KR20160045796A - Flame retardant prepared from amide derivatives and process for making the same - Google Patents

Abstract

As a method for producing a melamine derivative mixture, first, there is a method comprising the steps of: reacting at least a nitrogen-containing compound with a metal phosphite or hydrogen hypophosphate in an aqueous solution; And second, heating the reaction mixture produced in solid form in the presence of an oxidizing agent at a temperature comprised between 150 ° C and 500 ° C to obtain a melamine derivative mixture. The melamine derivative mixture thus obtained is found to be useful as a flame retardant in epoxy polymers and to help maintain its physical properties.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a flame retardant prepared from amide derivatives and a process for producing the flame retardant,

Cross reference to related application

This application claims priority to PCT International Application No. PCT / CN2013 / 082132, filed on August 23, 2013, the entire contents of which are incorporated herein by reference.

Technical field

The present invention relates to a process for preparing a melamine derivative mixture by reaction between at least an amide derivative and a metal phosphite, and to the use of said reaction for producing a flame retardant.

Flame retardants are additives used in plastics and other industrial products to inhibit or resist the spread of fire. In recent years, due to the environmental advantages caused by finite halogen levels, the industrial application of halogen-free flame retardants has attracted much research attention. One commonly used halogen-free flame retardant (HFFR) is the phosphonate HFFR, such as melamine pyrophosphate (MPP), which is widely used in thermoplastics and has the general molecular formula C ₃ H ₆ N ₆ ^. (H ₃ PO ₄ ) _n . In the case of fire, nitrogen elements and phosphorus elements in the MPP can be combined to help form crosslinked char in the applied product, thereby enhancing its flame retardant performance.

Nevertheless, like other known phosphonate flame retardant additives, MPP has its own limitations and disadvantages when used in thermoplastics. For example, off-gassing and liquid bleed out have been found in thermoplastic systems incorporating MPP, and these problems have been linked to phosphonate slat / synergist interactions in the system . ≪ / RTI >

Moreover, many of the known phosphonate HFFR additives tend to migrate and / or volatilize away from the thermoplastic over time, or they may decompose at various thermoplastic processing temperatures (especially extrusion processing temperatures) Has been found to cause gradual loss problems. In addition, these existing phosphonate HFFR additives are also known for their hygroscopic properties, which will ultimately lead to unwanted water / water absorption.

Accordingly, the present invention seeks to provide an economical approach for producing novel phosphonate HFFR additives that overcomes the above-mentioned disadvantages of conventional phosphonate HFFR additives, Provides satisfactory and stable flame retardant properties while maintaining excellent mechanical properties of the resulting polymer.

The present invention relates to a melamine derivative mixture having flame retardant properties, and a process for producing the same.

In one aspect of the present invention, there is provided a process for preparing a melamine derivative mixture,

(i) providing an aqueous solution (solution (S)) of a metal phosphite or hydrogen phosphite having a pH of 1 to 7;

(ii) mixing the solution (S) with at least one nitrogen-containing compound [compound (N)] at a temperature of 5 ° C to 100 ° C to obtain a reaction mixture;

(iii) separating the reaction mixture obtained in step (ii) by a solid-liquid separation method to obtain a solid phase; And

(iv) heating the solid phase obtained in step (iii) in the presence of an oxidizing agent at a temperature of from 150 DEG C to 500 DEG C to obtain a melamine derivative mixture

At least,

The compound (N) is a compound of the formula (I) or (II)

(I)

