Organic phosphonate flame retardant as well as preparation method and application thereof

Abstract

The organic phosphonate flame retardant prepared by the invention is obtained by reacting dialkyl hypophosphorous acid or dialkyl hypophosphite with halogenated alkyl phosphine oxide in a solvent and then separating and purifying, the synthesis method is simple, the use of high-pollution and high-toxicity substances is avoided, the synthesis structure is clear, and the temperature resistance is not influenced by residues of reactive hydrogen on phosphorus. Meanwhile, the synthesized ester group-containing organic phosphonate flame retardant provides better flame retardant property under the condition of lower additive amount, and the resin has higher retention rate of mechanical property and electrical property due to the low additive amount.

Description

Technical Field

[0001] This invention relates to the field of flame retardant technology, and in particular to an organophosphonate flame retardant, its preparation method, and its application. Background Technology

[0002] Organic polymers are a class of materials used extensively in the current materials market. Organic compounds are generally divided into rubber, which has low hardness and high elongation, and plastics, which have high hardness and strength, as well as synthetic fibers, coatings, and other materials. However, polymer molecules contain a large number of C, H, O, and N elements, making them flammable materials. They will continue to burn when ignited, posing a significant risk to people's lives and property, especially electrical polymers such as those used in electronics, electrical appliances, wires, and cables, which can spread rapidly once ignited.

[0003] Many conventional phosphorus-based flame retardants have been developed, such as ADP, RDP, XDP, and DOPO. However, they either have short organic chains, such as ADP, which has only two carbon atoms in its organic chain, resulting in poor compatibility between the flame retardant and the resin; or they have low phosphorus content, such as RDP, XDP, and DOPO, which all have a phosphorus content of around 10%, resulting in low flame retardant efficiency; or they are water-soluble, such as dimethyl methylphosphonate, diethyl ethylphosphonate, and cyclic phosphates, which limit their application in resins. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the above-mentioned technologies and provide an organophosphonate flame retardant, its preparation method, and its application.

[0005] Therefore, the present invention provides an organophosphonate flame retardant having the following structure:

[0006] Structural Formula I

[0007] or,

[0008] Structural Form II

[0009] Wherein, R1 and R2 are selected from C1-C18 hydrocarbon groups; R3 and R5 are selected from C1-C18 hydrocarbon subgroups; R4 is selected from C1-C18 hydrocarbon groups, halohydrocarbon groups, alcohol hydrocarbon groups, or structures as shown in structural formula III; R6 is selected from hydrogen or C1-C18 hydrocarbon groups; x and y are both positive integers from 0 to 100.

[0010] Structural Formula III is

[0011] Structural Formula III.

[0012] A method for preparing an organophosphonate flame retardant includes the following steps:

[0013] The organophosphate flame retardant is obtained by reacting dihydrophosphoric acid or dihydrophosphoric acid salt with haloalkylphosphine oxide in a solvent, followed by separation and purification.

[0014] The reaction formula is:

[0015]

[0016] Preferably, the reactants also include alkylphosphite or alkylphosphite salts.

[0017] The reaction formula is:

[0018]

[0019] Preferably, the reaction temperature is 0-200℃, the reaction pressure is atmospheric pressure-10MPa, and the reaction time is 1-72 hours.

[0020] More preferably, the reaction temperature of the organophosphate flame retardant is 100-200℃; and the reaction pressure of the organophosphate flame retardant is atmospheric pressure to 5MPa.

[0021] Preferably, the molar ratio of dialkyl hypophosphite to haloalkyl phosphine oxide is 1:1 to 100:1.

[0022] Preferably, the haloalkylphosphine oxide is obtained by reacting trihydroxyalkylphosphine oxide with a halogenating agent.

[0023] Preferably, the halogen in the haloalkylphosphine oxide is selected from chlorine or bromine, and the remaining structure is consistent with that of trihydroxyalkylphosphine oxide.

[0024] Preferably, the trihydroxyalkylphosphine oxide is selected from any one of trihydroxymethylphosphine oxide, trihydroxyethylphosphine oxide, trihydroxypropylphosphine oxide, tri(hydroxymethylphenyl)phosphine oxide, trihydroxybutylphosphine oxide, hydroxymethyldihydroxyethylphosphine oxide, dihydroxymethylhydroxyethylphosphine oxide, trihydroxypentylphosphine oxide, and trihydroxyhexylphosphine oxide; the halogenating agent is selected from any one of thionyl chloride, oxalyl chloride, thionyl bromide, oxalyl bromide, N-bromosuccinimide, and N-chlorosuccinimide.

