JPH06321974A - Organophosphorus compound and flame-retardant composition containing the compound - Google Patents

Abstract

PURPOSE:To obtain a new compound having excellent heat-resistance and flame- retarding effect and useful for flame-retardant, etc., free from problems of deterioration and discoloration of resin in processing. CONSTITUTION:The compound of formula I [R1 and R2 are 1-8C alkyl or (substituted)6-12C aryl; A is bond, alkylene or (OCH2CH2)n ((n) is 1-5)], e.g. the compound of formula II. The compound of formula I can be produced e.g. by reacting a compound of formula III (X is halogen) with a compound of formula IV in the presence of an organic base (e.g. triethylamine) in an organic solvent. A flame-retardant resin composition can be produced by compounding 100 pts.wt. of a resin with 0.1-100 pts.wt. of the compound of formula I.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel non-halogenated organic phosphorus compound and a flame retardant resin composition containing the compound as a flame retardant and having excellent flame retardancy and heat resistance.

[0002]

BACKGROUND OF THE INVENTION Thermoplastic resins such as polypropylene, polystyrene and acrylonitrile-butadiene-styrene (ABS) resins; and organic polymers such as thermosetting resins such as polyurethane and phenolic resins are Since it has excellent properties such as being obtained at a relatively low cost and being easy to mold, it is widely used in general household products including electronic parts and automobile parts. However, since these organic polymers are flammable, there is a problem that once a fire occurs, they are easily burned and disappeared. Cable fires have a particularly great impact on society. Therefore, today, in some fields of application of these organic polymers such as electric products, automobile interior parts and textile products, flame retardation is obligatory. For example, the UL standard for electric appliances in the United States and the flame retardant regulation of MVSS-302 for automobiles are known.

In order to impart flame retardancy to organic polymers,
A method of adding a flame retardant at the time of preparing a resin molded product is adopted. Examples of the flame retardant added include inorganic compounds, organic phosphorus compounds, organic halogen compounds, halogen-containing organic phosphorus compounds, and the like. Among the above compounds, the organic halogen compound and the halogen-containing organic phosphorus compound exhibit excellent flame retardant effects. However, these halogen-containing compounds have a problem that they are thermally decomposed during resin molding to generate hydrogen halide to corrode the mold, deteriorate the resin itself, or cause coloration. Further, the halogen-containing compound has a problem that the working environment is deteriorated and that a toxic gas such as hydrogen halide which is harmful to the human body is generated when burned by a fire or the like.

As the flame retardant containing no halogen, there are inorganic compounds such as magnesium hydroxide. However, these inorganic compounds have a remarkably low flame retardant effect, and it is necessary to add a large amount of them in order to obtain a sufficient effect, thereby deteriorating the original physical properties of the resin.

As a flame retardant containing no halogen and capable of obtaining a relatively good flame retardant effect, an organic phosphorus compound containing no halogen is generally used. For example, aromatic phosphorus compounds such as triphenyl phosphate (TPP), tricresyl phosphate (TCP) and cresyl diphenyl phosphate (CDP), which are typical organic phosphorus compounds, are phenolic resins, epoxy resins and polyurethane resins. It is used as a flame retardant in various engineering plastics. However, since triphenyl phosphate and the like have a low phosphorus content, it is difficult to impart sufficient flame retardancy to the resin, and it is usually used in combination with a halogen-based flame retardant. Further, when used alone, triphenyl phosphate or the like needs to be blended in a large amount, which causes a problem that various physical properties of the resin are deteriorated and the resin is liable to be colored and deteriorated.

In addition, polyolefin, polypropylene,
As a flame retardant used for resins such as polystyrene, ABS and polyurethane, a compound represented by the formula (A):

[Chemical 2] The compound represented by
No. 2 is described. However, this compound
Since the phosphorus content is low, it is necessary to add a large amount to obtain satisfactory flame retardancy, which has the drawback of deteriorating the physical properties of the resin. Further, in the above formula (A), in the case of a compound in which all of R _{1 to} R ₅ are methyl groups, there is a drawback that the heat resistance is poor and therefore the resin is colored and deteriorated during molding.

