JPH1030017A - Phosphorus-containing epoxy oligomer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject oligomer having a high phosphorus content, good in workability and capable of making cast articles, laminated plates, etc., flame resistant by reacting an aromatic dihydroxy compound with a diglycidyl ester of an arylphosphonic acid. SOLUTION: This phosphorus-containing epoxy oilgomer is expressed by the formula [R<1> is a 6-14C aryl; (n) 0-50; (m) is 0-50; the oligomer of the formula is a mixture of random oligomers, except a pure material when (n)=(m)=0.]. This oligomer is obtained by reacting (A) an arylphosphonic acid compound with (B) an arylphosphonic acid diglycidyl ester. The amounts of the ingredients to be compounded are preferably 100 pts.wt. of the ingredient A and 250-1000 pts.wt. of the ingredient B. Thus, the viscosity can be suitably adjusted.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a phosphorus-containing epoxy oligomer having excellent flame retardancy and a method for producing the same.

[0002]

2. Description of the Related Art Originally, most of epoxy resins were used as adhesives by making use of the properties of cured products. Subsequently, new uses such as paints and glass fiber reinforced plastics have increased due to the excellent mechanical strength and electrical insulation properties of the cured products. Recently, applications for electric and electronic materials such as laminates, molding materials, Applications such as stopper materials have become noticeable. In the wake of a series of fires and fire accidents in home appliances, the demand for flame-retardant insulating materials has increased, and the use of flame-retardant epoxy resins has started in insulating materials, vehicles, ships, aircraft, and building materials. It is also used for flame retardation of housings and the like.

Conventionally, as a method of making an epoxy resin flame-retardant, for example, "Plastic Age" (published by Plastic Age Co., Ltd.), June 1991, Nos. 146-15.
As described on page 3, a method using a halogen-containing epoxy compound such as diglycidyl ether of tetrabromobisphenol A, polyglycidyl ether of brominated phenol novolak, or a halogen-containing organic compound such as decabromobiphenyl ether is known. Have been. However, these flame retardants reduce heat resistance, electrical insulation, and the like, and may generate toxic gas during fire combustion. In addition, since a communication network was paralyzed by a fire at a nuclear power plant or a telephone office, it has been desired to reduce hydrogen halide and reduce smoke.

On the other hand, as phosphorus-based flame retardants,
Inorganic compounds such as polyphosphates and red phosphorus, and organic compounds mainly containing phosphate esters, particularly triphenyl phosphate (TPP), are widely used. However, these phosphorus-based flame retardants have the moisture resistance of epoxy resin,
There was a problem that heat resistance and the like were reduced.

[0005] Phosphorus-containing epoxy compounds have been studied as phosphorus-based reactive flame retardants, and aromatic compounds having a phosphorus atom incorporated in the skeletal chain (JP-A-61-134395, JP-A-2-272014). And aliphatic ether compounds (JP-A-62-223215), aromatic compounds having a phosphorus atom in the side chain (JP-A-5-39345, JP-A-61-148219) and the like are known. . However, compounds in which an aromatic ring is not directly bonded to a phosphorus atom (JP-A-62-223215, JP-A-61-223215)
No. 148219) is an aromatic compound having low heat resistance and two or more aromatic rings bonded to a phosphorus atom like triphenylphosphine oxides (JP-A-61-134395, JP-A-5-39345). Is expensive and the purification of synthetic products is not easy. Aromatic compound having only one aromatic ring bonded to a phosphorus atom (JP-A-2-272014)
Is a low-viscosity liquid. For example, when it is used as a casting resin, its viscosity cannot be adjusted, or when it is used as a laminated board material, there is a problem that the prepreg has stickiness and is inferior in workability. Further, the aromatic compound disclosed in JP-A-5-39345 has a problem that the phosphorus content is low.

[0006]

An object of the present invention is to provide a phosphorus-containing epoxy oligomer having a high phosphorus content and good workability.

