaryl ether, xylylenebis( Diphenylphosphine oxide), 4,4'-bis(diphenylphosphinylmethyl)-1,1'-biphenyl, ethylenebis-1,2-bis-(9,10-dihydro-9-oxy- 10-phosphaphenanthrene-10-oxide)ethane, melem, melam, melon or dimelamine zinc pyrophosphate.

One particular embodiment relates to a synergistic mixture comprising a flame retardant of the present invention and aluminum tris(diethylphosphinate).

For example, a flame retardant of the present invention may be in the range of 100:1 to 1:100 by weight of the additional flame retardant, synergist or adjuvant and the total weight of the flame retardant of the present invention to the additional flame retardant, synergist, and adjuvant. can be combined with Depending on the additional flame retardant, synergist or adjuvant, excellent results can be obtained using the flame retardant to the additional flame retardant, synergist and/or adjuvant in the range from 10:1 to 1:10 (by weight), e.g. For example weight ratios ranging from 7:1 to 1:7, 6:1 to 1:6, 4:1 to 1:4, 3:1 to 1:3 and 2:1 to 1:2 are used for good effect. . The flame retardants of the present invention are usually the main component in such combinations, for example, the weight ratio of the flame retardant material of the present invention to the additional flame retardant, synergist and/or adjuvant is from 10:1 to 1.2:1 or from 7:1 to 2 :1, but the material of the invention may also be a minor component of a mixture, for example the ratio of the flame retardant to the further flame retardant, synergist and/or adjuvant synergist is from 1:10 to 1:1.2 or from 1:7 to It is 1:2.

The flame retardant polymer composition of the present invention will also contain one or more of the conventional stabilizers or other additives commonly encountered in the art, such as phenolic antioxidants, hindered amine light stabilizers (HALS), ultraviolet light Absorbents, phosphites, phosphonates, alkali metal salts of fatty acids, hydrotalcite, metal oxides, borate, epoxidized soybean oil oil, hydroxylamine, tertiary amine oxide, lactone, thermal reaction product of tertiary amine oxide, thio thiosynergists, basic co-stabilizers such as melamine, melem, etc., polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, hydrotalcites, alkali metal salts and alkaline earth metal salts of higher fatty acids, such as Ca stearate, calcium stearoyl lactate, calcium lactate, Zn stearate, Zn octoate, Mg stearate, Na ricinoleate and K palmyrate, antimony pyrocatecholate or zinc pyrocatecholate, nucleating agents, clarifying agents and the like.

Other additives may also be present, for example plasticizers, lubricants, emulsifiers, pigments, dyes, optical brighteners, other flame retardants, antistatic agents, blowing agents, anti-drip agents, for example PTFE and the like.

Optionally, the polymer may include fillers and reinforcing agents, such as calcium carbonate, silicates, glass fibers, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black and graphite. Such fillers and adjuvants can often be present in relatively high concentrations, including formulations in which the filler or adjuvant is present in concentrations greater than 50% by weight, based on the weight of the final composition. More typically, fillers and reinforcing agents are present in an amount of from 5% to 50% by weight, for example from 10% to 40% by weight or from 15% to 30% by weight, based on the weight of the total polymer composition.

Example

Comparative Example 1

210 To a solution of 96.0 g of methylphosphonic acid (1.00 mol) in mL of deionized water is slowly added 54.1 g of aluminum ethoxide (0.334 mol) under nitrogen. The reaction mixture is then stirred at room temperature for 16 h. The solution is then concentrated and dried in vacuo at 100° C. to give a clear colorless solid. Thermal analysis indicated a loss of 1 mol of water starting at approximately 250°C. Elemental analysis: 29.8% P, 9.0% Al; Calculated: 29.8% P, 8.7% Al.

20 Parts salt and 30 parts glass were blended into 50 parts polyamide 66 using a Haake Rheocord 90 equipped with a 3 piece Brabender measuring head. A decrease in torque was observed during blending, which could indicate polymer degradation, resulting in a wet newspaper-like material, which was brittle upon cooling and dusty after grinding. Analysis by gel permeation chromatography (GPC) and differential scanning calorimetry (DSC) of the hybridized material that could not be molded provided further evidence of degradation.

Example 1 - Flame retardant from methylphosphonic acid aluminum salt,<b>FR</b><b>-</b><b>INV1</b><b></b>

210 To a cooled solution of 48.0 g of methylphosphonic acid (500 mmol) in ml of deionized water is slowly added 27.0 g of aluminum ethoxide (167 mmol) under nitrogen. The reaction is then allowed to warm to room temperature and stirred for 16 h. The solution is then concentrated and dried in vacuo at 100° C. to give a clear colorless solid. Thermal analysis indicated a loss of 1 mol of water starting at 250°C. The colorless solid was heated at 280° C. for 4 hours, resulting in an off-white solid that was stable to above 400° C. Elemental analysis: 31.5% P, 9.0% Al.