In recent years, high-performance plastics such as engineering plastics and super engineering plastics have been developed. Since these plastics have high resin molding temperatures, the flame retardant used must also have high heat resistance. As a method of improving the heat resistance of the flame retardant, there is a method of adding an ordinary antioxidant (hindered phenol compound, sulfur compound, amine compound, etc.) to the resin in combination with the flame retardant. However, even when such an antioxidant is added to the resin together with, for example, the above organic phosphorus compound (A), 20
At a temperature of 0 ° C or higher, coloring of the resin is unavoidable.

The present invention solves the above-mentioned drawbacks of the prior art, and the purpose thereof is to be able to use it as a flame retardant capable of imparting excellent flame retardancy to various resins. It is to provide a novel compound which has excellent heat resistance and does not deteriorate or corrode the resin because it does not contain halogen when mixed with the resin and molding is performed. . Further, another object of the present invention is to contain the above compound and a resin, have excellent heat resistance and flame retardancy, have the flame retardancy continuously, and, when burned, drop molten resin ( It is intended to provide a flame-retardant resin composition capable of forming a molded product free from dripping).

[0009]

The inventors of the present invention have conducted extensive studies in view of the above problems, and as a result, have excellent heat resistance, and do not cause deterioration, corrosion, or coloring of the resin, which makes the resin excellent in difficulty. The present invention has found an organophosphorus compound that is flammable and does not generate hydrogen halide or the like because it is a non-halogen type and that can form a molded product that does not adversely affect the human body and does not deteriorate the mold. Has been completed. That is, according to the present invention, the formula (I):

[0010]

[Chemical 3] [In the formula, R ₁ and R ₂ are the same or different and each represents C _1-8.
A linear or branched alkyl group or an optionally substituted C _6-12 aryl group, A is a bond, an alkylene group or a-(OCH ₂ CH ₂ ) _n- group (n is an integer of 1 to 5) And an organic phosphorus compound (hereinafter referred to as compound (I)
And a flame-retardant resin composition comprising the compound (I) and a resin.

Examples of the "C _1-8 linear or branched alkyl group" represented by R ₁ and R ₂ in the above formula (I) include methyl, ethyl, propyl, isopropyl, butyl and isobutyl. , Pentyl, isopentyl, hexyl,
Examples thereof include 2-ethylhexyl, n-octyl and isooctyl groups, and among them, a methyl or ethyl group is particularly preferable. The formula (I), represented by R ₁ and R ₂ "which may be substituted C ₆ ~ ₁₂ aryl group"
Examples of the aryl group in are phenyl and naphthyl groups, and among them, a phenyl group is particularly preferable. These aryl groups are 1 to 3 C ₁
It may be substituted with ~ ₃ alkyl groups and examples of such substituents include methyl, ethyl and propyl groups. Preferred examples of substituted aryl groups are cresyl and xylyl. In the above formula (I), the "alkylene group" represented by A include lower alkylene group of C ₁ ~ _5, and examples _{thereof, -CH 2 -, - CH 2} CH 2 - and -CH ₂ CH ₂ CH ₂ -, etc. group. Among them, the —CH ₂ CH ₂ — group is particularly preferable. Further, in the above formula (I), the represented by A _{'- (OCH 2 CH 2) n} - group "
Examples of include —OCH ₂ CH ₂ — groups (n = 1) and —
_{OCH 2 CH 2 OCH 2 CH 2} - group (n = 2), and the like. Among them, the —OCH ₂ CH ₂ — group is particularly preferable.

The compound (I) of the present invention has the formula (III):

[0013]

[Chemical 4] [Wherein R ₁ and R ₂ are the same as defined in formula (I), X represents a halogen atom], and the formula (IV): HO ( CH ₂ CH ₂ O) _n H (IV) [wherein n is the same as the definition of formula (I)] [hereinafter abbreviated as compound (IV)], or formula (V): HO ( CH ₂ ) _m OH (V) [wherein m represents an integer of 2 to 8] [a compound (V)] is reacted in the presence of an organic base in an organic solvent. Can be obtained.

In this reaction, the organic base acts as an acid acceptor. Examples of the organic base include triethylamine, tributylamine, pyridine and dimethylaminopyridine, and these may be used as a mixture of two or more kinds. The amount of the organic base used is preferably 2 to 2.5 mol, and preferably 2.05 to 2.2, relative to 1 mol of the compound (IV).
Molar is more preferred. The reaction is carried out in an organic solvent, and the organic solvent used is preferably an inert organic solvent such as benzene, toluene, dichloroethane, dioxane and acetonitrile. In this reaction, the compound (II
The amount of I) used is 2 to 2. per mol of compound (IV).
5 mol is preferable and 2-2.1 mol is more preferable. The reaction is carried out at 25-80 ° C, preferably 30-70 ° C,
The reaction time is about 2 to 10 hours, preferably about 5 to 7 hours. The reaction product can be isolated and purified by known means, for example, solvent extraction, liquid conversion, salting out, crystallization, recrystallization and the like.