[0025] More preferably, the trihydroxyalkylphosphine oxide is selected from any one of trihydroxymethylphosphine oxide, trihydroxyethylphosphine oxide, trihydroxypropylphosphine oxide, tri(hydroxymethylphenyl)phosphine oxide, and trihydroxybutylphosphine oxide.

[0026] Preferably, the halogenating agent is selected from any one of thionyl chloride, oxalyl chloride, thionyl bromide, oxalyl bromide, N-bromosuccinimide, and N-chlorosuccinimide.

[0027] More preferably, the halogenating agent is selected from any one of thionyl chloride, oxalyl chloride, N-bromosuccinimide, and N-chlorosuccinimide.

[0028] Preferably, the dialkylphosphonic acid / dialkylphosphonate is selected from dimethylphosphonic acid and its alkali metal salt or alkaline earth metal salt, diethylphosphonic acid and its alkali metal salt or alkaline earth metal salt, dipropylphosphonic acid and its alkali metal salt or alkaline earth metal salt, dibutylphosphonic acid and its alkali metal salt or alkaline earth metal salt, dipentylphosphonic acid and its alkali metal salt or alkaline earth metal salt, dihexylphosphonic acid and its alkali metal salt or alkaline earth metal salt, diphenylphosphonic acid and its alkali metal salt or alkaline earth metal salt, dicyclohexylphosphonic acid and its alkali metal salt or alkaline earth metal salt, dinaphthylphosphonic acid and its alkali metal salt or alkaline earth metal salt, didodecylphosphonic acid and its alkali metal salt or alkaline earth metal salt, dioctadecylphosphonic acid and its alkali metal salt or alkaline earth metal salt, methylethylphosphonic acid and its alkali metal salt or alkaline earth metal salt, methylpropylphosphonic acid, dimethyl ... Phosphonic acid and its alkali metal salt or alkaline earth metal salt, methylpentyl phosphonic acid and its alkali metal salt or alkaline earth metal salt, methylbutyl phosphonic acid and its alkali metal salt or alkaline earth metal salt, methylphenyl phosphonic acid and its alkali metal salt or alkaline earth metal salt, ethylpropyl phosphonic acid and its alkali metal salt or alkaline earth metal salt, ethylbutyl phosphonic acid and its alkali metal salt or alkaline earth metal salt, ethylpentyl phosphonic acid and its alkali metal salt or alkaline earth metal salt, ethylhexyl phosphonic acid and its alkali metal salt or alkaline earth metal salt, ethylphenyl phosphonic acid and its alkali metal salt or alkaline earth metal salt, propylbutyl phosphonic acid and its alkali metal salt or alkaline earth metal salt, propylpentyl phosphonic acid and its alkali metal salt or alkaline earth metal salt, propylhexyl phosphonic acid and its alkali metal salt or alkaline earth metal salt, propylphenyl phosphonic acid and its alkali metal salt or alkaline earth metal salt.

[0029] More preferably, the dialkylphosphonic acid / dialkylphosphonate is selected from any one of dimethylphosphonic acid and its alkali metal salt or alkaline earth metal salt, diethylphosphonic acid and its alkali metal salt or alkaline earth metal salt, dipropylphosphonic acid and its alkali metal salt or alkaline earth metal salt, dibutylphosphonic acid and its alkali metal salt or alkaline earth metal salt, dipentylphosphonic acid and its alkali metal salt or alkaline earth metal salt, dihexylphosphonic acid and its alkali metal salt or alkaline earth metal salt, diphenylphosphonic acid and its alkali metal salt or alkaline earth metal salt, dicyclohexylphosphonic acid and its alkali metal salt or alkaline earth metal salt, methylethylphosphonic acid and its alkali metal salt or alkaline earth metal salt, methylpropylphosphonic acid and its alkali metal salt or alkaline earth metal salt, methylphenylphosphonic acid and its alkali metal salt or alkaline earth metal salt, ethylpropylphosphonic acid and its alkali metal salt or alkaline earth metal salt, and ethylbutylphosphonic acid and its alkali metal salt or alkaline earth metal salt.