≪ RTI ID = 0.0 &

In this formula,

R ₁ , R ₂ , and R ₃ are independently hydrogen, hydroxyl, amino, or mono- or di C ₁ -C ₈ alkylamino; Or C ₁ -C ₈ alkyl, C ₅ -C ₁₆ cycloalkyl, -alkylcycloalkyl, each optionally substituted by hydroxyl or C ₁ -C ₄ hydroxyalkyl, C ₂ -C ₈ alkenyl, C ₁ -C ₈ alkoxyl , Acyl, -acyloxy, C ₆ -C ₁₂ aryl, -OR _1, and -N (R ₁ ) R ₂ ; Or N-alicyclic or N-aromatic, wherein the N-alicyclic group represents a cyclic nitrogen-containing compound such as pyrrodiline, piperidine, imidazolidine, piperazine and the N -aromatic represents pyrrole, pyridine, Lt; / RTI > represents a nitrogen-containing heteroaromatic cyclic compound such as benzothiazole, benzothiazole, benzothiazole, benzothiazole, X is phosphoric acid or pyrophosphoric acid; q is 1, 2, 3, or 4; a is 1, 2, 3, or 4; Provided that at least one of R ₁ , R ₂ , and R ₃ has an amino end group;

A metal phosphite or hydrogen phosphite refers to a salt containing a metal cation and one anion of HPO ₃ ^{2 -} or H ₂ PO ₃ ^- .

Unexpectedly, the Applicant has found that by the above-mentioned method, a melamine derivative mixture can be produced that provides excellent flame retardant properties and helps maintain good mechanical properties of the polymer to be added. Particularly, in the flame retardant performance test, the melamine derivative mixture produced by the above method exhibits superior stability and polymer compatibility as compared with the commercial MPP flame retardant, and a vapor-phase flame retardant and a condensed-phase flame retardant Both can be effective. Moreover, as compared to the commercial MPP, the melamine mixture obtained from the process of the present invention is also found to be less acidic in aqueous solution, which provides better compatibility in the resin matrix.

Thus, in another embodiment of the present invention, this is a melamine derivative mixture produced by the above-mentioned process, or

(i) a metal element in the range of 1% to 20% by weight, a phosphorus element in the range of 5% to 25% by weight and a nitrogen element in the range of 15% to 40% by weight, based on the total weight of the melamine derivative mixture box; And

(ii) a mixture of phosphorus species containing P (III) in a molar percentage of 5% to 100%

To a melamine derivative mixture.

In another aspect of the present invention, this relates to the use of a reaction between at least one compound (N) and a metal phosphite or hydrogen phosphite in an aqueous solution to produce a flame retardant, wherein the compound (N) Phosphate or hydrogen phosphite is as defined above.

The compound (N) suitable for the present invention can be selected from the group consisting of melamine, melamine cyanurate, melamine phosphate compound, dimelamine phosphate compound, melamine pyrophosphate compound, melem, melam, melon, . In a preferred embodiment, the compound (N) is melamine.

For purposes of the present invention, a compound of "melamine" refers to a compound of formula III:

(III)

.

.

According to the present invention, a metal phosphite or hydrogen hypophosphate refers to a salt containing a metal cation and one anion of HPO ₃ ^{2 -} or H ₂ PO ₃ ^- wherein the metal cation is an alkali metal, an alkaline earth metal, Metal, and the like. Examples of metal phosphites or hydrogen phosphites include Li ₂ HPO ₃ , LiH ₂ PO ₃ , Na ₂ HPO ₃ , NaH ₂ PO ₃ , K ₂ HPO ₃ , KH ₂ PO ₃ , CaHPO ₃ , Ca (H ₂ PO ₃ ) ₂ , ZnHPO ₃ , Zn (H ₂ PO ₃ ) ₂ , MgHPO ₃ , Mg (H ₂ PO ₃ ) ₂ , Al ₂ (HPO ₃ ) ₃ and Al (H ₂ PO ₃ ) ₃ , ₃ .

In one embodiment of the present invention, the solution (S) is an aqueous solution comprising a metal phosphite or a hydrogen phosphite.

Typically, in step (i) of the inventive method described above, solution (S) is acidic and preferably has a pH value of 1.0 to 6.0, more preferably of 1.5 to 4.5. As used throughout this application, the term "acidic" refers to a pH value of less than about 7, and the pH value refers to the pH of an aqueous phase. The pH value of the solution (S) can be adjusted by carefully adding acid or base thereto. Solution, if having a higher pH value than the (S) the desired pH value, pH value by the addition of an appropriate acid _{(e.g., HCl, HNO 3, H 3} PO 3, H 3 PO 2 or H ₃ PO ₄₎ . Conversely, if the solution S has a lower pH value than the desired pH value, the pH value is adjusted by adding an appropriate base (e.g. NaOH, KOH KOH, Ca (OH) ₂ , or NH ₃ ) .