Another object of the present invention is to provide a suitable method for producing the above-mentioned phosphorus-containing epoxy oligomer.

[0008]

The present invention provides a compound represented by the general formula (I):

[0009]

Embedded image (Wherein, R ¹ represents an aryl group having 6 to 14 carbon atoms;
Is 0 to 50, m is 0 to 50, and the oligomer represented by the formula (I) is a mixture of random oligomers. However, this excludes the case where only n = m = 0 pure substance. ) Is provided.

[0010] The present invention also provides a method for producing the above-mentioned phosphorus-containing epoxy oligomer, which comprises reacting (A) an arylphosphonic acid compound with (B) an arylphosphonic acid diglycidyl ester.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The phosphorus-containing epoxy oligomer of the present invention is represented by the above general formula (I), and the aryl group represented by R ¹ in the general formula (I) includes, for example,
Examples include a phenyl group and a naphthyl group, and among them, a phenyl group is more preferable. The aromatic nucleus such as phenyl group and naphthyl group may have a substituent such as alkyl group, hydroxyl group and amino group.

In the general formula (I), n is from 0 to 50, and m is from 0 to
50, and the oligomer represented by the general formula (I) is a mixture of random copolymers. (However, this does not apply to the case where the arylphosphonic acid diglycidyl ester of n = m = 0 alone is used.) When the values of m and n exceed 50, the properties of the cured product deteriorate. n is preferably from 0.1 to 10, and more preferably from 0.1 to 5. m is preferably from 0.1 to 10, more preferably from 0.1 to 5.

The phosphorus-containing epoxy oligomer of the present invention preferably has a phosphorus content of 10 to 15% by weight from the viewpoint of flame retardancy. The epoxy equivalent is 270 to 780 g /
eq, weight average molecular weight by GPC is 510 to 148
0, the number average molecular weight is preferably from 304 to 880.

The phosphorus-containing epoxy oligomer of the present invention comprises
It is obtained by reacting (A) an arylphosphonic acid compound with (B) an arylphosphonic acid diglycidyl ester.

As the (A) arylphosphonic acid compound, unsubstituted arylphosphonic acids such as phenylphosphonic acid and naphthylphosphonic acid, alkyl-substituted phenylphosphonic acid, hydroxyphenylphosphonic acid, aminophenylphosphonic acid, alkyl-substituted naphthylphosphonic acid, Substituted arylphosphonic acids such as hydroxynaphthylphosphonic acid and aminonaphthylphosphonic acid are used, and among them, phenylphosphonic acid is preferable.

The (B) arylglyconic acid diglycidyl esters include unsubstituted arylphosphonic acid diglycidyl esters such as phenylphosphonic acid diglycidyl ester and naphthylphosphonic acid diglycidyl ester.
Alkyl-substituted phenylphosphonic acid diglycidyl ester, hydroxyphenylphosphonic acid diglycidyl ester, aminophenylphosphonic acid diglycidyl ester,
Substituted arylphosphonic acid diglycidyl esters such as alkyl-substituted naphthylphosphonic acid diglycidyl ester, hydroxynaphthylphosphonic acid diglycidyl ester, and aminonaphthylphosphonic acid diglycidyl ester are used, and among them, phenylphosphonic acid diglycidyl ester is preferable.

In the present invention, the amount of each component is as follows:
Component (B) 250 to 100 parts by weight of component (A)
Preferably, the content is 1,000 parts by weight.
The amount is more preferably 0 to 600 parts by weight, and particularly preferably 250 to 350 parts by weight.
When the amount of the component (B) is less than 250 parts by weight, the number of epoxy groups tends to be extremely small due to a side reaction.
When the amount is more than the weight part, the workability tends to be deteriorated because the laminated material is sticky.