[0030] Preferably, the alkylphosphonic acid / alkylphosphonate is selected from any one of methylphosphonic acid and its alkali metal salt or alkaline earth metal salt, ethylphosphonic acid and its alkali metal salt or alkaline earth metal salt, propylphosphonic acid and its alkali metal salt or alkaline earth metal salt, butylphosphonic acid and its alkali metal salt or alkaline earth metal salt, pentylphosphonic acid and its alkali metal salt or alkaline earth metal salt, hexylphosphonic acid and its alkali metal salt or alkaline earth metal salt, cyclohexylphosphonic acid and its alkali metal salt or alkaline earth metal salt, phenylphosphonic acid and its alkali metal salt or alkaline earth metal salt, naphthylphosphonic acid and its alkali metal salt or alkaline earth metal salt, dodecylphosphonic acid and its alkali metal salt or alkaline earth metal salt, and octadecylphosphonic acid and its alkali metal salt or alkaline earth metal salt.

[0031] Preferably, the solvent is an aqueous solution, an alcoholic solution, or a polar aprotic solution, specifically selected from at least one of water, acetone, methyl ethyl ketone, methanol, ethanol, butanol, benzene, toluene, xylene, chlorobenzene, naphthalene, chloronaphthalene, dimethylformamide, tetrahydrofuran, dichloromethane, chloroform, dimethylacetamide, dichloroethane, trichloroethane, hexafluoroisopropanol, furan, dioxane, and dimethyl sulfoxide.

[0032] An organophosphonate flame retardant is used to synergistically retard flames alone or with other halogen-free flame retardants such as melamine cyanurate (MCA), melamine polyphosphate (MPP), zinc borate, spirophosphate (pentaerythritol dimethylphosphonate, CU), dimethyl methylphosphonate (DMMP), diethyl ethyl phosphate (DEEP), resorcinol bis(diphenyl phosphate) (RDP), bisphenol A bis(diphenyl phosphate) (BDP), aluminum diethylphosphonate (ADP), zinc diethylphosphonate (ZDP), and aluminum diisobutylphosphonate.

[0033] An application of an organophosphonate flame retardant that can be used in polyethylene (PE), polypropylene (PP), polyisobutylene (PIB), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycarbonate (PC), acrylonitrile-butadiene-styrene terpolymer (ABS), nylon (PA), polyurethane (PU), and thermoplastic elastomer (TPE) to improve the flame retardant properties of the polymers.

[0034] This invention provides an organophosphonate flame retardant, its preparation method, and its application, which have the following beneficial effects:

[0035] The organophosphonate flame retardant synthesized in this invention not only provides flame retardancy to resins but also offers a certain degree of toughening with minimal impact on mechanical properties. Furthermore, compared to traditional diethylaluminum hypophosphite flame retardants, it exhibits higher flame retardancy at the same dosage. Its structure contains ester groups, resulting in excellent compatibility with polar polymers compared to traditional diethylaluminum hypophosphite—a property not found in traditional phosphorus-based flame retardants like diethylaluminum hypophosphite. Additionally, due to the absence of metal ions, this flame retardant causes relatively less corrosion to equipment screws, reducing its impact on the electrical properties of materials.

[0036] The organophosphonate flame retardant synthesized in this invention is not only simple in structure and easy to synthesize, but also avoids the use of highly polluting and toxic substances. Its synthetic structure is clearly defined, preventing residual active hydrogen on phosphorus that could affect temperature resistance. Furthermore, the ester-containing organophosphonate flame retardant synthesized in this invention provides good flame retardant performance at low addition levels, and due to the low addition amount, the resin also retains higher mechanical and electrical properties. Detailed Implementation

[0037] The present invention will be further described below with reference to specific embodiments to aid in understanding its content. Unless otherwise specified, the methods used in this invention are conventional methods; the raw materials and apparatus used, unless otherwise specified, are conventional commercially available products.

[0038] Example 1

[0039] Dissolve 132g of potassium dimethylphosphonate (1mol) in 200mL of deionized water, then add 108.57g (1mol) of tribromomethylphosphine oxide, reflux at 50℃ under normal pressure for 72h, and obtain the organophosphate flame retardant after separation;

[0040] Example 2

[0041] Except for lowering the reaction temperature to 0°C, the implementation process is the same as in Example 1;

[0042] Example 3

[0043] Except for replacing potassium dimethylphosphonate with an equimolar amount of sodium methylethylphosphonate, the implementation process is the same as in Example 1;

[0044] Example 4

[0045] Except for replacing water with dioxane, the implementation process is the same as in Example 1;

[0046] Example 5

[0047] Except for replacing water with dichloromethane, the implementation process is the same as in Example 1;

[0048] Example 6

[0049] Except for replacing water with chloroform, the implementation process is the same as in Example 1;

[0050] Example 7

[0051] Except for replacing water with tetrahydrofuran, the implementation process is the same as in Example 1;

[0052] Example 8

[0053] Except for replacing water with hexafluoroisopropanol, the implementation process is the same as in Example 1;

[0054] Example 9

[0055] 172g of sodium ethyl isobutyl phosphonate (1mol) was dissolved in 2L of THF and placed in a 3L pressure vessel. Then, 122.1g (0.33mol) of tris(2-bromoethyl)phosphine oxide was added. After purging with nitrogen three times, the temperature was raised to 150℃ and the reaction was carried out at a pressure of about 10MPa for 1h. After cooling, the organic phosphate flame retardant was obtained by separation.

[0056] Example 10

[0057] Except for lowering the reaction temperature to 120°C, the reaction pressure to approximately 1.3 MPa, and the reaction time to 10 hours, the implementation process is the same as in Example 8.

[0058] Example 11

[0059] Except for replacing 1 mol of sodium ethyl isobutyl phosphite with 0.5 mol of magnesium methyl phosphite, the implementation process is the same as in Example 8;

[0060] Example 12

[0061] Except for replacing 1 mol of sodium ethyl isobutyl phosphite with 0.33 mol of magnesium methyl phosphite and 0.33 mol of potassium diphenyl phosphite, the implementation process is the same as in Example 8;

[0062] Example 13

[0063] 1 mol of ethylpropylphosphonic acid was dissolved in 2 L of DMSO, and then 0.33 mol of tribromoethylphosphine oxide was added. The temperature was raised to 170 °C and refluxed at atmospheric pressure for 72 h. After cooling, the organic phosphate flame retardant was obtained by separation.

[0064] Example 14

[0065] Except for replacing ethylpropylphosphonic acid with 0.5 mol of dinaphthylphosphonic acid, the implementation process is the same as in Example 12;

[0066] Example 15

[0067] 1 mol of ethylpropylphosphonic acid and 1 mol of methylphosphonic acid were dissolved in 2 L of DMSO. Then, 1 mol of tri(bromoethyl)phosphine oxide was added and the temperature was raised to 170 °C. The mixture was refluxed under normal pressure for 72 h. After cooling, the mixture was separated to obtain the organophosphate flame retardant.

[0068] Example 16

[0069] 1 mol of sodium ethyl butyl phosphonate and 1 mol of sodium methyl phosphonate were dissolved in a mixture of 2 L of DMSO and 1 L of water. Then 1 mol of tris(3-bromobutyl)phosphine oxide was added. The temperature was raised to 170 °C and refluxed at atmospheric pressure for 72 h. After cooling, the organic phosphate flame retardant was obtained by separation.

[0070] Example 17

[0071] 1 mol of trihydroxyethylphosphine oxide was placed in a dry three-necked flask equipped with a reflux condenser. Simultaneously, 4 mol of thionyl chloride was added to a constant pressure funnel. The system temperature was raised to 60°C and nitrogen gas was continuously purged for 30 minutes. Then, thionyl chloride was slowly added dropwise. After the addition was completed, water was added to quench the thionyl chloride, and the mixture was neutralized. Then, 3 mol of potassium dimethylphosphonate was added, and the mixture was heated to 150°C and refluxed for 48 hours. After separation, the organophosphate flame retardant was obtained.

[0072] Example 18

[0073] Except for replacing 4 mol of thionyl chloride with 4 mol of oxalyl chloride, the implementation process is the same as in Example 16, and the organophosphate flame retardant is obtained after separation.

[0074] Example 19

[0075] Except for replacing 3 mol of potassium dimethylphosphonate with 1.5 mol of lithium hexylphosphonate, the implementation process is the same as in Example 16, and the organophosphate flame retardant is obtained after separation.

[0076] Example 20 group

[0077] In a 30% GF-reinforced PBT system, 12% of the organophosphate flame retardant synthesized in Example 3 was added and mixed evenly. The mixture was then extruded and granulated to obtain reinforced flame-retardant PBT. The PBT was then injection molded to obtain standard test specimens to test its mechanical and flame-retardant properties, as shown in Table 1.

[0078] Example 21 group

[0079] In a 30% GF reinforced PET system, 10% of the organophosphate flame retardant synthesized in Example 4 was added and mixed evenly. The mixture was then co-extruded and granulated to obtain reinforced flame retardant PET. Then, standard test specimens were obtained by injection molding to test their mechanical properties and flame retardant properties, as shown in Table 1.

[0080] Example 22 group

[0081] In a 30%GF-reinforced PA66 system, 15% of the organophosphate flame retardant synthesized in Example 5 was added and mixed evenly. The mixture was then co-extruded and granulated to obtain reinforced flame retardant PA66. Then, standard specimens were injection molded to test its mechanical and flame retardant properties, as shown in Table 1.

[0082] Example 23

[0083] In a 30%GF-reinforced PA6 system, 13% of the organophosphate flame retardant synthesized in Example 15 was added and mixed evenly. The mixture was then co-extruded and granulated to obtain reinforced flame-retardant PA6. Then, standard specimens were injection molded to test its mechanical and flame-retardant properties, as shown in Table 1.

[0084] Example 24

[0085] In a 30%GF-reinforced PA6 system, 10% of the organophosphate flame retardant synthesized in Example 17 and 2% of anhydrous zinc borate were added and mixed evenly. The mixture was then extruded and granulated to obtain reinforced flame retardant PA6. Then, standard specimens were obtained by injection molding to test its mechanical properties and flame retardant properties, as shown in Table 1.

[0086] Comparative Example 1

[0087] 12% diethyl aluminum hypophosphite was added to a 30% GF reinforced PBT system for co-extrusion granulation to obtain reinforced flame retardant PBT. Then, standard specimens were obtained by injection molding to test their mechanical properties and flame retardant properties, as shown in Table 1.

[0088] Comparative Example 2

[0089] 15% diethyl aluminum hypophosphite was added to a 30% GF-reinforced PA66 system for co-extrusion granulation to obtain reinforced flame-retardant PA66. Then, standard specimens were obtained by injection molding to test their mechanical and flame-retardant properties, as shown in Table 1.

[0090] Comparative Example 3 Groups

[0091] In a 30%GF reinforced PA6 system, 10% diethyl aluminum hypophosphite and 42% anhydrous zinc borate were added for blending, extrusion granulation, and then reinforced flame-retardant PA6 was obtained. Then, standard specimens were obtained by injection molding to test its mechanical properties and flame-retardant properties, as shown in Table 1.

[0092] The experimental performance comparison is as follows:

[0093] Table 1

[0094]

[0095] As can be seen from Examples 20-24 and Comparative Examples 1-3, organophosphonate flame retardants, in addition to their flame-retardant effect on resins, also provide a certain toughening effect with minimal impact on mechanical properties. Furthermore, compared to traditional diethylaluminum hypophosphite flame retardants, they exhibit higher flame retardancy at the same dosage. Their structure contains ester groups, resulting in better compatibility with polar polymers compared to traditional diethylaluminum hypophosphite—a property not found in traditional phosphorus-based flame retardants like diethylaluminum hypophosphite. Additionally, due to the absence of metal ions, this flame retardant causes relatively less corrosion to equipment screws, reducing its impact on the electrical properties of the material.

[0096] In summary, the organophosphonate flame retardant synthesized in this invention is not only simple in structure and easy to synthesize, but also avoids the use of highly polluting and toxic substances. Its synthetic structure is clearly defined and will not result in residual active hydrogen on phosphorus affecting temperature resistance. Furthermore, the ester-containing organophosphonate flame retardant synthesized in this invention provides good flame retardant performance at low addition levels, and due to the low addition amount, the resin also exhibits higher retention rates of mechanical and electrical properties.