The starting compound (III) used in the above method for producing the compound (I) can be obtained by reacting phosphorus oxyhalide with a diol compound such as neopentyl glycol. In addition, compound (IV)
Is ethylene glycol when n = 1. n = 2
When, it is diethylene glycol. Examples of the other compound (IV) include triethylene glycol and tetraethylene glycol. further,
The compound (V) is ethylene glycol when m = 2, propylene glycol when m = 3, and butylene glycol when m = 4.

In the above method for producing compound (I),
By appropriately selecting the types and amounts of the raw material compounds (III) and (IV), the organophosphorus compound (I) having a desired phosphorus content and molecular weight can be obtained. The organophosphorus compound (I) thus obtained can be used alone or in combination of two or more as a flame retardant.

The flame-retardant resin composition of the present invention comprises a resin and the above-mentioned organic phosphorus compound (I), and optionally contains an antioxidant and other additives. Examples of the antioxidant that is optionally added to the flame-retardant resin composition of the present invention include formula (II):

[0018]

[Chemical 5] [Wherein R ₃ , R ₄ , R ₅ and R ₆ are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 14 carbon atoms] and a trivalent compound The organic phosphorus compounds of

Examples of the hydroquinone compound (II) include hydroquinone, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone and octylhydroquinone. Particularly preferred hydroquinone compounds having excellent heat resistance are 2,5-di-tert-amylhydroquinone and 2,5-di-tert-butylhydroquinone.

Examples of the above trivalent organic phosphorus compound include:
Triphenyl phosphite, tris (nonylphenyl)
Phosphite, diphenylisodecyl phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite and tetrakis (2,4
-Di-tert-butylphenyl) 4,4-diphenylenephosphonite and the like.

Examples of additives include halogen flame retardants, inorganic flame retardants, fillers and lubricants. The type and amount of the organophosphorus compound (I) used are
It is appropriately determined depending on the resin used and the degree of flame retardancy required. The organic phosphorus compound (I) is usually the resin 1
It is used in a proportion of 0.1 to 100 parts by weight, preferably 5 to 50 parts by weight, relative to 00 parts by weight.

A flame-retardant molded article can be obtained by kneading the resin, the organophosphorus compound (I) and, if necessary, the above-mentioned antioxidant and other additives by a known method and molding. At this time, the organophosphorus compound (I) may be added together with the monomer charged when the resin is produced by bulk polymerization, or may be added at the end of the reaction of the bulk polymerization of the resin. Further, it may be added at the time of molding the resin. By adding the organic phosphorus compound (I) as described above, flame retardancy is imparted to the obtained molded article.

Examples of resins used in the present invention include thermoplastic resins and thermosetting resins. Examples of thermoplastic resins include chlorinated polyethylene, polyethylene, polypropylene, polybutadiene, styrene resins, high impact polystyrene, polyvinyl chloride, AC.
Examples include S resin, AS resin, ABS resin, polyphenylene oxide, polymethylmethacrylate, polyamide, polyester and polycarbonate. Examples of thermosetting resins include polyurethane, phenolic resins, melamine resins, urea resins and unsaturated polyesters. You may use the said resin 1 type or in mixture of 2 or more types.

When the compound (I) is used for a resin such as modified polyphenylene oxide (PPO), polystyrene or ABS resin, it is used in combination with an inorganic flame retardant such as magnesium hydroxide or antimony trioxide. Can be used. When it is used for polyurethane foam, it can be used in combination with a non-halogen compound such as melamine or urea.

[0025]

The present invention will be described with reference to the following examples.
These examples do not limit the scope of the invention. In the following examples, unless otherwise indicated,
All parts are by weight and all temperatures are given in degrees Celsius.