Comparative Example 2

150 To a stirred solution of 37.9 g of ethylphosphonic acid (344 mmol) in mL of deionized water is added a solution of 27.7 g of aluminum chloride hexahydrate (115 mmol) in 150 mL of deionized water. The solution is then concentrated in vacuo to remove water and HCl. Drying in a vacuum oven at 130° C. yields a white powder. Thermal analysis indicated a loss of 1 mol of water starting at approximately 200°C. Elemental analysis: 25.0% P, 6.9% Al.

20 Parts salt and 30 parts glass were hybridized into 50 parts polyamide 66 using a Haake Rheocord 90. Low torque was observed throughout the blending, which could indicate polymer degradation, where the formulation swelled out of the bowl towards the end of this run, resulting in foaming due to escaped gases and brittleness upon cooling. After grinding, a dusty material was produced.

Example 2 - Flame retardant from ethylphosphonic acid aluminum salt,<b>FR</b><b>-</b><b>INV2</b>:

500 To a stirred solution of 149.5 g of ethylphosphonic acid (1.36 mol) in mL of deionized water is added a solution of 109.3 g of aluminum chloride hexahydrate (.453 mol) in 250 mL of deionized water. The solution is then concentrated and dried in vacuo at 130° C. to remove water and HCl. Thermal analysis indicated a loss of 1 mol of water starting at 180°C. The dried salt is heated at 225° C. for 3 hours to obtain a white powder that is stable to approximately 400° C. Elemental analysis: 27.3% P, 7.6% Al.

Example 3 - Flame retardant from ethylphosphonic acid calcium salt,<b>FR</b><b>-</b><b>INV3</b>:

250 To a stirred solution of 52.1 g of ethylphosphonic acid (473 mmol) in mL of deionized water is slowly added 17.5 g of calcium hydroxide (236 mmol). The solution is then concentrated and dried at 100° C. in vacuo. Thermal analysis indicated a loss of 1 mol of water starting at 220°C. The dried salt is heated at 290°C for 3 hours to give a white powder that is stable to above 400°C. Elemental analysis: 25.3% P, 16.3% Ca.

Example 4 - Flame retardant from intermediate salt complex produced from methylphosphonic acid, ethyl phosphonic acid and aluminum ethoxide:

27.0 g of aluminum ethoxide (167 mmol) was added to a stirred solution of methylphosphonic acid (250 mmol) and ethylphosphonic acid (250 mmol) in deionized water under nitrogen, then concentrated and dried in vacuo at 100° C. to medium After providing the salt complex and heating it at 280° C. for 4 hours, the flame retardant material of the present invention is provided.

Example 5 - Flame retardant from intermediate salt complex produced from methylphosphonic acid, ethyl phosphonic acid and calcium hydroxide:

17.5 g of calcium hydroxide (ca. 235 mmol) was added to a stirred solution of methylphosphonic acid (ca. 225 mmol) and ethylphosphonic acid (ca. 250 mmol) in deionized water under nitrogen, concentrated and dried in vacuo at 100° C. After providing the intermediate salt complex and heating it at 290° C. for 3.5 hours, the flame retardant material of the present invention is provided.

Example 6 - Flame retardant from ethyl phosphonic acid and an intermediate salt complex produced from a mixture of aluminum ethoxide and calcium hydroxide:

Aluminum ethoxide (ca. 85 mmol) and calcium hydroxide (ca. 120 mmol) were added simultaneously to a stirred solution of ethylphosphonic acid (500 mmol) in deionized water under nitrogen, concentrated and dried in vacuo at 100° C. to medium salt complex. and heating it at 290° C. for 4 hours to provide the flame retardant material of the present invention.

