JP2001089489A - Phosphorus compound, flame-retardant and flame retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a phosphorus compound low in bleeding in the case of compounding to a resin, having excellent flame retardancy and thermal stability. SOLUTION: The compound is expressed by formula (1) (R is H, a 1-9C alkyl or hydroxyl, X is a monocyclic aromatic compound or a polycyclic aromatic compound. m is an integer of 1-20, n is an integer of 0-20, q is 1 or 2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel phosphorus compound useful as a flame retardant that can be used in a wide range, a flame retardant containing the compound as an active ingredient, and a flame retardant resin composition containing the compound.

[0002]

BACKGROUND OF THE INVENTION Halogen-free flame retardants include tricresyl phosphate, reaction products of diphenyl phosphorochloridate and bisphenol A, reaction products of resorcinol and diphenyl phosphorochloridate, cresyl diphenyl phosphate, and the like. Has been used as a flame retardant for thermoplastic resins and thermosetting resins.

However, when these flame retardants are incorporated into a resin, there are problems such as easy bleeding, easy coloring, and a large required amount of addition.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve these disadvantages of the prior art, and to provide a novel phosphorus compound having less bleeding when blended with a resin and having excellent flame retardancy and thermal stability. Is to provide.

[0005]

The present inventors have conducted intensive studies to solve the above-mentioned problems. As a result, when a specific phosphorus compound is used as a flame retardant, the specific phosphorus compound has little bleed and excellent flame retardancy. And found that it can be used for a wide range of resins with thermal stability, and completed the present invention.

That is, the present invention provides a phosphorus compound, a flame retardant and a flame-retardant resin composition as shown below. Item 1. General formula (1)

[0007]

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Wherein R represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms or a hydroxyl group, X represents a mononuclear aromatic group or a polynuclear aromatic group, m is an integer of 1 to 20, and n is 0-2
Integer of 0, q is 1 or 2. A) a phosphorus compound represented by Item 2. Item 6. A flame retardant comprising the phosphorus compound according to Item 1 as an active ingredient. Item 3. A flame-retardant resin composition containing a resin and the phosphorus compound according to item 1.

The phosphorus compound of the present invention has a phosphorus atom in a side chain and a main chain, and has an optimum molecular weight as a flame retardant.
Further, it has a large phosphorus content, has less bleeding than conventional low molecular weight phosphorus compounds, and has high flame retardancy and thermal stability.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, R in the general formula (1) represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms or a hydroxyl group. The alkyl group may be linear or branched, for example, a methyl group, an ethyl group, an n-
Examples include a propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, an i-pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Preferred alkyl groups include a methyl group and a t-butyl group. X represents a divalent mononuclear aromatic group or a polynuclear aromatic group such as a phenylene group and a biphenylene group. m is an integer of 1 to 20, preferably 1 to 5. n is an integer of 0 to 20, preferably 0 to 5. q is 1 or 2.

The phosphorus compound of the present invention can be produced by applying a known method, for example, as follows. (1) The amount of 2- (6) required to obtain a desired molecular weight is obtained.
-Oxide-6-H-dibenzo [c, e] [1,2] oxaphospholin-6-yl) -1,4-benzenediol

[0012]

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And monohydric phenols (containing one hydroxyl group)
And / or a mixture with a divalent mononuclear phenol (containing two hydroxyl groups) or a divalent polynuclear phenol (containing two hydroxyl groups) in the presence or absence of a dehydrohalogenating agent, A method in which phosphorus oxyhalide (preferably phosphorus oxychloride) is reacted to carry out dehydrohalogenation. (2) Monohydric phenols, dihydric mononuclear phenols, and dihydric polynuclear phenols each of phosphorochloridate and / or phosphorodichloridate and 2- (6-oxide-6-H-dibenzo [ c, e] [1,2 oxaphosphorin-6-yl) -1,4-benzenediol in the presence or absence of a dehydrohalogenating agent. (3) Monochlorophenols, divalent mononuclear phenols, and divalent polynuclear phenols each of phosphorochloridate and / or phosphorodichloridate and 2- (6-oxide-6-H-dibenzo [ c, e] [1,2] oxaphospholin-6-yl) -1,4-benzenediol and a divalent mononuclear or polynuclear phenol in the presence or absence of a dehydrohalogenating agent How to react.

