KR101147548B1 - Compositions for production of fire-retardant polyarylate resin - Google Patents

Abstract

The present invention relates to a composition for producing a flame retardant polyarylate resin. More specifically, flame retardant polyarylate comprising 4,4′-dihydroxyphenylacetylene (DHPA) of specific structure, phthaloyl chloride (PC) of specific structure and bishydroxyphenol (BHP) of specific structure It relates to a composition for producing a resin.

Description

Compositions for producing flame retardant polyarylate resins {Compositions for production of fire-retardant polyarylate resin}

The present invention is for producing a flame retardant polyarylate resin comprising 4,4'-dihydroxyphenylacetylene (DHPA) of a specific structure, phthaloyl chloride (PC) of a specific structure and bishydroxyphenol (BHP) of a specific structure It relates to a composition.

Synthetic polymers are widely used, such as plastics, rubber, fibers, etc., but since the high combustibility of most polymer resins is high, the flame retardancy of polymer resins has become an important research subject. Flame-retardant resins have been used to reduce the combustibility by taking part in the polymer resin or the polymer backbone with small molecules having flame retardancy, and many halogenated molecular compounds such as brominated aromatics have been used to reduce the flammability of the polymer. Brominated aromatic flame retardants have been used in a wide range of plastic products such as computers, textiles, furniture, building materials, etc., but the use of halogenated flame retardants is regulated by the accumulation of toxic substances such as dioxins produced by the use of halogenated flame retardants. There has been a need for development of non-halogen-based alternative flame retardants. Moreover, halogenated flame retardants emit hydrogen chlorine gas or hydrobromic acid gas upon combustion, which is undesirable for airtight spaces such as airplanes and ships. Inorganic non-halogen flame-retardant additives such as aluminum hydroxide is used in excess to achieve flame retardancy, there is a problem that it is difficult to maintain the physical mechanical properties of the polymer.

An ideal flame retardant resin with low flammability is a non-halogen resin, which has high thermal stability, low combustion heat, low heat release rate (HRR), and minimal emission of toxic gases. Low combustible polymers essentially create a large number of chars by heat, forming a fireproof layer on the surface of the polymer to block the combustible gases that are decomposed and released by heat, preventing combustion from continuing. The generation of such char can also be accomplished by preparing the additives and composite materials that provide the char.

The material's heat dissipation rate (HRR) is the main characteristic of the polymer's flammability, and there are several calorimetry methods to measure the heat dissipation rate. It is also developed to measure. PCFC measures the amount of heat dissipation and total heat dissipation of a polymer material. The amount of heat dissipation is determined by the oxygen consumption and is expressed by the heating rate. Heat dissipation is defined as the maximum amount of heat released from a unit weight and is known as a key indicator of the material's uniqueness and flammability (See, Richard N. Walters, Richard E. Lyon, Journal of Applied Polymer Science, 87 (3). ), 548-563, 2002).

Aromatic polyarylates made from bisphenol-A and phthalic acid are well known and widely used as important high-performance engineering plastics, but their heat dissipation (HRC) is 359 J / gK, which is flammable. Appears high. Aromatic polyarylates containing 1,1-dichloro-2,2-bis (4-hydroxyphenyl) ethylene (BPC), previously known as self-extinguishing polymers, are transparent and have excellent mechanical properties and are also resistant to combustion. High resistivity heat dissipation (HRC = 21 and 29 J / gK) and high char formation capacity of 50-55% ( Macromolecules, 39 (10), 3553-3558, 2006). However, the polyarylate resin based on the BPC has a limitation in its use as a material for mass production or industrial products by releasing hydrogen chloride gas at high temperature.

Recently, aromatic polyarylate resins containing 4,4′-bishydroxydeoxybenzoin {4,4′-bishydroxydeoxybenzoin, BHDB} have been reported to exhibit low heat dissipation rate (HRR). It is reported to aromatize to form high chars ( Macromolelecules, 39 (10), 3553-3558, 2006). The heat dissipation rate of the polyarylate resin containing BHDB measured by the thermo-combustion calorimetry was less than 100 J / gK (RN Walters, M. Smith, and MR Nyden, International SAMPE Symposium and Exhibition 2005 , 50, 1118) Not satisfactory.