Examples 7 to 11 - Flame retardants from phosphonic acid mixtures and intermediate salt complexes from aluminum ethoxide:

167 The process of Example 4 is repeated using mmol of aluminum ethoxide and a mixture of the following phosphonic acids:

Example 7 400 mmol of methylphosphonic acid and 100 mmol of ethyl phosphonic acid

Example 8 300 mmol of methylphosphonic acid and 200 mmol of ethyl phosphonic acid

Example 9 200 mmol of methylphosphonic acid and 300 mmol of ethyl phosphonic acid

Example 10 100 mmol of methylphosphonic acid and 400 mmol of ethyl phosphonic acid

Example 11 450 mmol of methylphosphonic acid and 50 mmol of phenyl phosphonic acid

Example 12 - Flame retardant from intermediate salt complex produced from methylphosphonic acid, ethyl phosphonic acid and aluminum ethoxide:

A solution prepared by adding aluminum ethoxide (167 mmol) to a stirred solution of methylphosphonic acid (500 mmol) in deionized water was mixed with aluminum ethoxide (167 mmol) with a stirring of ethylphosphonic acid (500 mmol) in deionized water. After mixing with the solution prepared by adding it to the prepared solution, it is concentrated and dried at 100° C. in vacuo to give a salt mixture, which is heated at 280° C. for 4 hours to provide the flame retardant material of the present invention.

Example 13 - Flame retardant from a salt blend produced from methylphosphonic acid, ethyl phosphonic acid and calcium hydroxide:

A solution prepared by adding calcium hydroxide (236 mmol) to a stirred solution of methylphosphonic acid (473 mmol) in deionized water, calcium hydroxide (236 mmol) was added to a stirred solution of ethylphosphonic acid (473 mmol) in deionized water After mixing with the solution prepared by doing so, concentration and drying at 100° C. in vacuo to give a salt mixture, which is heated at 280° C. for 4 hours to provide the flame retardant material of the present invention.

Example 14 - Flame retardant from ethyl phosphonic acid and a salt blend produced from a mixture of aluminum ethoxide and calcium hydroxide:

A solution prepared by adding aluminum ethoxide (167 mmol) to a stirred solution of ethylphosphonic acid (500 mmol) in deionized water, calcium hydroxide (236 mmol) into a stirred solution of ethylphosphonic acid (473 mmol) in deionized water After mixing with the solution prepared by adding to , concentrated and dried at 100 ° C. in vacuo to give a salt mixture, which is heated at 280 ° C. for 4 hours to provide the flame retardant material of the present invention.

Examples 15 to 19 - Flame retardants from phosphonic acid mixtures and salt mixtures from aluminum ethoxide:

167 The process of Example 12 is repeated using mmol of aluminum ethoxide and a mixture of the following phosphonic acids:

Example 15 400 mmol of methylphosphonic acid and 100 mmol of ethyl phosphonic acid

Example 16 300 mmol of methylphosphonic acid and 200 mmol of ethyl phosphonic acid

Example 17 200 mmol of methylphosphonic acid and 300 mmol of ethyl phosphonic acid

Example 18 100 mmol of methylphosphonic acid and 400 mmol of ethyl phosphonic acid

Example 19 450 mmol of methylphosphonic acid and 50 mmol of phenyl phosphonic acid

Formulations comprising flame retardants and various synergists from Examples 1, 2 and 3 were blended into polyamide 66 with glass using a Haake Rheocord 90, using a BabyPlast Mini-Molder was molded into 1/16" bars, which were subjected to standard UL 94 vertical burn testing. Formulations and results are listed in Table 1 below.