The reaction temperature in the present invention is 70 to 130.
° C, more preferably 80 to 120 ° C, and particularly preferably 80 to 100 ° C. If the reaction temperature is lower than 70 ° C., the reaction rate tends to decrease significantly. If the reaction temperature exceeds 130 ° C., side reactions such as a polymerization reaction due to ring opening of the epoxy ring tend to occur.

The reaction time in the present invention is preferably from 0.1 to 5 hours, more preferably from 0.5 to 3 hours, particularly preferably from 1 to 2 hours.
If the reaction time is less than 0.1 hour, the reaction tends to be insufficient, and if it exceeds 5 hours, a side reaction such as a polymerization reaction tends to easily occur due to ring opening of the epoxy ring.

In the present invention, the components (A) and (B) are reacted with a suitable inert solvent such as a reaction solvent such as toluene, xylene, acetone, methyl ethyl ketone, dimethylformamide, N-methyl-2-pyrrolidone or the like. May be carried out, or the reaction may be carried out without solvent.

[0021] The pressure in the reaction system in the present invention is not particularly limited. Therefore, the reaction can usually be carried out at normal pressure.

The method for producing the phosphorus-containing epoxy oligomer of the present invention includes, in addition to the above components, amines such as dimethylaminopyridine, imidazoles such as 2-ethyl-4-methylimidazole, and quaternary ammonium such as tetramethylammonium chloride. Catalysts such as salts and amine hydrochlorides such as triethylamine hydrochloride can be used. This amount is preferably 0.001 to 5% by weight based on the total amount of the components (A) and (B),
More preferably, the content is 0.01 to 2% by weight.

[0023]

The present invention will be described below with reference to examples. However, the present invention is not limited to the following examples.

Example 1 100 parts by weight of glycidol (manufactured by Wako Pure Chemical Industries, Ltd.) and triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) 121 were placed in a reactor equipped with a stirrer, a thermometer, and a dropping funnel in a draft. 1239 parts by weight of acetone and 1239 parts by weight of acetone (manufactured by Wako Pure Chemical Industries, Ltd., adjusted to a water content of 0.06%) were added in sequence, and the inside of the reaction vessel was kept at -10 to -5 ° C under an argon stream. While stirring with, a solution of 114 parts by weight of phenylphosphonic dichloride (manufactured by Wako Pure Chemical Industries, Ltd.) in 103 parts by weight of acetone was added dropwise over 90 minutes. After the completion of the dropwise addition, the cooling was stopped, and the stirring was further continued for 2 hours. After completion of the reaction, the mixture was filtered to remove triethylamine hydrochloride, and acetone was distilled off over 90 minutes at room temperature and a vacuum of 13 Pa to obtain a pale brown liquid. As a result of analysis by IR and NMR, it was confirmed to be diglycidyl phenylphosphonate.

Next, 100 parts by weight of phenylphosphonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 344 parts by weight of the above-mentioned diglycidyl phenylphosphonate are placed in a reaction vessel equipped with a stirrer and a thermometer in the fume hood. The mixture was added sequentially, and the inside of the reaction vessel was maintained at 97 to 103 ° C, and stirring was continued for 1 hour. After the completion of the reaction, a yellow semi-solid phosphorus-containing epoxy oligomer was obtained. The yield was 99%. The epoxy oligomer has an acid value of 2.5 (mgKOH / g) and an epoxy equivalent of 6
12 (g / eq), phosphorus content is 13.3% by weight, GP
The weight average molecular weight by C is 1164, and the number average molecular weight is 6
91. In the obtained epoxy oligomer, R ¹ in the general formula (I) is a phenyl group, and n and m are 0.49.
belongs to. IR, confirmed the structure NMR, ¹ H
-NMR peaks at 4.1 to 4.3 ppm and 4.4 to 5
n and m were determined from the integration ratio of the ppm peak.

Example 2 A phosphorus-containing epoxy oligomer was obtained in the same manner as in Example 1, except that the amount of diglycidyl phenylphosphonate was changed to 516 parts by weight. The epoxy oligomer has an acid value of 2.4 (mg KOH / g), an epoxy equivalent of 379 (g / eq), and a phosphorus content of 12.7.
% By weight, the weight average molecular weight by GPC was 869, the number average molecular weight was 521, and n and m were 0.29.