Accordingly, there is an increasing demand for new polyarylate resins that are environmentally friendly and have excellent flame retardancy.

Accordingly, the present inventors have studied to solve the problem of the existing flame retardant resins, as a result, polyarylate resin containing 4,4'-dihydroxyphenylacetylene (DHPA) is a lower heat dissipation amount than the general resin while forming a high content char It was found that the (Heat Release Capacity, HRC), and also found the optimal composition ratio of the polyarylate resin containing the DHPA to complete the present invention.

An object of the present invention is to provide a polyarylate resin having excellent flame retardancy.

An object of the present invention is to provide a composition for producing a flame retardant polyarylate resin.

In order to solve the above problems, the present invention is characterized by a polyarylate resin having excellent flame retardancy having a repeating unit structure of the formula (1).

In Formula 1, R ₁ is a hydrogen atom or C ₁ ~ C ₅ Alkyl, x is an integer of 1 to 4; R ₂ is substituted or unsubstituted alkylene, substituted or unsubstituted phenylene, or substituted or unsubstituted arylene; R ₃ is - C (O) -, -CH 2 -, -C (CH 3) 2 - or -S (O) ₂ - and; m ₁ and m ₂ is an integer satisfying 0≤m and 1≤m ₁ ≤100 ≤100 _2; n is an integer satisfying 1 ≦ n ≦ 100; Substituents of the substituted alkylene, substituted phenylene and substituted arylene of R ₂ are saturated alkyl, unsaturated alkyl, phenyl, alkoxy group, phenoxy group, aryl, carboxyl group, nitro group, amino group, alkyl substituted amino group, sulfo Or a silyl group or sulfamoyl group.

In addition, in order to solve the above problems, the present invention is a 4,4'-dihydroxyphenylacetylene compound represented by the formula (2), a phthaloyl chloride compound represented by the formula (3) and bishydroxy represented by the formula (4) It is characterized by the composition for manufacture of flame-retardant polyarylate resin containing a phenol (hereinafter collectively referred to as 'BHP') compound.

In Formula 2, R ₁ and x are as defined in Formula 1.

In Chemical Formula 3, R ₂ is as defined in Chemical Formula 1.

In Chemical Formula 4, R ₃ As defined in Formula 1 above.

The polyarylate resin of the present invention is environmentally friendly because it does not contain halogen, and has high heat resistance, and carbonized char is produced significantly higher to form a thick film on the surface of the resin, and has a low heat dissipation amount. In addition, since the polyarylate resin of the present invention can increase the solubility in industrial solvents commonly used, it is easy to process, and because it has a sufficient molecular weight, it is excellent in thermal stability and can provide commercially useful mechanical properties. have.

1 is a ¹ H-NMR spectra measurement result of the polyarylate compound synthesized in Example 1.
2 is a result of a thermal stability measurement experiment performed in the experimental example.

The present invention described above will be described in more detail below.

The present invention relates to a polyarylate resin having a repeating unit structure of the following Chemical Formula 1 and excellent in flame retardancy, and specific examples thereof are as shown in the following Chemical Formulas 1a, 1b and 1c.

[Formula 1]

In Formula 1, R ₁ is a hydrogen atom or C ₁ ~ C ₅ Alkyl, x is an integer of 1 to 4; R ₂ is substituted or unsubstituted alkylene, substituted or unsubstituted phenylene, or substituted or unsubstituted arylene; R ₃ is - C (O) -, -CH 2 -, -C (CH 3) 2 - or -S (O) ₂ - and; m ₁ and m ₂ is an integer satisfying 0≤m and 1≤m ₁ ≤100 ≤100 _2; n is an integer satisfying 1 ≦ n ≦ 100; Substituents of the substituted alkylene, substituted phenylene and substituted arylene of R ₂ are saturated alkyl, unsaturated alkyl, phenyl, alkoxy group, phenoxy group, aryl, carboxyl group, nitro group, amino group, alkyl substituted amino group, sulfo Or a silyl group or sulfamoyl group.

The polyarylate resin of the present invention is characterized in that the weight average molecular weight (Mw) is 10,000 or more, the char yield is 25% (at 800 ℃) or more.

 The polyarylate resin of the present invention can be obtained by polymerizing the compound of Chemical Formulas 2 to 4 as shown in Scheme 1 below, wherein the polyarylate resin is a copolymer, a random copolymer or a block copolymer, or It may be a hybrid copolymer.

Scheme 1

In Scheme 1, R ₁ , R ₂ , R ₃ , x, m ₁ , m ₂ , and n are the same as in Chemical Formula 1.

The present invention also provides a 4,4′-dihydroxyphenylacetylene compound represented by the following formula (2), a phthaloyl chloride compound represented by the following formula (3) and a bishydroxyphenol (BHP) compound represented by the following formula (4) It relates to a composition for producing a polyarylate resin containing.

[Formula 2]

In Formula 2, R ₁ is a hydrogen atom or C ₁ ~ C ₅ alkyl, x is an integer of 1-4.

(3)

In Formula 3, R ₂ is substituted or unsubstituted alkylene, substituted or unsubstituted phenylene, or substituted or unsubstituted arylene, and the substituted alkylene, substituted phenylene and substitution Substituted arylene substituents are saturated alkyl, unsaturated alkyl, phenyl, alkoxy group, phenoxy group, aryl, carboxyl group, nitro group, amino group, alkyl substituted amino group, sulfonyl group or sulfamoyl group.

[Formula 4]

In the above Formula 4, R ₃ is - C (O) -, -CH 2 -, -C (CH 3) 2 - or -S (O) ₂ - _a.

4,4'-dihydroxyphenylacetylene (hereinafter referred to as 'DHPA') compound represented by the formula (2) is a material that provides flame retardancy to the polyarylate resin of the present invention, by the method shown in Scheme 2 You can get it.

Scheme 2

In Scheme 2, R ₁ and x are the same as R ₁ and x in Chemical Formula 2. Specific examples of the DHPA compound represented by the formula (2) are shown in the following formula 2-a, 2-b and 2-c, in order to increase the solubility in industrial solvents commonly used to give convenience in processing It is more preferable to use compounds having two or more methyl groups, such as Formula 2-b and Formula 2-c.

One of the composition materials of the present invention, the phthaloyl chloride compound represented by Chemical Formula 3 (hereinafter, referred to as 'PC') is represented by Chemical Formula 3, wherein R ₂ is substituted or unsubstituted alkylene, substituted or Unsubstituted phenylene or substituted or unsubstituted arylene may be used. Substituents of the substituted alkylene, the substituted phenylene and the substituted arylene are saturated alkyl, unsaturated alkyl, phenyl, alkoxy group, phenoxy group, aryl, carboxyl group, nitro group, amino group, alkyl substituted amino group, sulfonyl group Or sulfamoyl groups. In addition, the phthaloyl chloride compound is a phenyl unsubstituted R ₂ , terephthaloyl chloride represented by the following formula 3-a or isophthaloyl chloride represented by the formula 3-b Can be used.

The bishydroxyphenol compound represented by Formula 4, which is one of the other composition materials of the present invention, is a material constituting an aromatic polyester together with Formula 3, and is typically represented by Formulas 4-a, 4-b, and 4 below. One or more bishydroxyphenols (BHP) selected from the compounds represented by -c and 4-d may be used, but may be selected according to required physical properties of the material, and generally bisphenol represented by the following compound 4-a Preference is given to using -A (called BPA).