In step (ii), the reaction of the compound (N) with the solution (S) is usually carried out at a temperature of from 5 캜 to 100 캜, preferably from 15 캜 to 50 캜, more preferably from 15 캜 to 25 캜, .

The reaction time of step (ii) of the present process invention can be varied from 15 minutes to 3 hours, preferably from 30 minutes to 1 hour, and is selected to be a period sufficient to produce the desired reaction mixture in the appropriate yield. In particular, the reaction time of step (ii) of the present process invention is affected to a considerable extent by the reaction temperature, the concentration and selectivity of the reactants, the presence of the catalyst, and other factors in step (ii) selected by those skilled in the art.

Preferably, in the reaction in step (ii), the molar ratio of the sum of the phosphite and the hydrogen phosphite in the compound (N) to the solution (S) is from 1: 5 to 5: 1, 2: 1, more preferably 1.1: 1 to 1: 1.1.

In step (iii) of the process invention, the reaction mixture obtained in step (ii) is separated by a suitable solid-liquid separation process to obtain a solid phase, wherein the solid-liquid separation process may be filtration, spray drying and the like.

In the next step (iv), the solid phase separated from step (iii) is heated in the presence of an oxidizing agent at a temperature of from 150 캜 to 500 캜. In particular, step (iv) generally has a dry loss of 10% to 40% by weight, based on the weight of the solid phase isolated from step (iii).

The heating temperature set in step (iv) is generally 150 ° C to 500 ° C, preferably 200 ° C to 400 ° C, more preferably 300 ° C to 380 ° C.

The oxidant used in step (iv) may be selected from air, oxygen, gaseous oxidant precursors such as oxides of nitrogen (N _x O _y ) and ozone, or other gaseous oxidants commonly used in the art.

The heating time in step (iv) is selected to be generally from 1 hour to 8 hours, preferably from 2 hours to 4 hours, depending on the heating temperature, the presence of the catalyst, and other conditions used. Typically, the heating time in step (iv) is selected by those skilled in the art to obtain a loss on drying of 10% to 40% by weight based on the weight of the solid phase isolated from step (iii).

The invention also relates to the products obtainable by the process of the invention described above.

Elemental analysis of the final product obtained after the step (iv)

(i) a metal element in the range of 1% to 20% by weight, a phosphorus element in the range of 5% to 25% by weight and a nitrogen element in the range of 15% to 40% by weight, based on the total weight of the melamine derivative mixture box; And

(ii) a mixture of phosphorus species containing P (III) species in a molar percentage of 5% to 100%

. ≪ / RTI >

It has been found that the melamine derivative mixtures according to the invention provide improved stability. The stability of the mixture can be evaluated by measuring the onset of decomposition of the mixture by thermogravimetric analysis (TGA). Procedures for such analysis are well known in the art. In one implementation, a melamine derivative mixture is more than 300 ℃ a TGA temperature for a 3% weight loss under a N ₂ atmosphere. In a preferred embodiment, a mixture of melamine derivative is more than 330 ℃ a TGA temperature for a 3% weight loss under a N ₂ atmosphere. Typically, the heating rate of the TGA analysis is 10 ° C / min.

According to another aspect of the present invention, there is provided a polymer composition (composition (P)) comprising at least one polymer and a melamine derivative mixture as described above.