Example 3 A phosphorus-containing epoxy oligomer was obtained in the same manner as in Example 1 except that 0.01 parts by weight of 2-ethyl-4-methylimidazole was added as a catalyst. The epoxy oligomer has an acid value of 2.3 (mg KOH / g), an epoxy equivalent of 625 (g / eq), and a phosphorus content of 13.
The weight average molecular weight by GPC was 1281, the number average molecular weight was 705, and n and m were 0.51.

Example 4 100 parts by weight of the phosphorus-containing epoxy oligomer of Example 1
50 parts by weight of novolak type epoxy, 44 parts by weight of phenol novolak, and 3 parts by weight of triphenylphosphine as a catalyst were added to the resin, and the mixture was heated and mixed at 100 ° C. to obtain a uniform mixture. A resin plate having a phosphorus content of 6.9% by weight was prepared by pressing for 5 hours, and a combustion test in accordance with the UL94V method was performed. As a result, the total combustion time is 72 seconds, and the maximum combustion time is 15 seconds.
Seconds, indicating the flame retardancy of V-1. Further, the above resin composition was made into a methyl ethyl ketone solution, impregnated into a glass cloth, and then the solvent was removed at 120 ° C. for 5 minutes using a vertical hot-air drier to prepare a prepreg. The obtained prepreg had no stickiness and had good workability such as handleability.

Comparative Example 1 Example 4 was repeated except that the resin of Example 4 was changed to 100 parts by weight of novolak epoxy and 53 parts by weight of phenol novolak.
A resin plate was prepared in the same manner as described above, and a combustion test was performed. As a result, the resin plate was completely burned.

Comparative Example 2 In Example 4, instead of the phosphorus-containing epoxy oligomer, 100 parts by weight of diglycidyl phenylphosphonate of n = m = 0, 39 parts by weight of phenol novolak, and 3 parts by weight of triphenylphosphine based on the resin were used. And a prepreg was prepared in the same manner as in Example 4.
Since the prepreg was very sticky, it was wrapped around the top roll of the hot air dryer, and the prepreg could not be produced.

[0031]

The phosphorus-containing epoxy oligomer of the present invention is excellent in that the phosphorus content is high and the workability is good.
By changing the molecular weight of the oligomer, the viscosity can be adjusted in the case of a liquid, and the melt viscosity can be adjusted in the case of a semi-solid or solid. When it is used for a casting resin, its viscosity needs to be adjusted, and by using the phosphorus-containing oligomer of the present invention, it is possible to adjust the viscosity to an appropriate value and improve the casting workability. Further, when used as a laminate material, the molecular weight can be increased so as to be semi-solid or solid, the prepreg can be made non-sticky, and workability can be improved. Due to these effects, the phosphorus-containing epoxy oligomer of the present invention can be used for cast products, laminates,
It is suitable for flame-retarding molded articles, sealing materials, fibers, vehicles, ships, aircraft, building materials, housings, and the like.

Further, according to the method for producing a phosphorus-containing epoxy oligomer of the present invention, the above-mentioned phosphorus-containing epoxy oligomer can be produced with high yield.

Claims (2)

[Claims] 1. A compound of the general formula (I) (Wherein, R ¹ represents an aryl group having 6 to 14 carbon atoms;
Is 0 to 50, m is 0 to 50, and the oligomer represented by the formula (I) is a mixture of random co-oligomers. However, this excludes the case where only n = m = 0 pure substance. A) a phosphorus-containing epoxy oligomer represented by the formula: 2. The method for producing a phosphorus-containing epoxy oligomer according to claim 1, wherein (A) an arylphosphonic acid compound and (B) diglycidyl ester of an arylphosphonic acid are reacted.