In addition, the polyarylate resin composition of the present invention is preferably such that the DHPA compound represented by Formula 2 and the BHP compound represented by Formula 4 have a molar ratio of 5 to 95:95 to 5, preferably It is good to have a molar ratio of 10-90: 90-10, More preferably, it has a molar ratio of 20-70: 80-30. At this time, when the molar ratio of the DHPA compound: BHP compound is outside the range of 5 to 95: 95 to 5, the amount of DHPA compound included in the polyarylate resin is too small to generate less char, resulting in reduced flame retardancy or poor compatibility. If the amount of the DHPA compound is too large, the solubility of the polyarylate resin in the organic solvent may be deteriorated, and the range of selection of the organic solvent may be too narrow. Therefore, it is preferable to have a molar ratio within the above range.

In more detail, the composition has a molar ratio of DHPA compound: PC compound: BHP compound = 1 to 9: 10: 9 to 1 is preferred in terms of solubility and thermal properties, more preferably It is good to have a molar ratio of 2 to 8:10:10 to 2. The polyarylate resin and polyarylate resin composition of the present invention described above can be used alone, and also N-methyl pyrrolidone (NMP), m-cresol (m-cresol), chloroform ( By dissolving in one or more organic solvents selected from chloroform, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO) and dimethylformamide (DMF), processability and compatibility can be increased. In addition, the polyarylate resin of the present invention is excellent in solubility with respect to the organic solvent. In addition, the organic solvent may be mixed with other plastic materials in addition to the polyarylate resin to be used as a flame retardant material such as fibers, building materials, and furniture.

Hereinafter, the present invention will be described in more detail based on the following examples, but the scope of the present invention is not limited to the following examples.

[Synthesis Example]

Synthesis Example 1. Synthesis of 4,4′-dihydroxyphenylacetylene (DHPA)

4,4′-dihydroxyphenylacetylene was prepared using 4-iodophenol and acetylene gas and palladium catalyst (See, Chao-jun Li, Dong-Li Chen, Christopher W Castello, Organic Process Research). & Development 1997, 1, 325-327).

4-iodinephenol (8.8 g, 40 mmol), CuI (0.76 g, 10 mol%), Pd (Ph ₃ ) ₄ (2.3 g, 5 mol%) was added to acetonitrile (120 ml) and stirred, Ferridine (40 ml) was added, the reaction system was then replaced with acetylene gas, and then the temperature was gradually raised to 75 ° C.

Next, the reaction product is monitored by thin layer chromatography, and when the reaction is completed, the reaction mixture is cooled to room temperature. The solid is filtered off and then neutralized with 2N HCl. The product is extracted using ethyl acetate, and the organic layer is washed with water and brine. Next, the organic layer was dried with anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure to obtain 3.5 g of 4,4′-dihydroxyphenylacetylene. The structure was confirmed by ¹ H NMR and ¹³ C NMR.

¹ H NMR (400 MHz, acetone-d ₆ ) δ 6.85 (d, 4H, 2phenyl), 7.35 (d, 4H, 2phenyl), 8.70 (s, 2H, 2OH); ¹³ C NMR (acetone-d ₆ ) δ 88.3, 115.4, 116.3, 133.6, 158.3

Synthesis Example 2. Synthesis of 3,3 ″ -Dimethyl-4,4′-Dihydroxyphenylacetylene (DHPAM)

3,3 ″ -dimethyl-4,4′-dihydroxyphenylacetylene was synthesized in the same manner as in Synthesis example 1, using 3-methyl-4-iodinephenol instead of 4-iodinephenol, and the structure thereof. Was confirmed by ¹ H NMR and ¹³ C NMR as follows.

¹ H NMR (acetone-d ₆ ) δ 2.16 (s, 6H, 2CH ₃ ), 6.77 (d, 2H, 2phenyl), 7.11˜7.12 (dd, 4H, 2phenyl), 9.72 (s, 2H, 2OH); ¹³ C NMR (acetone-d ₆ ) δ 88.3, 115.4, 116.3, 133.6, 158.3, 206.12

EXAMPLES Preparation of Flame Retardant Polyarylate Resin

Examples 1 to 9 and Comparative Example 1

Pour distilled water (27 ml) into a 1-neck round flask (250 ml), dissolve by adding NaOH (1.66 g, 41.4 mmol), and bisphenol-A (0.41 g, 7.88 mmol, BPA), which is a kind of BHP compound. 4,4'-dihydroxymethylphenylacetylene (0.41 g, 1.97 mmol, DHPA) was added and dissolved. Next, after Et ₃ BzNCl (0.11 g, 0.48 mmol) is added, stirring is continued. Isophthaloyl chloride (IPC, 9.85 mmol) was dissolved in CH ₂ Cl ₂ in an additional funnel, added dropwise for 30 minutes under vigorous stirring, then precipitated in 500 ml of methanol (MeOH) after 2 hours and filtered. do. Next, the precipitate was washed three times with distilled water (50 ml) and methanol (50 ml), and then dried in a vacuum oven at 30 ° C. for 12 hours to obtain a target product.

With the above embodiment Synthesizing polyarylate resin in the same manner, but fixed the amount of IPC, as shown in Table 1, polyarylate resin was synthesized while changing the molar ratio (molar ratio) of DHPA and BPA. However, Examples 8 and 9 synthesized a polyarylate resin using DHPAM of Synthesis Example 2 instead of DHPA.

The synthesized polyarylate resin was subjected to basic analysis through FT-NMR, FT-IR and GPC, followed by thermogravimetric analysis (TGA), to measure solubility in organic solvents and thermal properties and flame retardance of polymers. Differential scanning calorimetry (DSC) and thermal combustion calorimetry (PCFC) was measured, the results are shown in Table 1 below. In addition, ¹ H NMR measurement graph is shown in FIG.

Example 1 and Synthesizing polyarylate resin in the same manner, but fixed the amount of IPC, as shown in Table 1, polyarylate resin was synthesized while changing the molar ratio (molar ratio) of DHPA and BPA. However, Examples 8 and 9 synthesized a polyarylate resin using DHPAM of Synthesis Example 2 instead of DHPA.

division Molar ratio of DHPA: BPA
(molar ratio) Polyarylate Resin Yield (%) GPC ^a feed incorporated ^b Weight average
Molecular Weight (Mw) Number average
Molecular Weight (Mn) Dispersion Example 1 5:95 7:93 74 6,154 5,260 1.17 Example 2 10:90 9:91 81 15,987 9,930 1.61 Example 3 20:80 21:79 78 30,734 19,090 1.61 Example 4 30:70 29:71 77 46,426 26,650 1.61 Example 5 40:60 38:62 83 46,846 30,030 1.56 Example 6 50:50 51:49 57 40,025 18,880 2.12 Example 7 100: 0 100: 0 60 23,284 15,840 1.47 Example 8 10:90 12:88 88 23,805 15,870 1.75 Example 9 20:80 21:79 85 25,549 13,170 1.94 Comparative Example 1 0: 100 0: 100 66 32,853 21,060 1.56 a: Molecular weight and eluent calculated by polystyrene measurement are gel permeation column chromatography results measured using DMF.
b: Calculated by integratio of ¹ H NMR spectra.

[Experimental Example]

The physical properties of the polyarylate resins prepared in Examples and Comparative Examples were measured as follows.

1) Solubility Measurement Experiment

N-methyl pyrrolidone (NMP), m-cresol, chloroform (CHCl ₃ ), tetrahydrofuran (THF), methyl chloride (MC), ethyl acetate (EA), toluene, methanol ( Solubility was measured by dissolving the polyarylate resin prepared in Examples and Comparative Examples in MeOH), hexane and acetone, respectively, and the results are shown in Table 2 below.

division NMP m-cresol CHCl ₃ THF MC EA toluene Methanol Hexane Acetone Example 1 ++ ++ ++ ++ ++ - - - - - Example 2 ++ ++ ++ ++ + - - - - - Example 3 ++ ++ ++ + + - - - - - Example 4 ++ ++ ++ + + - - - - - Example 5 ++ ++ + + + - - - - - Example 6 ++ + + + + - - - - - Example 7 + - - - - - - - - - Example 8 ++ ++ ++ ++ ++ - - - - - Example 9 ++ ++ ++ ++ ++ - - - - - Comparative Example 1 ++ ++ ++ ++ ++ - - - - -  ++: Very soluble, +: Very soluble,-: Not soluble.

