JPS58187451A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:The titled resin composition having improved flame retardane without lowering thermal properties, obtained by blending a polyphenylene ether with a specific bicyclophosphoric ester compound. CONSTITUTION:100pts.wt. polyphenylene ether, preferably poly(2,6-dimethyl-1,4- phenylene)ether or a mixture (a mixture of polystyrene or impact-resistant polystyrene to improve molding properties) of it and another high polymer compound, is blended with 0.1-20pts.wt. preferably 1-10pts.wt. bicyclophosphoric ester such as 2,6,7-trioxa-1-phosphobicyclo[2,2,2]octane-1-oxide, etc. shown by the formula (l is 0-2; m and n are 1-3; R is 1-20C methylene).

Description

[Detailed description of the invention] (Background of IJ invention Technical field The present invention relates to a novel flame retardant resin composition.

In detail, the present invention relates to a flame-retardant 411 resin composition with excellent thermal properties, consisting of a mixture of polyphenylene ether and other polymeric substances, and a cyclophosphate ester compound.

Polyphenylene ether resin has excellent mechanical properties, thermal properties, and self-extinguishing properties, so it is attracting attention as a material for engineering/senioring plastics.

However, the flame retardancy of polyphenylene ether resin is not necessarily sufficient, and the molding processability of polyphenylene ether resin is extremely poor.
It is used by blending it with various resins, including (see Japanese Patent Publication No. 17812) to improve moldability. For this reason, the self-extinguishing property of polyphenylene ether mflll itself is impaired, and polyphenylene ether I1M resin alone has the disadvantage of becoming extremely flammable, and there is a desire for improvement in flame retardancy.

PRIOR ART In order to remedy these drawbacks, the aromatic phosphate compound, fljt,)liphenyl phosphate, has been used as a flame retardant.

However, since triphenyl phosphate also acts as a plasticizer, it imparts flame retardance and at the same time poses another problem of lowering the heat distortion temperature.

Therefore, at present, there is no satisfactory flame retardant method for polyphenylene ether meat fat compositions.

[Summary] Purpose of the Invention The present inventors aimed to improve the shortcomings of conventional flame retardant technology.
After investigating various flame retardant methods, it was discovered that by adding a bicyclophosphate ester compound, flame retardancy could be achieved without deteriorating thermal properties, and the present invention was achieved.

The purpose of the present invention is to make polyphenylene ether resin flame retardant, and to improve the moldability of polyphenylene ether resin, which is a drawback of polyphenylene ether resin, polyphenylene ether mm or polyphenylene ether resin is used. This object is achieved by adding a biachlorophosphate compound to a polyphenylene ether resin composition in an arbitrary proportion.

Accordingly, the polyphenylene ether resin composition according to the present invention comprises (a) 100 parts by weight of a resin comprising a mixture of polyphenylene ether, polyphenylene ether, polyphenylene ether, and a polymeric substance having compatibility with polyphenylene ether; and (b) Biachlorophosphate compound 0.1 represented by the general formula (wherein jIIiQ is an integer of 2, m and nij are each an integer of 1 to 3, and R is 1 representing a methine group or a methine group derivative having 1 to 20 carbon atoms) It is a polyphenylene ether resin composition consisting of ~20 parts.

Effects The novodiphenylene ether 4M resin composition of the present invention not only imparts flame retardancy, but also causes less deterioration in thermal properties due to the addition of a flame retardant, compared to conventional flame retardant methods.

[1 Detailed Description of the Invention (1) Resin The polyphenylene ether used in the present invention is described in many publications including U.S. Pat. ing.

Also preferred in A is polyphenylene niterol, which is a polymer having a general cyclic structural unit. where the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjacent unit, n is a positive integer of at least 50, and Q is hydrogen, halogen, tertiary hawk-carbohydrate without carbon atoms. Hydrogen radicals, halohydrocarbon radicals having at least 2 carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy radicals, and halohydrocarbonoxy radicals having at least 2 gA of carbon atoms between the halogen atom and the phenyl nucleus represents a monovalent substituent selected from the group consisting of

A typical example of polyphenylene ether is Ho17
(2,6-cy5uriru-1,4-phenylene)ether 1. t'lJ (2,6-diphenyl-1,4-phenylene)ether, poly(2,6-dimethoxy7-1.4-
phenylene) ether, poly(2,6-ethoxy-1)
, 4-phenylene) ether, poly(2-methoxy-
6-nitoxy1.4phenylene)ether, poly(2
-ethyl-6-stearyloxy-1,4-phenylene) ether, ho 1J (z, a-cyclo1,4-phenylene) ether, poly(2-methyl-6-phenyl-
1,4-phenylene) ether, HoIJ (2,6-cypenzyl-1,4-phenylene) ether, poly(2-ethoxy-1,4-phenylene) ether, poly(2-chloro-1,-Il/4 -phenylene)'11--thyl,
Poly(2,5-dibromo-1,4-phenylene) ether and the like. Examples of polyphenylene ethers corresponding to the above general formula can be found in the aforementioned US patent specifications.