The monohydric phenols used for producing the phosphorus compound of the present invention include, for example, phenol, cresol, tert-butylphenol, amylphenol,
Octylphenol, xylenol, di-tert-butylphenol, dioctylphenol and the like can be mentioned. When phosphorochloridate or phosphorodichloridate is used, those derived from the same phenols can be used. For example, diphenyl phosphorochloridate derived from phenol

[0015]

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Phenylphosphorodichloridate

[0017]

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And the like.

Examples of the divalent mononuclear phenol used for producing the phosphorus compound of the present invention include resorcinol and hydroquinone. Examples of divalent polynuclear phenols include bisphenol A, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxybenzophenone,
4,4'-dihydroxydiphenyl sulfone, 4,4 '
-Dihydroxydiphenyl ether and the like.

In the production of the phosphorus compound of the present invention, when dehydrohalogenation is carried out without using a dehydrohalogenating agent, the catalyst may be magnesium chloride or iron chloride of about 0.1 to 5% by weight of the total amount of the reactants. (FeCl ₃ ), aluminum chloride, titanium chloride and the like are preferably used.

Incidentally, an inert gas,
An inert solvent or the like can also be used.

When the phosphorus compound of the present invention is produced using a dehydrohalogenating agent, examples of the dehydrohalogenating agent include tertiary amines such as triethylamine, triallylamine, pyridine, dimethylaniline and diethylaniline. You.

Examples of the inert solvent which can be used if necessary include, for example, methylene chloride, chloroform,
Examples thereof include chlorinated solvents such as toluene, xylene, chlorobenzene, and dichlorobenzene, and aromatic solvents.

When the phosphorus compound of the present invention is produced without using a dehydrohalogenating agent, examples of the inert gas which can be used for removing hydrogen halide include nitrogen gas and argon gas. .

At the end of the reaction, it is preferable to carry out the reaction under reduced pressure in order to sufficiently remove the hydrogen halide out of the reaction system.

When a dehydrohalogenating agent is used, the reaction temperature is preferably about 0 to 100 ° C, more preferably about 0 to 80 ° C. When a dehydrohalogenating agent is not used, the temperature is preferably about 50 to 180 ° C, and 70 to 180 ° C.
The degree is more preferred.

The use of a dehydrohalogenating agent is preferred because the reaction proceeds at a low temperature and coloration and side reactions hardly occur.

The phosphorus compound of the present invention exhibits an excellent flame retardant effect when blended with a resin such as a thermoplastic resin, a thermosetting resin, or a thermoplastic elastomer.

Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, polystyrene, high impact polystyrene (HIPS),
Styrene resins such as styrene-acrylonitrile (SAN) resin, ABS resin (styrene-acrylonitrile-butadiene copolymer), saturated polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyamide resins;
Examples include polycarbonate resin, polymethacrylate resin, polyacrylate resin, butadiene resin, and polyphenylene ether (PPE) resin. These resins may be a homopolymer, a copolymer, or a mixture thereof.

Examples of the thermosetting resin include an epoxy resin, a phenol resin, an unsaturated polyester resin, a polyurethane resin, an allyl resin and the like.

The amount of the phosphorus compound of the present invention relative to the above resin is not particularly limited, but is usually about 1 to 100 parts by weight, preferably about 1 to 60 parts by weight, per 100 parts by weight of the resin. It is.

The resin composition containing the phosphorus compound of the present invention may further contain, if necessary, a compound such as red phosphorus, melamine, melamine isocyanurate, zinc borate, barium metaborate as a flame retardant aid. , Can enhance the flame retardant effect.

These flame-retardant resin compositions may contain, if necessary, other flame retardants, ultraviolet absorbers, antioxidants,
Release agents, lubricants, coloring agents, plasticizers, fillers, foaming agents, heat stabilizers, and reinforcing agents such as glass fibers, carbon fibers, and aramid fibers can be added.