Looking at Table 2, the polyarylate resin Solubility is As the content of DHPA increases, solubility decreases. That is, since the solubility of the polyarylate resin increases as the content of DHPA with poor solubility increases, it is preferable to use it with a molar ratio of DHPA: PC: BPA = 1 ~ 9: 10: 9 ~ 1. Do.

2) Experimental Measurement of Thermal Properties and Char Yield of Polyarylate Resins

Combustibility such as the heat dissipation amount (HRC) of the polymer was measured by using PFC (Pyrolysis Combustion Flow Calorimetry) taking samples 1 ~ 5 mg, the sample was pyrolyzed at 900 ℃ at 1 ℃ / s under nitrogen, 900 ℃ After complete combustion at, the decomposition temperature of the polyarylate resin was measured. The glass transition temperature (Tg) was measured using differential scanning calorimetry (DSC), and the char yield was obtained by comparing the difference in resin weight before and after the test.

division Intrinsic viscosity
(dl / g) Resin
Glass transition temperature
(T _g , ℃) Decomposition Temperature of Resin
(T _d , ℃) Char yield
(%, at 800 ℃) Air N ₂ Example 1 0.57 172 450 460 29.60 Example 2 0.85 183 427 450 30.05 Example 3 1.03 190 435 446 33.23 Example 4 1.35 196 442 443 35.00 Example 5 1.42 203 434 438 37.08 Example 6 1.17 215 398 407 40.34 Example 7 0.97 256 351 360 52.08 Example 8 1.05 154 434 431 29.28 Example 9 1.05 159 432 429 32.81 Comparative Example 1 1.19 157 441 435 25.36

The glass transition temperature (Tg) range of the polyarylate resin of the present invention is higher than Comparative Example 1 as 186 to 256 ° C. As the content of DHPA increases, the rigidity of the polymer chain increases and the flame retardancy is very high. Can be used as high performance engineering plastics. In addition, the polyarylate resin of the present invention does not exhibit a melting point or crystallization temperature up to 300 ° C.

Char yield is showing a production rate of 30% or more at 800 ℃, in the case of the Example, it can be confirmed that the char yield is high compared to Comparative Example 1. Therefore, it is preferable to use the polyarylate resin of this invention in the molar ratio of DHPA: PC: BPA = 1-9: 10: 10-9.

3) Thermal Stability Measurement Experiment

Thermogravimetric analysis (TGA) was used to measure the thermal stability of the polyarylate resin, and the results are shown in FIG. 2.

Referring to Figure 2, in the embodiment of the present invention, it is shown that the stable to 400 ~ 460 ℃, showing a weight loss rate of less than 5% by TGA (thermogravimetric analysis) in this range.

As the content of DHPA increases, the thermal stability decreases, but the carbonization property (char yield) increases indirectly.

4) Flame retardancy test

In order to measure the flame retardancy of the polyarylate resin, the heat dissipation amount was measured by a pyrolysis compression flow calorimetry (PCFC), and the results are shown in Table 4 below.

division Heat dissipation ^a)
{J / (gK)} Total heat dissipation
(kJ / g) Char yield (%) PCFC ^b) TGA ^c) Example 1 353 15.0 25.7 29.6 Example 2 335 14.8 25.8 30.0 Example 3 231 12.5 29.1 33.2 Example 4 213 11.4 31.6 35.0 Example 5 175 10.3 37.3 37.0 Example 6 119 7.8 47.3 40.3 Example 7 33 3.3 58.2 52.0 Example 8 280 15.1 28.6 29.28 Example 9 211 13.5 33.0 32.81 Comparative Example 1 356 16.2 24.0 24.1 a) Heat dissipation: Heat Release Capacity, HRC
b) Pyrolysis Combustion Flow Calorimetry (PCFC)
c) thermogravimetric analysis (TGA): thermogravimetric analysis