Example 1 A four-necked flask was equipped with a stirrer, a thermometer and a condenser connected to a water scrubber, and 104 parts (1 mol) of neopentyl glycol and 100 parts of toluene were placed in this flask and oxychlorinated at 50 ° C. Phosphorus 153.5
Part (1 mol) was added over 1 hour, and dehydrochlorination reaction was carried out for 4 hours to complete the reaction. To the reaction solution was added 150 g of toluene, 31 parts (0.5 mol) of eletin glycol and 200 parts of dioxane were added at 20 ° C., and a mixed solution of 111 parts of triethylamine and 0.5 part of dimethylaminopyridine was added at 50 ° C. for about 2 minutes. Dropped for hours. Then, the temperature was raised to 80 ° C. and aging was carried out for 5 hours to complete the reaction. The solvent was removed by filtration to precipitate the desired product and the hydrochloride of the amine, and then the hydrochloride of the amine was removed with methanol to obtain 1
It was dried under reduced pressure at 00 ° C. The obtained crystals were white powdery crystals, and the yield was 155 g and the yield was 87%. This crystal has a structure represented by the following formula (this is referred to as Compound 1). Table 1 shows the results of elemental analysis of Compound 1 (C ₁₂ H ₂₄ O ₈ P ₂ ) having an mp of 164 to 166 ° C. The NMR measurement results are shown in FIG.

[0027]

[Chemical 6]

Example 2 A white powder crystal having the structure of the following formula was obtained in the same manner as in Example 1 except that 51 parts of diethylene glycol was used instead of 31 parts of ethylene glycol. Yield 16
With 1 g, the yield was 80% (this is compound 2). Table 1 shows the results of elemental analysis of mp116 ° C. compound 2 (C ₁₄ H ₂₈ O ₉ P ₂ ). The NMR measurement results are shown in FIG.

[0029]

[Chemical 7]

Example 3 A white powdery crystal having the structure of the following formula was obtained in the same manner as in Example 1 except that 45 parts of 1,4-butanediol was used in place of 31 parts of ethylene glycol. Yield is 1
The yield was 85% at 64 g. (This is referred to as Compound 3.). Table 1 shows the results of elemental analysis of mp127 ° C. compound 3 (C ₁₄ H ₂₈ O ₈ P ₂ ).

[0031]

[Chemical 8]

[0032]

[Table 1] Although the organophosphorus compound of the present invention may contain a side reaction product, it does not affect heat resistance and flame retardancy when used as a flame retardant. In Examples 4 to 6 below, the performances of the above-mentioned organic phosphorus compounds 1 and 2 and the following conventional flame-retardant compounds (flame retardants) were evaluated. Compound A (compound described in JP-A-49-62424)

[0033]

[Chemical 9] Compound B

[0034]

[Chemical 10] Compound C

[0035]

[Chemical 11] Compound D

[0036]

[Chemical 12] Compound E

[0037]

[Chemical 13] Compound F

[0038]

[Chemical 14]

Example 4 Components of flame-retardant resin composition Polyol (Mitsui Toatsu Chemicals, Inc., trade name MN-3050 ONE) 100 parts Isocyanate (Mitsui Toatsu Chemicals, trade name TDI 80/20) 55. 1 part Polyol silicon oil (Nippon Yunika Co., Ltd., trade name L-520) 1.2 parts Tin-based catalyst 0.25 parts Amine-based catalyst 0.15 parts Water 4.5 parts Methylene chloride 3.0 parts Flame-retardant compound (Predetermined amount shown in Table 1)

Using the above components, a soft urethane foam was produced by the one shot method as follows. First, among the above-mentioned components, polyol, silicone oil, catalyst, methylene chloride, water and flame-retardant compound are blended, and 3000
The mixture was stirred for 1 minute with a stirrer having a rotation speed of rpm and mixed uniformly. Then add the isocyanate for another 300
After stirring at 0 rpm for 5-7 seconds, the contents were quickly poured into a carton with a square cross section. Foaming occurred immediately and reached maximum volume after a few minutes. This for another 30 minutes at 120 ℃
Cured in an oven. The obtained foam was a white soft foam having open cells.

Samples were cut from the various foams obtained by the above-mentioned method and subjected to a combustion test by MVSS-302. Furthermore, a new sample is placed in a microwave oven (500W) for 3
It was heat-treated for 2 minutes and then at 140 ° C. for 2 hours. At this time, the change in color of the test piece (presence or absence of scorch) was observed. The results are shown in Tables 2 and 3. In the "scorch" section of Table 3, ◯ means that almost no color change was observed, and x means that the color changed to brown.