[0034]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 Preparation of Compound A (phosphorus compound of the formula (1), wherein R is a hydrogen atom, m is 1 and n is 0)

[0036]

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Phenol 1 was added to a reactor equipped with a stirrer, a thermometer, a cooling condenser and an inert gas injection pipe.
8.8 g (0.2 mol), phosphorus oxychloride 15.3 g
(0.1 mol) and 0.2 g of magnesium chloride, and the mixture was heated and stirred at 60 to 120 ° C. for 4 hours. Then
2- (6-oxide-6-H-dibenzo [c, e]
[1,2] oxaphospholin-6-yl) -1,4-benzenediol (hereinafter also referred to as HCA-HQ)
6.2 g (0.05 mol) was added, and the mixture was heated and stirred at 120 to 180 ° C. for 4 hours while passing a small amount of nitrogen gas. Then, this was cooled, neutralized, washed with water and dried under reduced pressure.
36.7 g of the target compound A as a pale yellow solid (yield 93.3)
%)Obtained. Melting point = 148 ° C (recrystallized from n-butanol) Elemental analysis Calculated values: P (11.80%), C (63.94%), H (3.93%)
%), O (20.27%) Actual values: P (11.64%), C (64.09%), H (3.63%)
%), O (20.32%) FIG. 1 shows an IR chart.

Example 2 Preparation of Compound B (phosphorus compound of the formula (1), wherein R is a hydrogen atom, X is a phenylene group, m is 1 and n is 1)

[0039]

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In the same reactor as in Example 1, phenol 1 was added.
5.6 g (0.17 mol), phosphorus oxychloride 15.3
g (0.1 mol), resorcinol 3.67 g (0.03
3 mol) and 0.3 g of iron chloride (FeCl ₃ ), and the mixture was heated and stirred at 60 to 120 ° C. for 4 hours. Then H
10.8 g (0.033 mol) of CA-HQ was added, and the mixture was heated with stirring at 120 to 180 ° C. for 4 hours while passing a small amount of nitrogen gas. Then, this was cooled, neutralized, washed with water, and dried under reduced pressure to obtain a high-viscosity pale yellow liquid of target compound B (3).
1.5 g (91.2% yield) was obtained. Elemental analysis Calculated values: P (11.97%), C (62.53%), H (3.85%)
%), O (21.58%) Observed values: P (11.85%), C (62.83%), H (3.71%)
%), O (21.66%) FIG. 2 shows an IR chart.

Example 3 Preparation of Compound C (phosphorus compound of the general formula (1), wherein R is a methyl group, m is 1, n is 0, and q is 1)

[0042]

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In the same reactor as in Example 1, cresol 2 was added.
1.6 g (0.2 mol), phosphorus oxychloride 15.3 g
(0.1 mol) and 16.2 g (0.0%) of HCA-HQ.
5 mol) and 20 g of toluene, and after cooling to 10 ° C., 30.6 g (0.3 mol) of triethylamine.
l) was added dropwise at 10 to 20 ° C, and then at room temperature for 3 hours, 40
The reaction was performed at ６０60 ° C. for 2 hours. After cooling, the reaction product was filtered, washed with water, dehydrated and concentrated under reduced pressure to obtain 39.5 g (yield 93.6%) of the target compound C as a high-viscosity yellow liquid. Elemental analysis Calculated: P (11.02%), C (65.39%), H (4.62%)
%), O (18.94%) Actual values: P (10.83%), C (65.58%), H (4.39%)
%), O (19.01%) FIG. 3 shows an IR chart.

Example 4 Preparation of Compound D (phosphorus compound of the formula (1), wherein R is a hydrogen atom, m is 2, and n is 0)

[0045]

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In the same reactor as in Example 1, phenol 1 was added.
5.7 g (0.167 mol), phosphorus oxychloride
3 g (0.1 mol) and 0.3 g of magnesium chloride
And heated and stirred at 80 to 90 ° C. for 1 hour and at 110 to 120 ° C. for 2 hours. Next, HCA-HQ was added to 21.6.
g (0.067 mol) and heated and stirred at 140-170 ° C. for 4 hours while passing a small amount of nitrogen gas.
The pressure was reduced at 10 ° C. and 10 Pa for 1 hour. Next, this was cooled, crushed and washed with water, and dehydrated and dried to obtain 38.8 g (yield: 93%) of the target compound D as a light yellow-brown solid. Melting point = 137 ° C (recrystallized from n-butanol) Elemental analysis Calculated values: P (12.40%), C (63.35%), H (3.76%)
%), O (20.40%) Observed values: P (12.38%), C (63.55%), H (3.69%)
%), O (20.51%) FIG. 4 shows an IR chart.