Typically, at least one polymer in the composition (P) is selected from the group consisting of polyphenylene ethers, polyamides such as PA66, PA6, PA610, or high temperature polyamides (PPA / PA4.6 / PA9T / PA66.6T / PA10T / PA6.6T And blends of polyamides such as PA / PET, PA / ABS or PA / PP), polyesters, polycarbonates, epoxy resins; Phenolic resin; Acrylonitrile butadiene styrene (ABS); Styrene acrylonitrile (SAN); A mixture of high impact polystyrene (HIPS) and polyphenylene ether (e.g., PPO / HIPS); Styrene butadiene rubber and lattices (SBR and SB); And halogenated polymers such as polyvinyl chloride (PVC), and blends and blends of these polymers, expandable polystyrene (EPS), and polybutylene terephthalate (PBT).

Further, the composition (P) may further comprise one or more additional flame retardant additives, such flame retardant additives being selected from the group consisting of flame retardant properties such as endothermic cracking, heat shielding, dilution of the gas phase, dilution of the combustible fraction, and radical quenching quenching can be improved.

Additional flame retardant additives in composition (P) are described in particular in US 6344158 , US 6365071 , US 6211402 , and US 6255371 .

Preferably, the additional flame retardant additive (s) used in composition (P) is selected from the group comprising:

A) phosphorus-containing flame retardant additives such as:

- Oxidophosphines such as triphenyl oxide phosphine, tri- (3-hydroxypropyl) oxazine phosphine and tri- (3-hydroxy-2-methylpropyl) oxide phosphine;

- Phosphonic acids and salts thereof, and phosphinic acids and salts thereof such as phosphinic acids of zinc, magnesium, calcium, aluminum or manganese, in particular aluminum salts of diethylphosphinic acid, aluminum salts of dimethylphosphinic acid, or zinc salts of dimethylphosphinic acid ;

- Cyclic phosphonates such as diphosphate cyclic esters such as Antiblaze 1045;

- Organic phosphates such as triphenyl phosphate;

- Inorganic phosphates such as ammonium polyphosphate and sodium polyphosphate; And

- Which can be found in various shapes, such as a stabilized shape, a coated shape, a shape as a powder,

B) nitrogen-containing flame retardant additives such as: triazine, cyanuric acid and / or isocyanuric acid, melamine or derivatives thereof such as cyanurate, oxalate, phthalate, borate, sulfate, phosphate, polyphosphate and / Phosphate, condensation products of melamine such as melem, melam, melon, tris (hydroxyethyl) isocyanurate, benzoguanamine, guanidine, allantoin and glycoluril,

C) halogen-containing flame retardant additives such as:

- Brominated flame retardant additives such as polybrominated diphenyl oxide (PBDPO), brominated polystyrene (BrPS), poly (pentabromobenzyl acrylate), brominated indane, tetradecabromodiphenoxybenzene (Saytex 120), ethane- , 2-bis (pentabromophenyl) or Saytex 8010 (Albemarle), tetrabromobisphenol A and brominated epoxy oligomers. In particular, the following compounds may be used: PDBS-80 from Chemtura, Saytex HP 3010 from Albemarle or FR-803P from Dea Sea Bromine Group, FR-1210 from Dea Sea Bromine Group, Phenyl ether (OBPE), FR-245 from Dead Sea Bromine Group, FR-1025 from Dead Sea Bromine Group and F-2300 or F2400 from Dead Sea Bromine Group; And

- a chlorine-containing flame-retardant additives, such as Dechlorane plus ^® from OxyChem captured (CAS 13560-89-9), and

D) inorganic flame retardant additives such as antimony trioxide, aluminum hydroxide, magnesium hydroxide, cerium oxide, boron-containing compounds such as calcium borate.

These listed flame retardant additive compounds may be used alone or in combination in the composition (P). If desired, a charring agent and a charring catalyst may also be added.

Furthermore, the composition (P) can also contain fillers and reinforcing materials and / or other additives such as lubricants (e.g. stearic acid or stearate such as calcium stearate), glass fibers, or antidriping agents such as poly (Tetrafluoroethylene), for example PTFE SN3306.

In addition, the composition (P) may also contain additives commonly used in the production of polymer compositions such as plasticizers, nucleating agents, catalysts, photostabilizers and / or heat stabilizers, antioxidants, antistatic agents, colorants, pigments, Such as carbon black, molding additives, and the like.

For the preparation of the composition (P), the fillers and additives may be added by any conventional means, for example during polymerization or as a molten mixture. Preferably, the additive is added to the polymer during the melt process, for example during the melt extrusion step. Alternatively, the additive may be added to the polymer in a solid state process in a mechanical mixer to produce a solid mixture which can then be melted, for example, by an extrusion process.

The composition (P) can be used as a raw material in the field of plastic processing for the production of articles which are formed, for example, by injection molding, injection / blow molding, extrusion or by extrusion / blow molding. According to one customary embodiment, the composition (P) is extruded in the form of a rod, for example in a twin screw extruder, and then the rod is chopped into granules. The molded component is then produced by melting the granules produced above and feeding the molten composition into the injection-molding device.

Examples of articles made from composition (P) include vehicle components, such as tubes, tanks, bodywork components, or components under the engine hood, as well as articles for electrical and electronic applications, such as connectors.

If the disclosure of any patent, patent application, and publication incorporated herein by reference contradicts the description of the present application to such an extent that the term may be obscured, the description will be prioritized.

The present invention will be further illustrated by reference to the following examples.

material

PA 66: aliphatic polyamides obtained from Solvay Advanced Polymers;

PBT 1200: polybutylene terephthalate resin available from Taiwan Changchun Ltd;

Exolit OP1230: aluminum phosphinate from Clariant GmbH;

MPP (Melapur-200): obtained from BASF

Example  One

78 g of H ₃ PO ₃ were added to a mixture of 70.86 g of Ca (OH) ₂ and 400 g of H ₂ O under stirring. Then, the resulting mixture was stirred at 40 DEG C for 2.5 hours and then filtered to obtain a solid mixture containing calcium phosphite. The solid mixture was washed by using deionized water (DI water) and dried at 105 DEG C for 3 hours.

A 250 mL reactor equipped with a mechanical stirrer was charged with 120 g of water and 30.46 g of the calcium phosphite mixture obtained as described above. Under stirring, 53.3 g of 85% orthophosphoric acid solution at room temperature was added to the resulting mixture. After the addition, the mixture was stirred for 30 minutes and then filtered to remove undissolved solids to give a clear solution. Then 58 g of melamine was slowly added to the filtrate with stirring for an additional hour of the reaction. The mixture was then evaporated to remove all water, yielding a white solid. This white solid was heated at 330 < 0 > C for 3 hours to a weight loss of 22% to convert it to calcium melamine phosphorous salt. The thus obtained calcium melamine salt was found to have 27.68% by weight of N, 12.24% by weight of C, 2.40% by weight of H, 19.68% by weight of P% and 7.09% by weight of Ca. The percentage of the remaining oxygen element is calculated to be 30.91% by weight in the salt which is calcium melamine. Thus, based on the total valence balance, the mantissa of the phosphorus element in the salt which is calcium melamine can be calculated to be 4.66 by the formula a:

[Formula a]

From this mantissa value, the P (III) mole percentage in the phosphorus species of the salt, which is calcium melamine, can be calculated to be 17%.

Further analysis showed that the 10 wt% aqueous slurry of calcium melamine salt had a pH of 5.4 and a 10 wt% aqueous solution of MPP had a pH of 5.0. Thus, as compared to MPP, the salt of calcium obtained in this example is less acidic, thus providing better resin matrix compatibility. Moreover, TGA analysis of the salt product of this example showed 3% weight loss at 383 ° C under an N ₂ atmosphere.

Example  2

A 500 mL reactor equipped with a mechanical stirrer was charged with 400 g of water and 60 g of calcium phosphite mixture. Under stirring, 91.34 g of a 38% hydrochloric acid acid solution at room temperature was added to the resulting mixture. After the addition, the mixture was stirred for 30 minutes and then filtered to remove undissolved solids to give a clear solution. Then 144 g of melamine was slowly added to the filtrate with stirring for an additional hour of the reaction. The reaction mixture was then filtered to remove the aqueous solution and a white solid was obtained. This white solid was then heated to 330 ° C for 3 hours to a weight loss of 23% to convert it to a salt that is calcium melamine. The thus obtained calcium melamine salt contained 41.55% of N, 7.27% of P%, and 7.98% of Ca according to the elemental analysis. The percentage of the remaining oxygen element is calculated to be 23.67% by weight in the calcium melamine salt. Thus, based on formula a above, the salt product has a phosphorus number of 4.41, which corresponds to a P (III) percentage of 29.5% of its phosphorus species.

Further analysis indicates that the 10% by weight aqueous slurry of the salt, which is the calcium melamine obtained in this example, has a pH of 5.2 and is less acidic than the 10% by weight aqueous solution of MPP in particular, thus providing relatively better compatibility in the resin matrix Respectively. Moreover, TGA analysis of the salt product showed a 3% weight loss at 369 ° C under an N ₂ atmosphere.

Example  3

A 500 mL reactor equipped with a mechanical stirrer was charged with 400 g of water and 65.5 g of a calcium phosphite mixture. Under stirring, 91.34 g of a 38% hydrochloric acid acid solution at room temperature was added to the resulting mixture. After the addition, the mixture was stirred for 30 minutes and then filtered to remove undissolved solids to give a clear solution. Then 144 g of melamine was slowly added to the filtrate with stirring for an additional hour of the reaction. The mixture was then filtered to remove the aqueous solution, yielding a white solid. This white solid was heated at 330 [deg.] C for 3 hours to produce a salt that was calcium melamine, with a 23% weight loss during heating. The thus obtained calcium melamine salt contained 31.5% N, 16.0% C, 2.60% H, 14.2% P and 7.98% Ca according to elemental analysis. The percentage of the remaining oxygen element is 27.72% by weight in the calcium melamine salt. Thus, based on formula a above, the salt product has a phosphorus number of 4.11, which corresponds to a P (III) percentage of 44.5% of its phosphorus species.

Further analysis indicates that the 10% by weight aqueous slurry of the salt, which is the calcium melamine obtained in the above procedure, is also less acidic than the 10% by weight aqueous solution of MPP, and thus has a comparatively better compatibility in the resin matrix, Respectively. Moreover, TGA analysis of this salt product showed 3% weight loss at 335 ° C under N ₂ atmosphere.

Example  4

A 500 mL reactor equipped with a mechanical stirrer was charged with 400 g of water and 65.5 g of calcium phosphite mixture. Under stirring, 66 g of 67% nitric acid acid solution at room temperature was added to the resulting mixture. After the addition, the mixture was stirred for 30 minutes and then filtered to remove undissolved solids to give a clear solution. Then 106 g of melamine was slowly added to the filtrate with stirring for an additional hour of the reaction. Thereafter, the mixture was filtered to remove all of the aqueous solution to obtain a white solid. This white solid was heated at 330 [deg.] C for 3 hours to produce a salt that was calcium melamine, with a 21% weight loss during heating. The thus obtained calcium melamine salt contained 27.68% N, 13.21% C, 2.39% H, 18.55% P% and 7.89% Ca according to the elemental analysis. The percentage of the remaining oxygen element is calculated to be 30.28% by weight in the calcium melamine salt. Thus, based on formula a above, the salt product has a phosphorus number of 4.23, which corresponds to a P (III) percentage of 38.5% of its phosphorus species.

Further analysis indicates that the 10% by weight aqueous slurry of the salt, which is the calcium melamine obtained in the above procedure, is also less acidic than the 10% by weight aqueous solution of MPP, and thus has a comparatively better compatibility in the resin matrix, Respectively. Furthermore, TGA analysis of the salt product was characterized by that there was a 3% weight loss at 400 ℃ under N ₂ ambience.

exam Example  One: Example  1 to Example  Determination of Flame Retardant Capacity of 4

The salts, which are calcium melamine obtained from Examples 1 to 4, were each tested as a flame retardant agent for an epoxy resin. Specifically, various resin samples were prepared by mixing calcium melamine salt with glass fibers and selected monomers (see Table 1) in an injection molding machine, then cured and then extruded into granules. For comparison, two additional resin samples were prepared in the same manner, except that no calcium melamine salt according to the invention was added (see CE 1 and CE 2 in Table 1). The flame retardant performance of these resin samples was tested according to the UL94 vertical burn test procedure using sample thicknesses of both 1.6 mm and 0.8 mm.

Trail No. One 2 3 4 5 6 Melamine calcium salt Example 1 Example 2 Example 3 Example 4 CE1 CE2 Resin formulation ( weight% ) PA66 (26A) 45 40 70 PBT (1200) /% 45 40 70 glass fiber/% 30 30 30 30 30 30 Melamine calcium salt /% 25 30 25 30 Flammability test ( Ul - 94 ratings ) For 1.6 mm thick resin v0 v0 v0 v0 HB HB For 0.8 mm thick resin v0 v0 v0 v0 HB HB

As can be seen in Table 1, the resin samples incorporating the salts of calcium melamine of Examples 1 to 4 achieved V0 grades in the UL 94 vertical burn test procedure, respectively, , CE1 and CE2) and exhibits a satisfactory level of fire protection and greatly improved flame retardancy.

exam Example  2: Example  1 and the flame retardancy of MPP

For comparison, a resin sample containing a given amount of MPP or a salt that is the calcium melamine of Example 1 was tested for flame retardancy. Specifically, by mixing MPP (melapur-200) or the salt product of Example 1 into a blend of glass fibers, selected monomers (see below) and Zn ₃ (BO ₃ ) ₂ (with an equivalent percentage of each component) Two resin samples were prepared, then cured and extruded in granular form. The flame retardant performance and physical properties of both resin samples were tested and the results are shown in Table 2 below.

Trail number 7 8 Resin formulation ( weight% ) PA66 (26A) 52 52 glass fiber 30 30 Exolit OP1230 11.6 11.6 Melamine calcium salt (Example 1) 5.8 MPP (Melapur-200) 5.8 Zn ₃ (BO ₃ ) ₂ 0.6 0.6 Flammability test ( Ul - 94 ratings ) For 1.6 mm thick resin v0 v0 For 0.8 mm thick resin v0 v0 Resin Properties Tensile Strength (Mpa) 153 130 Elongation (%) 2.70 2.30 Notched Charpy Impact Strength (KJ / m ² ) 8.78 6 Charpy impact strength (KJ / m ² ) 63.38 55

As can be seen in Table 2, the resin sample incorporating the calcium melamine salt of Example 1 attained the same excellent flame retardancy as the MPP-added sample, particularly achieving improved physical properties than the latter.

Claims (16)

A method for producing a melamine derivative mixture,
(i) providing an aqueous solution (solution (S)) of a metal phosphite or hydrogen phosphite having a pH of 1 to 7;
(ii) mixing the solution (S) with at least one nitrogen-containing compound [compound (N)] at a temperature of 5 ° C to 100 ° C to obtain a reaction mixture;
(iii) separating the reaction mixture obtained in step (ii) by a solid-liquid separation method to obtain a solid phase; And
(iv) heating the solid phase obtained in step (iii) in the presence of an oxidizing agent at a temperature of from 150 DEG C to 500 DEG C to obtain a melamine derivative mixture
At least,
Wherein the compound (N) is a compound of formula I or formula II.
(I)

≪ RTI ID = 0.0 &

In this formula,
R ₁ , R ₂ , and R ₃ are independently hydrogen, hydroxyl, amino, or mono- or di C ₁ -C ₈ alkylamino; Or C ₁ -C ₈ alkyl, C ₅ -C ₁₆ cycloalkyl, -alkylcycloalkyl, each optionally substituted by hydroxyl or C ₁ -C ₄ hydroxyalkyl, C ₂ -C ₈ alkenyl, C ₁ -C ₈ alkoxyl , Acyl, -acyloxy, C ₆ -C ₁₂ aryl, -OR _1, and -N (R ₁ ) R ₂ ; Or N-alicyclic or N-aromatic, wherein the N-alicyclic group represents a cyclic nitrogen-containing compound such as pyrrodiline, piperidine, imidazolidine, piperazine and the N -aromatic represents pyrrole, pyridine, Lt; / RTI > represents a nitrogen-containing heteroaromatic cyclic compound such as benzothiazole, benzothiazole, benzothiazole, benzothiazole, X is phosphoric acid or pyrophosphoric acid; q is 1, 2, 3, or 4; a is 1, 2, 3, or 4; Provided that at least one of R ₁ , R ₂ , and R ₃ has an amino end group;
A metal phosphite or hydrogen phosphite refers to a salt containing a metal cation and one anion of HPO ₃ ^{2 -} or H ₂ PO ₃ ^- . The method according to claim 1, wherein the metal phosphite or hydrogen phosphite is selected from the group consisting of Li ₂ HPO ₃ , LiH ₂ PO ₃ , Na ₂ HPO ₃ , NaH ₂ PO ₃ , K ₂ HPO ₃ , KH ₂ PO ₃ , CaHPO ₃ , Ca consisting of _{H 2 PO 3) 2, ZnHPO} 3, Zn (H 2 PO 3) 2, MgHPO 3, Mg (H 2 PO 3) 2, Al 2 (HPO 3) 3, and Al (H ₂ PO _{3) 3} ≪ / RTI > The method of claim 2, wherein the metal phosphite is CaHPO ₃ the method. 4. The compound according to any one of claims 1 to 3, wherein the compound (N) is at least one compound selected from the group consisting of melamine, melamine cyanurate, melamine phosphate compound, dimelamine phosphate compound, melamine pyrophosphate compound, melem, melam, melon, ≪ / RTI > and amelide. 5. The method of claim 4, wherein the compound (N) is melamine. 6. The method according to any one of claims 1 to 5, wherein in step (i), the solution (S) is acidic and has a pH value of from 1.0 to 6.0, preferably from 1.5 to 4.5. 7. The process according to any one of claims 1 to 6, wherein in step (ii) the molar ratio of the compound (N) to the phosphite and / or hydrogen phosphite in solution (S) is from 1: 5 to 5: Preferably from 1: 2 to 2: 1, more preferably from 1.1: 1 to 1: 1.1. 8. The method according to any one of claims 1 to 7, wherein in step (iv), the heating temperature is 200 ° C to 400 ° C, preferably 300 ° C to 380 ° C. Any one of claims 1 to 8 according to any one of, wherein, the one in step (iv), wherein the oxidizing agent used is selected from air, oxygen, nitrogen (N _x O _y) and ozone. 10. A process according to any one of claims 1 to 9, wherein in step (iv), to obtain a dry loss of from 10% to 40% by weight, based on the weight of the solid phase separated from step (iii) Wherein the heating time is from 1 hour to 8 hours, preferably from 2 hours to 4 hours. 10. A product obtainable by the process of any one of claims 1 to 10. (N) and a metal phosphite or hydrogen hypophosphate in an aqueous solution, wherein the compound (N) and the metal phosphite or hydrogen phosphite are used for producing a flame retardant as defined in claim 1 Lt; / RTI > (i) a metal element in the range of 1% to 20% by weight, a phosphorus element in the range of 5% to 25% by weight and a nitrogen element in the range of 15% to 40% by weight, based on the total weight of the melamine derivative mixture box; And
(ii) a mixture of phosphorus species containing P (III) species in a molar percentage of 5% to 100%
≪ / RTI > The method of claim 13, wherein the melamine derivative is a mixture N ₂ less than the TGA temperature for a 3% weight loss 300 ℃ atmosphere, a mixture of melamine derivative. A polymer composition comprising at least one polymer and a melamine derivative mixture obtained by any one of claims 1 to 10 (composition (P)]. A polymer composition comprising at least one polymer and a melamine derivative mixture of claims 13 or 14 (composition (P)).