[0042]

[Table 2]

[Table 3]

As is clear from Tables 2 and 3, the organophosphorus compound of the present invention can impart better flame retardancy than the conventional halogen-based flame retardant compound,
And no scorch is recognized. Even if the above-mentioned organophosphorus compound of the present invention is kept at a temperature of 80 ° C. for 14 days,
There was no change in the flame retardancy imparting effect.

Example 5 100 parts by weight of a high impact polystyrene / PPO resin (45/55) mixture was added to the organophosphorus compound 10 shown in Table 4.
Parts by weight were added and blended uniformly with a 10 L V-blender for about 15 minutes. This was pelletized with an extruder having an inner diameter of 40 mm, and the pellet was used to prepare a predetermined test piece with a molding machine having a capacity of 4 ounces.

The flame retardancy of these test pieces was evaluated by UL-9.
It carried out according to the test method prescribed in 4. Five test pieces were made for each organophosphorus compound, and the time from ignition to extinction was measured twice for each test piece, and the total time of the two times was taken as the combustion time, and the combustion of the five test pieces was performed. The average value of time was calculated. Then, set the heat distortion temperature to ASTM
It was measured according to standard D648. Regarding the juicing, the surface of the molded product was visually observed. The results are shown in Table 4.

[0046]

[Table 4]

Example 6 ABS resin (Cevian-V, manufactured by Daicel Chemical Industries, Ltd.) 100
10 parts of the organophosphorus compound shown in Table 5, 5 parts of tetrabromobisphenol A and 2.5 parts of Sb ₂ O ₃ were added to parts by weight and uniformly blended for about 15 minutes with a 10 L V-type blender. Pellet this with an extruder with an inner diameter of 40 mm,
It was molded into a predetermined test piece with a 4 ounce molding machine.

The flame retardancy of these test pieces was evaluated by UL-9.
It carried out according to the test method prescribed in 4. Five test pieces were made for each organophosphorus compound, and the time from ignition to extinction was measured twice for each test piece, and the total time of the two times was taken as the combustion time, and the combustion of the five test pieces was performed. The average value of time was calculated. Then, set the heat distortion temperature to ASTM
It was measured according to standard D648. Regarding the juicing, the surface of the molded product was visually observed. The results are shown in Table 5.

[0049]

[Table 5]

[0050]

The novel organophosphorus compound (I) of the present invention
Can give the resin excellent flame retardancy when mixed with various resins. The organophosphorus compound (I) has low volatility, is excellent in heat resistance, does not cause coloring and deterioration of the resin due to thermal decomposition during molding, and further hardly deteriorates the physical properties of the resin. Further, since the organophosphorus compound (I) of the present invention is a non-halogen type, it does not generate hydrogen halide and does not adversely affect the human body. Furthermore, when the flame-retardant resin composition according to the present invention is used, a molded article can be formed which does not cause dripping of molten resin when burned.

[Brief description of drawings]

FIG. 1 shows an NMR spectrum diagram of Compound 1.

FIG. 2 shows an NMR spectrum diagram of Compound 2.

Claims (8)

[Claims] 1. Formula (I): [In the formula, R ₁ and R ₂ are the same or different and each represents C _1-8.
A linear or branched alkyl group or an optionally substituted C _6-12 aryl group, A is a bond, an alkylene group or a-(OCH ₂ CH ₂ ) _n- group (n is an integer of 1 to 5) And an organic phosphorus compound represented by. 2. The organophosphorus compound according to claim 1, wherein in the definition of formula (I), R ₁ and R ₂ are methyl groups and A is a bond. 3. The organophosphorus compound according to claim 1, wherein in the definition of formula (I), R ₁ and R ₂ are methyl groups, and A is a —OCH ₂ CH ₂ — group. 4. The organophosphorus compound according to claim 1, wherein in the definition of formula (I), R ₁ and R ₂ are methyl groups, and A is a —CH ₂ CH ₂ — group. 5. A flame-retardant resin composition comprising the organic phosphorus compound according to claim 1 and a resin. 6. The flame-retardant resin composition according to claim 5, wherein the resin is a thermoplastic resin or a thermosetting resin. 7. A resin having an organophosphorus compound content of 100%.
The flame-retardant resin composition according to claim 5, which is 0.1 to 100 parts by weight with respect to parts by weight. 8. The content of the organic phosphorus compound is the resin 100.
The flame-retardant resin composition according to claim 7, which is 5 to 50 parts by weight with respect to parts by weight.