Example 5 Table 1 shows the results of thermogravimetric analysis of compound A, compound B and triphenyl phosphate (TPP).

[0048]

[Table 1]

Example 6 Epoxy resin (NPEL-127, manufactured by Nanya Corp.) 270
g, a curing agent (dicyandiamide, DICY) 42 g and a flame retardant (compound A, compound B, comparative compound RDP (resorcinol bisdiphenyl phosphate)) in 1
The composition was cured at 80 ° C. for 3 hours to prepare a 1.2 mm thick test piece. Table 2 shows the phosphorus content of this test piece and the results of a UL-94 combustion test.

[0050]

[Table 2]

Example 7 Phenol resin (BRG-556, manufactured by Showa Kogaku KK)
After mixing the curing agent (hexamethylenetetramine) and the flame retardant (Compound A, Comparative Compound RDP) at 120 ° C.
It was cured at 160 ° C. for 10 minutes to produce a 1.2 mm thick test piece. Table 3 shows the phosphorus content of the test piece and the results of a vertical burn test of UL-94.

[0052]

[Table 3]

Example 8 A polycarbonate resin and a flame retardant (compound A, compound B, comparative compound RDP) were melt-kneaded, and the resulting mixture was applied to a thickness of 1.2.
mm test pieces were prepared. Table 4 shows the phosphorus content of this test piece and the results of a vertical burn test of UL-94.

[0054]

[Table 4]

Example 9 Polycarbonate resin (PC), ABS resin and flame retardant (compound A, compound B, comparative compound RDP)
After kneading at ℃, a test piece having a thickness of 1.2 mm was prepared.
Table 5 shows the results of UL-94 vertical combustion tests performed on the test pieces.

[0056]

[Table 5]

Example 10 A modified PPE resin (HIPS / PPE = 74/26) and a flame retardant (compound A, compound B, comparative compound TPP (triphenyl phosphate)) were kneaded at 230 ° C.
A test piece having a thickness of 1.2 mm was prepared. Table 6 shows the results of the UL-94 vertical combustion test performed on this test piece.

[0058]

[Table 6]

Example 11 75 g of a styrene-acrylonitrile (SAN) resin composed of 75% by weight of styrene and 25% by weight of acrylonitrile
After adding 25 g of a flame retardant (compound D, comparative compound TPP) to the mixture, the mixture was kneaded at 230 ° C., and a test piece having a length of 100 mm, a width of 6.5 mm, and a thickness of 3.0 mm was prepared. About this test piece, JIS-K7201 (Oxygen Index method)
A combustion test was performed. The OI (oxygen index) when compound D was used as the flame retardant was 29.5, and the OI when TPP was used as the flame retardant was 24.1. This indicates that Compound D has an excellent flame retardant effect.

[0060]

The phosphorus compound of the present invention has a low bleed when incorporated into a resin, and has excellent flame retardancy and thermal stability.

[Brief description of the drawings]

FIG. 1 is an IR chart of Compound A obtained in Example 1.

FIG. 2 is an IR chart of Compound B obtained in Example 2.

FIG. 3 is an IR chart of Compound C obtained in Example 3.

FIG. 4 is an IR chart of Compound D obtained in Example 4.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 21/12 C09K 21/12 21/14 21/14 F-term (Reference) 4H028 AA35 AA46 BA06 4H050 AB80 BA51 BA92 BB11 BB12 BC10 WA15 WA23 4J002 BB031 BB121 BC031 BC041 BC061 BG041 BG051 BG061 BL011 BN141 BN151 CD001 CE001 CF061 CF071 CF081 CG001 CH071 CK021 CL001 CQ012 EW136 FD130 FD132 FD136 4J030 CA01

Claims (3)

[Claims] 1. A compound of the general formula (1) (Wherein, R represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms or a hydroxyl group, X represents a mononuclear aromatic group or a polynuclear aromatic group. M is an integer of 1 to 20, n is 0 to 20) The integer q
Is 1 or 2. A) a phosphorus compound represented by 2. A flame retardant comprising the phosphorus compound according to claim 1 as an active ingredient. 3. A flame-retardant resin composition containing a resin and the phosphorus compound according to claim 1.