[0097] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. An organophosphonate flame retardant characterized in that, The organic phosphonate flame retardant has the following structure: Structure I, or, Formula II, wherein, R1, R2 are selected from C1-C18 hydrocarbon group; R3, R5 are selected from C1-C18 alkylene group; R4 is selected from C1-C18 hydrocarbon group or halogenated hydrocarbon group or alcohol hydrocarbon group or structure as shown in structure III; R6 is selected from hydrogen or C1-C18 hydrocarbon group; x, y are both positive integers from 0 to 100; structure III is, Formula III.

2. A process for the preparation of an organophosphonate flame retardant, characterized in that, The method comprises the following steps: The organic phosphonate flame retardant is obtained by reacting dihydrocarbyl hypophosphite or dihydrocarbyl hypophosphite salt with halogenated hydrocarbyl phosphine oxide in a solvent and then separating and purifying.

3. The method for preparing an organophosphonate flame retardant according to claim 2, characterized in that, The reactants further comprise hydrocarbyl phosphite or hydrocarbyl phosphite salt.

4. A process for the preparation of an organophosphonate flame retardant according to claim 2 or 3, characterized in that, The reaction temperature is 0-200℃, the reaction pressure is normal pressure-10Mpa, and the reaction time is 1-72 hours.

5. A process for the preparation of an organophosphonate flame retardant according to claim 2 or 3, characterized in that, The molar ratio of dihydrocarbyl hypophosphite to halogenated hydrocarbyl phosphine oxide is 1:1-100:

1.

6. A process for the preparation of an organophosphonate flame retardant according to claim 2 or 3, characterized in that, The halogenated hydrocarbyl phosphine oxide is obtained by reacting trihydrocarbyl phosphine oxide with halogenating agent.

7. The method for preparing an organophosphonate flame retardant according to claim 6, characterized in that, The trihydrocarbyl phosphine oxide is selected from any one of trimethyl phosphine oxide, triethyl phosphine oxide, tripropyl phosphine oxide, tri(hydroxymethyl phenyl) phosphine oxide, tributyl phosphine oxide, hydroxymethyl dihydroxyethyl phosphine oxide, dihydroxymethyl hydroxyethyl phosphine oxide, trihydroxypentyl phosphine oxide, and trihydroxyhexyl phosphine oxide; and the halogenating agent is selected from any one of thionyl chloride, oxalyl chloride, thionyl bromide, oxalyl bromide, N-bromosuccinimide, and N-chlorosuccinimide.

8. A process for the preparation of an organophosphonate flame retardant according to claim 2 or 3, characterized in that, The solvent is selected from at least one of water, acetone, methyl ethyl ketone, methanol, ethanol, butanol, benzene, toluene, xylene, chlorobenzene, naphthalene, chloronaphthalene, dimethylformamide, tetrahydrofuran, dichloromethane, chloroform, dimethylacetamide, dichloroethane, trichloroethane, hexafluoroisopropanol, furan, dioxane, and dimethyl sulfoxide.

9. Use of an organophosphonate ester flame retardant characterized in that, The organic phosphonate flame retardant of any one of claims 1-8 can be used alone or in combination with other halogen-free flame retardants such as melamine cyanurate (MCA), melamine polyphosphate (MPP), zinc borate, spiro phosphonate (pentaerythritol dimethyl phosphonate, CU), dimethyl methylphosphonate (DMMP), diethyl ethylphosphonate (DEEP), resorcinol bis(diphenyl phosphate) (RDP), bisphenol A bis(diphenyl phosphate) (BDP), aluminum diethylphosphinate (ADP), zinc diethylphosphinate (ZDP), and diisobutyl aluminum phosphinate (ADP) to achieve synergistic flame retardation.

10. Use of an organophosphonate ester flame retardant according to claim 9, characterized in that, The organic phosphonate flame retardant can be applied to polyethylene (PE), polypropylene (PP), polyisobutylene (PIB), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycarbonate (PC), acrylonitrile-butadiene-styrene terpolymer (ABS), nylon (PA), polyurethane (PU), and thermoplastic elastomer (TPE) to improve the flame retardation of the polymers.

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