<tables num="1"><table><tgroup cols="13"><colspec align="justify" colname="col1" colnum="1" colwidth="1687" /><colspec align="justify" colname="col2" colnum="2" colwidth="870" /><colspec align="justify" colname="col3" colnum="3" colwidth="723" /><colspec align="justify" colname="col4" colnum="4" colwidth="870" /><colspec align="justify" colname="col5" colnum="5" colwidth="870" /><colspec align="justify" colname="col6" colnum="6" colwidth="870" /><colspec align="justify" colname="col7" colnum="7" colwidth="870" /><colspec align="justify" colname="col8" colnum="8" colwidth="870" /><colspec align="justify" colname="col9" colnum="9" colwidth="870" /><colspec align="justify" colname="col10" colnum="10" colwidth="870" /><colspec align="justify" colname="col11" colnum="11" colwidth="870" /><colspec align="justify" colname="col12" colnum="12" colwidth="870" /><colspec align="justify" colname="col13" colnum="13" colwidth="720" /><tbody><row><entry align="justify" nameend="col13" namest="col1"><b>FR</b><b> data</b></entry></row><row><entry align="justify" colname="col1">formulation</entry><entry align="justify" colname="col2">1</entry><entry align="justify" colname="col3">2</entry><entry align="justify" colname="col4">3</entry><entry align="justify" colname="col5">4</entry><entry align="justify" colname="col6">5</entry><entry align="justify" colname="col7">6</entry><entry align="justify" colname="col8">7</entry><entry align="justify" colname="col9">8</entry><entry align="justify" colname="col10">9</entry><entry align="justify" colname="col11">10 </entry><entry align="justify" colname="col12">11</entry><entry align="justify" colname="col13">12 </entry></row><row><entry align="justify" colname="col1">nylon 66</entry><entry align="justify" colname="col2">56.3</entry><entry align="justify" colname="col3">45</entry><entry align="justify" colname="col4">53.8</entry><entry align="justify" colname="col5">57.5</entry><entry align="justify" colname="col6">50.7</entry><entry align="justify" colname="col7">53</entry><entry align="justify" colname="col8">50.3</entry><entry align="justify" colname="col9">51.7</entry><entry align="justify" colname="col10">46.3</entry><entry align="justify" colname="col11">53.8</entry><entry align="justify" colname="col12">54.4 </entry><entry align="justify" colname="col13">45</entry></row><row><entry align="justify" colname="col1">glass</entry><entry align="justify" colname="col2">30</entry><entry align="justify" colname="col3">30</entry><entry align="justify" colname="col4">30</entry><entry align="justify" colname="col5">30</entry><entry align="justify" colname="col6">30</entry><entry align="justify" colname="col7">30</entry><entry align="justify" colname="col8">30</entry><entry align="justify" colname="col9">30</entry><entry align="justify" colname="col10">30</entry><entry align="justify" colname="col11">30 </entry><entry align="justify" colname="col12">30</entry><entry align="justify" colname="col13">30</entry></row><row><entry align="justify" colname="col1">FR-INV1</entry><entry align="justify" colname="col2">13.7</entry><entry align="justify" colname="col3">25</entry><entry align="justify" colname="col4">13.7</entry><entry align="justify" colname="col5">10</entry><entry align="justify" colname="col6">13.7</entry><entry align="justify" colname="col7">13.7</entry><entry align="justify" colname="col8">13.7</entry><entry align="justify" colname="col9">13.7</entry><entry align="justify" colname="col10">13.7</entry><entry align="justify" colname="col11">13.7</entry><entry align="justify" colname="col12" /><entry align="justify" colname="col13" /></row><row><entry align="justify" colname="col1">FR-INV2</entry><entry align="justify" colname="col2" /><entry align="justify" colname="col3" /><entry align="justify" colname="col4" /><entry align="justify" colname="col5" /><entry align="justify" colname="col6" /><entry align="justify" colname="col7" /><entry align="justify" colname="col8" /><entry align="justify" colname="col9" /><entry align="justify" colname="col10" /><entry align="justify" colname="col11" /><entry align="justify" colname="col12">15.6</entry><entry align="justify" colname="col13" /></row><row><entry align="justify" colname="col1">FR-INV3</entry><entry align="justify" colname="col2" /><entry align="justify" colname="col3" /><entry align="justify" colname="col4" /><entry align="justify" colname="col5" /><entry align="justify" colname="col6" /><entry align="justify" colname="col7" /><entry align="justify" colname="col8" /><entry align="justify" colname="col9" /><entry align="justify" colname="col10" /><entry align="justify" colname="col11" /><entry align="justify" colname="col12" /><entry align="justify" colname="col13">15</entry></row><row><entry align="justify" colname="col1">SYN1</entry><entry align="justify" colname="col2" /><entry align="justify" colname="col3" /><entry align="justify" colname="col4">2.5</entry><entry align="justify" colname="col5">2.5</entry><entry align="justify" colname="col6" /><entry align="justify" colname="col7" /><entry align="justify" colname="col8" /><entry align="justify" colname="col9" /><entry align="justify" colname="col10" /><entry align="justify" colname="col11" /><entry align="justify" colname="col12" /><entry align="justify" colname="col13" /></row><row><entry