In the case of the embodiment of the present invention, it can be confirmed that it has a lower heat dissipation than Comparative Example 1, through which it can be confirmed that the flame retardancy of the polyarylate resin of the present invention is excellent. In addition, in Example 6 in which the molar ratio is DHPA: PC: BPA = 5: 10: 10, it can be confirmed that the heat dissipation amount has a value of 120 J / gK or less, and this heat dissipation amount value is a poly having a known self-extinguishing property. Polyvinylidene fluoride (311 J / gK), polyphenylene sulfide (165 J / gK), polyetheretherketone (155 J / gK), polyphenylsulfone (153 J / gK) gK), polyetherimide (121 J / gK), and the like.

In the case of Example 7, since the heat dissipation amount is very low, about 33 J / gK, and the char yield is also high as 52%, it can be seen that the flame retardancy is greatly increased.

The polyarylate resin having excellent flame retardancy of the present invention and the composition for preparing the resin may be used as a plastic material exhibiting flame retardancy by being mixed as an additive in a thermoplastic resin or a thermosetting resin. The present invention reduces the corrosiveness of the plastics by halogen, and can reduce the human injury caused by the gas in the case of fire, further increase the human safety of the resin contained in various home appliances, industrial products, etc. It can be prepared, and also contribute to environmental stability, which can contribute to human safety and the environment. Industrial Applicability The present invention can be widely used as a material for implementing flame retardancy of plastics used in industries such as electric and electronics, construction, furniture, and textiles and future core industries such as automobiles, aviation, space, and robots.

Claims (7)

A flame retardant polya comprising 4,4′-dihydroxyphenylacetylene compound represented by the following formula (2), a phthaloyl chloride compound represented by the following formula (3) and a bishydroxyphenol compound represented by the following formula (4) Compositions for preparing the resins;
(2)

In Formula 2, R ₁ is a hydrogen atom or C ₁ ~ C ₅ Alkyl, x is an integer of 1 to 4;
(3)

In Formula 3, R ₂ is substituted or unsubstituted alkylene, substituted or unsubstituted phenylene, or substituted or unsubstituted arylene, the substituted alkylene, the substituted phenylene, and Substituents of the substituted arylene are saturated alkyl, unsaturated alkyl, phenyl, alkoxy group, phenoxy group, aryl, carboxyl group, nitro group, amino group, alkyl substituted amino group, sulfonyl group or sulfamoyl group;
[Chemical Formula 4]

In Chemical Formula 4, R ₃ is —C (O) —, —CH ₂ —, —C (CH ₃ ) ₂ — or —S (O) ₂ —.
The compound of claim 1, wherein R ₁ is a hydrogen atom or methyl, and R ₂ is

or

This is, and R ₃ is -CH ₂ -or -C (CH ₃ ) ₂ -The composition for producing a flame retardant polyarylate resin, characterized in that.
The molar ratio of the 4,4′-dihydroxyphenylacetylene compound represented by Formula 2 and the bishydroxyphenol compound represented by Formula 4 is from 5 to 95: 95 to 5 A composition for producing a flame retardant polyarylate resin, which is characterized by the above-mentioned.
The molar ratio of 4,4'-dihydroxyphenylacetylene compound represented by the formula (2), the phthaloyl chloride compound represented by the formula (3) and the bishydroxyphenol compound represented by the formula (4) (Molar ratio) is 2 to 8: 10: 8 to 2, characterized in that the composition for producing a flame-retardant polyarylate resin.
The flame retardant polyarylate resin of claim 1, further comprising at least one organic solvent selected from N-methyl pyrrolidone, m-cresol, chloroform, tetrahydrofuran, dimethyl sulfoxide, and dimethylformamide. Composition for preparation.
A flame-retardant plastic material comprising the composition of any one of claims 1 to 5.
The flame retardant plastic material according to claim 6, further comprising a thermoplastic resin or a thermosetting resin.

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