For the purposes of the present invention, a particularly preferred group of polyphenylene ethers are those having alkyl substituents in the two orno positions relative to the e*ether atom, i.e. each Q in the orno position is an alkyl group, preferably from 1 to 4 carbon atoms. The above general formula (1) having an alkyl group of 1 contains phenylene ether. Representative examples of this group include poly(2,6-dimethe-1,4-phenylene) ether, poly(2,6-dimeter-1,4-phenylene)
-diethyl-1,4-phenylene)ether, BoIJ(
2-Methyl-6-ethyl-1,4-phenylene) ether, poly(2-lfsil--broby-1,4-phenylene) ether, poly(2,6-diprobyl-1,4-
phenylene) ether, poly(2-ethyl-6-broby-1+4-phenylene) ether, and the like.

The most preferred polyphenylene ether resin M for the present invention is poly(2,6-dimethyl-1,4-phenylene) ether.

A polyphenylene ether composition obtained by mixing the above polyphenylene ether resin with a polymeric substance having compatibility with the polyphenylene ether resin shown below can be used.

Examples of polymeric substances that are compatible with polyphenylene ether resin include polystyrene, impact-resistant polystyrene, styrene-phtadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer,
Polyethylene, polypropylene, polymethyl methacrylate, polycarbonate), polyethylene 17-terephthalate, nylon.

There are styrene-crafted polyethylene, styrene-grafted polypropylene, styrene-grafted polyacrylonitrile-styrene co-conjugated compound, styrene-grafted polyacrylonitrile-pumediene-styrene co-conjugated compound, styrene-grafted polyisobutene, etc. Among these, single-molecule substances of aromatic compounds are preferred. However, the most preferred material is polystyrene or high impact polystyrene.

These polymeric substances are mixed with the polyphenylene ether at a loss of 1 to 99 molar mass, preferably 20 to 80 molar mass.

(2) Pi-chlorophosphate compound w The bi-chlorophosphate compound blended into polyphenylene ether in the present invention has the general formula (in the formula, gFio is an integer of 2, m and n are each 1-
The integer 3 represents a methine group or a methine group derivative having 1 to 20 carbon atoms. ), 0 rhyme ANICP) phantom S
Keigen decoy S C (Geese decoy song vo1.6 (WILEY-I
NTH Le 8CIfJ4CJ, a Divisiono
f John Wiley & 5ons, Inc.
) and many other publications.

Typical examples of bicyclophosphate compounds include:
2.6.7-Dryoxer 1-phosphobicyclo(2,2
, 2J octane-1-oxide, 2.6.7-trioxa-l-phosphovinclo(2,2,2)octane-4-
Methyl-1-oxide, 2,6.7-trioxa-1
-phosphobicyclo(2,2,2J octane-4-ethyl-1-oxide, 2,6.7-trioxa-1-phosphobicyclo(2,2,2J octane-4-hexyl-1-oxide)
-oxide, 2,6.7-trioxa-1-phosphobicyclo(2,2,2)octane-4-hexadecyl-1
-oxide, 2.6.7-trioxa-l-phospho and 7
Kuro (2,2,2J octane-4m; Toro l-Oki 7
Do, 2. L7-) lioxa-l-phosphobicyclo(2
, 2,2J octane-4-amino-1-oxide, 2.
6.7- Trioxa-1-phosphobi/gate (2,2,
2J octane-4 hydroxy 7methyl-1-oxide, 2
,8.9-)dioxa-1-phosphobicyclo(3,3
, 13 nonane-5-methyl-1-oxide, 2,6.7
- ) dioxa-1-phosphobicyclo(2,2,1)heptane-4-methyl-1-A oxide and the like.

Addition of pink chlorophosphate compound used in the present invention 1
is O-1 to 20 for polyphenylene ether, Mataha, a mixture of polyphenylene ether and a polymeric substance having compatibility with polyphenylene ether.
1 part by weight, preferably 1 to 1 part by weight. 0 added enemies
．． If it is less than 1 part by weight, the ti-burning effect will not be exhibited, and if it is more than 20 parts by weight, the f1 will be significantly lowered, which will be a practical problem.

(3) Blending method The blending method for working the flame-retardant polyphenylene resin-terresin composition of the present invention generally includes iJ cutting,
When blending stabilizers, colorants, etc., the above method can be applied.

For example, a so-called general mixer such as an extruder or plastomill may be used.

Specifically, an extruder with a screw diameter of 25 mm was used, the cylinder temperature was 240 to 330 °C, and the screw rotation speed was 20 mm.
By extruding outside the 0 rotation, the desired flame-retardant polyphenylene ether resin composition can be obtained.

Alternatively, it is also possible to perform melt mixing for 5 to 15 minutes at a screw rotation speed of 20 to 40 revolutions/minute in a nine plasto mill that maintains the temperature of the melting cell at 240 to 330°C.