align="justify" colname="col1">SYN2</entry><entry align="justify" colname="col2" /><entry align="justify" colname="col3" /><entry align="justify" colname="col4" /><entry align="justify" colname="col5" /><entry align="justify" colname="col6">5.6</entry><entry align="justify" colname="col7" /><entry align="justify" colname="col8" /><entry align="justify" colname="col9" /><entry align="justify" colname="col10" /><entry align="justify" colname="col11" /><entry align="justify" colname="col12" /><entry align="justify" colname="col13" /></row><row><entry align="justify" colname="col1">SYN3</entry><entry align="justify" colname="col2" /><entry align="justify" colname="col3" /><entry align="justify" colname="col4" /><entry align="justify" colname="col5" /><entry align="justify" colname="col6" /><entry align="justify" colname="col7">3.3</entry><entry align="justify" colname="col8" /><entry align="justify" colname="col9" /><entry align="justify" colname="col10" /><entry align="justify" colname="col11" /><entry align="justify" colname="col12" /><entry align="justify" colname="col13" /></row><row><entry align="justify" colname="col1">SYN4</entry><entry align="justify" colname="col2" /><entry align="justify" colname="col3" /><entry align="justify" colname="col4" /><entry align="justify" colname="col5" /><entry align="justify" colname="col6" /><entry align="justify" colname="col7" /><entry align="justify" colname="col8">6</entry><entry align="justify" colname="col9" /><entry align="justify" colname="col10" /><entry align="justify" colname="col11" /><entry align="justify" colname="col12" /><entry align="justify" colname="col13" /></row><row><entry align="justify" colname="col1">SYN5</entry><entry align="justify" colname="col2" /><entry align="justify" colname="col3" /><entry align="justify" colname="col4" /><entry align="justify" colname="col5" /><entry align="justify" colname="col6" /><entry align="justify" colname="col7" /><entry align="justify" colname="col8" /><entry align="justify" colname="col9">4.6</entry><entry align="justify" colname="col10" /><entry align="justify" colname="col11" /><entry align="justify" colname="col12" /><entry align="justify" colname="col13" /></row><row><entry align="justify" colname="col1">SYN6</entry><entry align="justify" colname="col2" /><entry align="justify" colname="col3" /><entry align="justify" colname="col4" /><entry align="justify" colname="col5" /><entry align="justify" colname="col6" /><entry align="justify" colname="col7" /><entry align="justify" colname="col8" /><entry align="justify" colname="col9" /><entry align="justify" colname="col10">10</entry><entry align="justify" colname="col11" /><entry align="justify" colname="col12" /><entry align="justify" colname="col13" /></row><row><entry align="justify" colname="col1">SYN7</entry><entry align="justify" colname="col2" /><entry align="justify" colname="col3" /><entry align="justify" colname="col4" /><entry align="justify" colname="col5" /><entry align="justify" colname="col6" /><entry align="justify" colname="col7" /><entry align="justify" colname="col8" /><entry align="justify" colname="col9" /><entry align="justify" colname="col10" /><entry align="justify" colname="col11">2.5</entry><entry align="justify" colname="col12" /><entry align="justify" colname="col13" /></row><row><entry align="justify" colname="col1">SYN8</entry><entry align="justify" colname="col2" /><entry align="justify" colname="col3" /><entry align="justify" colname="col4" /><entry align="justify" colname="col5" /><entry align="justify" colname="col6" /><entry align="justify" colname="col7" /><entry align="justify" colname="col8" /><entry align="justify" colname="col9" /><entry align="justify" colname="col10" /><entry align="justify" colname="col11" /><entry align="justify" colname="col12" /><entry align="justify" colname="col13">10</entry></row><row><entry align="justify" colname="col1">UL 94</entry><entry align="justify" colname="col2">V-1</entry><entry align="justify" colname="col3">V-0</entry><entry align="justify" colname="col4">V-0</entry><entry align="justify" colname="col5">V-1</entry><entry align="justify" colname="col6">V-0</entry><entry align="justify" colname="col7">V-0</entry><entry align="justify" colname="col8">V-0</entry><entry align="justify" colname="col9">V-0</entry><entry align="justify" colname="col10">V-0</entry><entry align="justify" colname="col11">V-1</entry><entry align="justify" colname="col12">V-0</entry><entry align="justify" colname="col13">V-0</entry></row></tbody></tgroup></table></tables>

Synergists used in the FR formulation:

SYN1: aluminum tris(diethylphosphinate), Exolit^® OP 1230

<img file="KR102403004B1_D0010.tif" />

SYN2: methylene-diphenylphosphine oxide-substituted polyaryl ether

<img file="KR102403004B1_D0011.tif" />

SYN3: p-xylylenebis(diphenylphosphine oxide)

<img file="KR102403004B1_D0012.tif" />

SYN4: 4,4'-bis(diphenylphosphinylmethyl)-1,1'-biphenyl

<img file="KR102403004B1_D0013.tif" />

SYN5: 1,2-bis-(9,10-dihydro-9-oxy-10-phosphaphenanthrene

-10-oxide) ethane

<img file="KR102403004B1_D0014.tif" />

SYN6: Melem, Delacal^® NFR HP

<img file="KR102403004B1_D0015.tif" />

SYN7: Aluminum hydrogen phosphite

<img file="KR102403004B1_D0016.tif" />

SYN8: Dimelamine Zinc Pyrophosphate, Safire^® 400

<img file="KR102403004B1_D0017.tif" />