Example-1 Manufacture of a composition 50 parts by weight of poly(2,6-dimethyl-1-4phenylene)ether with a specific density of 0.50 dj/9 (measured in chloroform at 25°C) and high impact polystyrene (Asahi Dow 475D) 50 parts by weight and 2.6.7-)
Dioxa-1-phosphobicyclo(,2,2゜2]octane-4-ethyl-1-oxide Melt for 10 minutes at a screw rotation speed of 40 revolutions/piece in a blast mill with the quintuple pupil kept at 250°C. The desired flame-retardant polyphenylene ether resin composition was obtained by replacing the gold with gold.

The combustion test of this polyphenylene ether resin composition was conducted and the heat distortion temperature was measured by the following method, and the results are shown in Table 1 and FIG.

Combustion Test: How to judge the flammability of the flame retardant 11 shield composition of the present invention? Last year, in accordance with the U.S. ULfi rating 5 object 94, the following was issued.

A test specimen 6 inches long, 1/2 inches wide, and 1/16 inches thick was installed from the top 4 in the direction of watch in a stationary position with no air movement, and then a 374 inch long blue Apply the flame of the Bunzeno burner adjusted to expose the flame from the ↑゛ end of the test piece. Apply the burner flame to the lower part of the test piece for 10 seconds, remove the front and rear burners, and record the burning time after removing the burners (11th! Jlii fire burning time).

Immediately after extinguishing the flame, moxibustion from a burner is again applied to the lower end of the test piece in the same manner for 10 seconds, and the time until the flame extinguishes 6 times is recorded (second ignition combustion time).

The cotton is also placed one foot below the specimen and the ignitability of the cotton due to dripping of the flaming resin during the test is also recorded.

The above tests were conducted on five test pieces, and the maximum burning time was within 30 seconds, the average burning time was within 25 seconds,
94VE if all 5 out of 5 test pieces do not ignite the cotton.
-I, if even one of the five cotton is ignited, it will be 94-VE.
-1 is determined. Do not ignite the cotton in all 5 of the 5 test pieces within the maximum burning time of 10 seconds and the average burning time of 5 seconds.
If so, it will be 94 V E -g.

Furthermore, if the average burning time of the five pieces is 25 seconds or more or the maximum burning time is 30 seconds or more, it is determined to be 948B.

Therefore, as is clear from the above explanation, in order of flame retardancy, it is 94VE-0, 94VE-■.

94VE-1,94HB;/zru.

Heat distortion temperature was measured in accordance with ASTM-D-648 as follows. .

Puchi, size 126am width 12.6aa thickness 6.3as
The test piece was heated at a rate of 2°C per minute with a bending stress of 18.6 + 4/- applied to the test piece, and the bending force was 0.254U.
It was calculated as the temperature when the temperature reached .

Example-2 An experiment similar to Leprosy Example-1 was conducted using the mixing ratios shown in Table 1. The results are shown in Table 1 and Figure 1.

Comparative Examples 1, 2, and 3 The same experiment as in Series 1 was carried out using fuel and triphenyl phosphate at the mixing ratio shown in Example 1. The results are shown in Table 1 and Figure 1.

Comparative Example 4 An experiment similar to Example 1 was carried out without milder pheasant burning. The results are shown in Table 1 and Figure 1.

Comparative Examples 5 and 6 Experiments similar to those in Example 1 were carried out using the mixing ratios shown in Table 1. The results are shown in Table 1 and Figure 1.

Example-3 In place of the polystyrene used in Example M-1, acrylonitrile-butadiene-styrene copolymer (Japan Synthetic Rubber Co., Ltd. J8-Is) was used, and the mixture ratio shown in Table 2 was used. An experiment similar to Example-1 was conducted. The results are shown in Table 2.

Examples-4 to 8 2, L? used in Example-1 -) 13oxa-1-
Phosphobicyclo(2,2,2)octane-4-ethyl-
Instead of 1-oxide, nine bicyclophosphoric acid ester compounds shown in Table 2 were used, and at a mixing ratio shown in No. 2%,
An experiment similar to Example-1 was conducted.

The results are shown in Table 2.

(Left below) Table 1 Table 2 Structure 4 of pinchlorophosphoric acid ester 8-product f1 in the drawing
Figure 1 shows the relationship between the heat distortion temperature and the average combustion time of the combustion test of the resin compositions obtained in the examples of the present invention and the comparative examples.
It is a graph.

Patent applicant Mitsubishi Yuka Co., Ltd. Agent: Patent Attorney Hidetoshi Furukawa (1 other person)

Claims (1)

[Scope of Claims] (a) 100 parts by weight of a resin consisting of polyphenylene ether or a mixture of polyphenylene ether and a polymeric substance that is compatible with polyphenylene ether; and Φ) 0.0 parts by weight of a bicyclophosphate ester compound represented by the general formula. 1-20
A polyphenylene ether resin composition comprising: