JPS587448A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:A composition having extremely improved moldability, releasability, and impact resistance, obtained by blending a composition of polyphenylene ether and a styrenic polymer with a polyphenylene ether graft polyolefin. CONSTITUTION:80-20pts.wt. polyphenylene ether and 20-80pts.wt. styrenic polymer are blended with 0.1-50wt% polyphenylene ether graft polyolefin based on the total amount of polyphenylene ether and styrenic polymer. The molecular weight of the polyphenylene ether part of the polyphenylene ether graft polyolefin is preferably 5,000-100,000, and the number-average molecular weight of the polyolefin continuous chain is preferably 3,000-50,000.

Description

Detailed Description of the Invention (1) Background of the Invention The present invention relates to a resin composition containing polyphenylene ether, and relates to a polyphenylene ether resin composition that has improved moldability, mold release properties, and impact resistance. be.

Polyphenylene ether is an extremely useful thermoplastic resin with excellent heat resistance, mechanical properties, electrical properties, water resistance, acid resistance, alkali resistance, self-extinguishing properties, etc., and is widely used as an engineering plastic material. Applications are being developed.

However, this resin has major drawbacks such as high glass transition humidity, high melt viscosity, and poor moldability. It also has disadvantages such as poor mold release during injection molding and poor impact resistance as an engineering plastic.

(2) Prior art In order to overcome these drawbacks, especially to improve moldability, it has been attempted to blend polyolefins or styrenic polymers such as polystyrene, rubber-modified polystyrene, and styrene-acrylonitrile-butadiene copolymers. I, Special Public Prosecutors Office No. 59 of 1970 and Special Public Prosecutors Office No. 4
3-178j No. 2, US Pat. No. 3,383,435, and the like.

However, in a composition consisting of polyphenylene nitrate and high molecular weight polyolefin, the two polymers do not mix uniformly and form a so-called "sea-island J structure. Furthermore, the two polymers are essentially incompatible. Therefore, the [sea-island] interface is extremely weak.As a result, the resulting composition is brittle and has low mechanical strength and impact strength.Also, when subjected to shear stress during molding such as injection molding, both Since the polymers are essentially incompatible, they aggregate in the same direction as the flow of the resin, forming a layered structure, and the resulting molded product peels off in layers, making it unusable. In order to improve this point, it has been proposed, for example, in Japanese Patent Publication No. 48-39015, to use a low molecular weight crystalline polyolefin instead of a high molecular weight polyolefin, but polyphenylene ether and polyolefin are essentially not compatible. The reality is that it does not solve the fundamental problem because we do not have it.

In a composition consisting of polyphenylene ether and boristyrene, increasing the amount of polystyrene added improves moldability, but on the other hand, heat resistance, mechanical strength,
Properties such as impact strength decrease on an arithmetic average basis. However, this resin composition is of high practical value, except for special uses, mainly for economic reasons.

(3) Summary of the Invention The present inventors have carried out extensive research in order to further improve the properties of the resin composition composed of polyphenylene ether and a styrene polymer. It has been found that a composition containing grafted polyolefin has extremely excellent moldability and mold releasability. Furthermore, since the polyphenylene ether-grafted polyolefin has essentially good compatibility with polyphenylene ether and polystyrene, there is no decrease in mechanical strength, and furthermore, surprisingly, impact strength is greatly improved. I discovered that.

That is, the present invention includes 80 to 20 parts by weight of polyphenylene ether, 20 to 80 parts by weight of styrene polymer, and Oj to 50% by weight of poly7-ethylene based on the total amount of polyphenylene ether and styrene polymer. The object of the present invention is to provide a polyphenylene ether resin composition with improved processability and impact resistance, which is characterized by containing an ether-grafted polyolefin.

(4) Detailed Description of the Invention The polyphenylene ether referred to in the present invention has a structure represented by the general formula, where Pl, R2, R3 and R4 each independently represent hydrogen, halogen, hydrocarbon or substituted hydrocarbon. , cyan group, alkoxy group or phenoxy group, nitro group, asano group or sulfo group. n is an integer indicating the degree of polymerization, and is from 20 to 800. Specific examples of R1, R2, R3 and R4 and 1. So,
Examples include hydrogen, chlorine, bromine, iodine, methyl, ethyl, propyl, butyl, allyl, phenyl, benzyl, methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, methoxy, ethoxy, phenoxy, nitro, amino, sulfo, etc. It will be done. Specifically, poly-2
, 6-dimethyl-1,4-phenylene ether, poly-
2,6-diethyl-1,4-phenylene ether, poly-2,6-diprobyl-1,4,-phenylene ether, poly-2-methyl-6-itubrobyl-1,4-phenylene ether, poly-2,6 -Simethoxy 1.4-
Phenylene ether, poly-2,6-cyclomethyl-1,4-phenylene ether, poly-2,6-di7enyl-1,4-phenylene ether, poly-2,6-cynitri-1,4-phenylene ether, poly -2,6-
Dichloro-1,4-phenylene ether, poly-2,5
-dimethyl-1,4-phenylene ether and the like.

The styrenic resin used in the present invention has the general formula (where R4 represents hydrogen, a lower alkyl group, or a halogen, R5 represents hydrogen, a lower alkyl group, or a vinyl group, and m represents an integer of 1 to 5. A polymer or copolymer having at least 25% of polymerized units derived from a compound having the following formula. Specific examples include homopolymers such as polystyrene, polyα-methylstyrene, or polychlorostyrene, polystyrenes such as rubber-modified polystyrene, and styrene-acrylonitrile copolymers;
Examples include styrene/butadiene/acrylonitrile copolymer, styrene/maleic anhydride copolymer, and styrene/maleic anhydride/butadiene copolymer.

In addition, the polyphenylene ether grafted polyolefin referred to in the present invention has the following general formula (in the margins): the present R3-C, the present 8-0 ↓ (R6, R7, R8, and Ro are each independently hydrogen, a methyl group, and an ethyl group). , methyl ester group, ethyl ester group, carboxyl group, maleic anhydride group and carbon@3~
Represents 5000 hydrocarbon branches. Horse.

and R11 each independently represent hydrogen, halogen, hydrocarbon, substituted hydrocarbon, alkoxy group or phenoxy group. U and W represent integers of 50 or more and 1000 or less. '9s CLs El and t indicate the content of the indicated component, p and q indicate that (p+q) is 50 or more 5
Represents an integer selected to be less than or equal to 000. 8 and t represent the number of herons selected so that (s + t) is 0.5 or more and 50 or less. ) is a compound in which polyphenylene ether is grafted to a run, dumb copolymer chain, or block copolymer chain of a polyolefin.

This polyphenylene ether graft polyolefin is a polyolefin having a carboxyl group or anhydride group in the main chain or side chain, which is obtained by reacting polyphenylene ether with epichlorohydrin in the presence of an alkali such as caustic soda. For example, in the presence of an alkali component, ethylene/acrylic copolymer, ethylene'/methacrylic acid copolymer, maleic anhydride-modified polyethylene, maleic anhydride-modified polyethylene, maleic anhydride-modified ethylene/vinyl acetate copolymer, etc. It can be obtained by grafting it on.

Polyphenylene ether-grafted polyolefin is produced by grafting polyphenylene ether onto a polyolefin having a glycidyl group in its side chain, such as ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, etc. You can also get The graft reaction is usually carried out in a solution or molten state using an alkali such as caustic soda, an amine such as tri-n-butylamine, etc., which are known as catalysts for the reaction between an epoxy ring and a hydroxyl group. Furthermore, at high temperatures of 150° C. or higher, the graft reaction proceeds without using any of these catalysts, and polyphenylene graft polyolefins can be obtained even without catalysts. Therefore, in some cases, the resin composition of the present invention can be obtained by kneading polyphenylene ether, styrene, and a polyolefin having a glycidyl group at 1'50°C or higher.

The molecular weight of the polyphenylene ether part of the gelama domer is preferably 5,000 or more and 100,000 or less.

When the molecular weight is less than 5,000, the Gla7tomer 61 is somewhat brittle, resulting in a decrease in the mechanical strength of the resulting composition. On the other hand, if a polyphenylene ether of 100,000 or more is used, the graft reaction with the polyolefin will not proceed completely due to the polymer effect. Further, the number average molecular weight of the polyolefin chain of the graftomer is 1000 to 100.
000 can be used, but from the physical property balance of the composition of the present invention obtained by blending the graftomer, 3000
50,000 is particularly preferred.

The preferred proportions of each component polymer in the present invention are 80 to 20 parts of polyphenylene ether and 2 parts of styrene polymer.
0 to 80 parts by weight, and 0.1 to 50% by weight, preferably 1 to 30% by weight, of the polyphenylene ether grafted polyolefin based on the total amount of the polyphenylene ether and the styrene polymer. Ink. If the polyphenylene ether content is less than 20% by weight, that is, if the styrenic polymer content is greater than 80% by weight, the resulting composition will have poor mechanical properties such as impact bag strength. Addition amount of polyphenylene ether graft polyolefin: 0.1% by weight
If it is less than 50% by weight, the effect of addition will be small, and if it is more than 50% by weight, tensile strength, heat distortion temperature, etc. will decrease.

When polyolefin is mixed into a homogeneous mixture of polyphenylene ether and styrene polymer, a sea-island structure is formed because the polyolefin and polyphenylene ether or styrene polymer are essentially incompatible. The interface between the two is extremely weak, and when subjected to stress such as impact, cracks occur from this interface and breakage is likely to occur. The rifhenylene ether-grafted polyolefin used in the present invention has essentially improved compatibility with the polyphenylene ether or styrene polymer that serves as the matrix.
The inventive composition obtained by adding polyphenylene ether graft polyolefin not only has excellent moldability and mold release properties, but also has greatly improved mechanical strength, especially impact strength. This is because the polyphenylene ether grafted polyolefin dispersed in a matrix consisting of a homogeneous mixture of polyphenylene ether or hapolyphene = L/:,/:L-tyl and a styrene polymer is essentially compatible with the matrix. Therefore, it is extremely small) minutes.

This is thought to be due to the fact that it is uniformly distributed as a dispersed unit, dispersing stress in the event of impact, and that the interface with the matrix is strengthened, thereby preventing the progressive force of fracture from the interface. .

The resin composition of the present invention is produced by melting and mixing each component in various kneading machines, such as a -screw extruder, twin-screw extruder, pan, <+J-mixer, roll, gravender blastogram, etc., and then cooling and solidifying. Either method may be used, such as a method in which each component of the polymer is formed into a solution or emulsion, mixed uniformly, and then the solvent is removed. Although the various polymeric components may be added in any possible order, it is advantageous from an economical point of view to mix all components simultaneously.

Furthermore, it goes without saying that rubber-like polymers, glass fibers, inorganic fillers, heat-resistant preservatives, flame retardants, coloring pigments, and the like may be added depending on practical needs.

EXAMPLES The present invention will be described below with reference to Examples in order to further clarify the present invention, but the scope of the present invention is not limited by these Examples.

First, the method for producing the polyphenylene ether graft polyolefin used in the present invention will be illustrated below.

Reference Example 1 Production details of glycidylated polyphenylene ether Fill a 30-ton stainless steel autoclave with 10 tons of Ebichlor and hydrin, and then add poly-2
, 300 g of 6-dimethyl-1,4-phenylene ether polymer powder (manufactured by Mitsubishi Yuka Co., Ltd., intrinsic viscosity 0.47 dt/g at 30°C in chloroform) is added. Next, the temperature was raised using an external jacket, and the temperature was raised to 100% while stirring.
After keeping at ℃ for about -30 minutes to completely dissolve the polymer,
Add 50 ccm of 0% caustic soda aqueous solution and react at 100°C for 3 hours under nitrogen atmosphere. After the reaction is completed, epichlorohydrin is distilled off under reduced pressure, and the resulting polymer is dissolved in 5 tons of chloroform. The solids liberated in the polymer solution (formed Nact and excess NaOH) were removed by p
After separate removal, a mixed solvent of methanol/water (50150) was added to reprecipitate the polymer, washed three times with the same lot of solvent, and dried at 100°C for about 10 hours. ) was obtained. The polymer obtained by this operation is I S 0-
As a result of titration using toluene as a solvent in accordance with the method specified in 3001, the amount of glycidyl groups contained in 100 g of polyv-v-1 was 5.6 x 10 mol. The number average molecular weight determined by the osmotic pressure method was 18,000, confirming that each molecule has one glycidyl group. Also, JApp, Polym, ,S
ci, Polym.

As described in S Fln p O,, ii+ p103,
As a result of quantifying the terminal hydroxyl groups before and after the reaction according to the method of 5hchori et al., it was confirmed that 94% of the hydroxyl groups had disappeared due to the reaction. From the above, it is clear that the following reaction proceeded almost quantitatively.

(Leaving space below) Reference Example 2 Production of Graftomer 8' Into an autoclave with an internal volume of 30 tons, 1 ol of toluene and 200 g of GPP obtained in Reference Example 1 were added, and ethylene/acrylic acid copolymer (manufactured by Mitsubishi Yuka Co., Ltd., ethylene content 96.
3wt%, acrylic alcohol content 3. Add 100 g of '7 wt % number average molecular weight 150 o, o ) and dissolve by heating to 110°C in a nitrogen atmosphere. Next, 5 dt of N.N-dimethylaniline was added, and the mixture was reacted for 8 hours with stirring under llo''c. After the reaction was completed, it was cooled to room temperature, and 15 t of acetone was added to precipitate the polymer, which was recovered separately. After dissolving the resulting polymer in hot xylene, cooling it at room temperature and centrifuging it twice, the amount of GPPO in the precipitate was determined using an infrared absorption spectrum and a calibration curve. 100g of ethylene/acrylic i-copolymer contained 164g of xylene-insoluble GPP0.On the other hand, unreacted GPPO recovered as xylene-soluble content was 18%.From this, as a result of the above reaction, Average of 1 per molecule of ethylene/acrylic acid copolymer
．． It can be seen that 4 molecules of GPPO were grafted. As the grafting reaction progressed, the carbonyl stretching vibration in the infrared absorption spectrum showed a shoulder attributable to the ester bond at 1745i', confirming that a graft copolymer with the following structure was obtained. It was done.

Ll ti3LJ H3 Reference Example 3 Production of Graftomer B 10 tons of xylene in an autoclave with an internal volume of 301, Reference Example 1 200 g of the obtained GPP, maleic anhydride-modified polypropylene (manufactured by Mitsubishi Yuka Co., Ltd., maleic anhydride content J3 wt%, number average (molecular weight 18,000) was added and dissolved by heating at 120°C under a nitrogen atmosphere, s+·N-dimethylaniline lomt was added, and the mixture was allowed to react at 120°C for 8 hours with stirring. After the reaction was completed, it was cooled to room temperature, and 15 tons of acetone was added to precipitate the polymer, which was recovered separately. When the polymer obtained by this operation was analyzed in the same manner as in Reference Example 2, it was found to be maleic anhydride-modified polypropylene.

It was confirmed that the maleic anhydride group of the polymer reacted with the terminal epoxy group of GPPO, and polyphenylene ether was grafted onto the polypropylene.

Reference Example 4 Production of Graftomer C Maleic anhydride-modified polypropylene of Reference Example 2 was replaced with maleic anhydride-modified polyethylene (manufactured by Mitsubishi Yuka Co., Ltd., maleic anhydride content 2.3 wt%, number average molecular weight 120
Polyethylene grafted with polyphenylene ether was obtained in the same manner as in Reference Example 2 except that 00) was used.

Reference Example 5 Production details of Graftomer D 10t1 of toluene was added to an autoclave of fjJ3ot.
Poly-2,6-ditathyl-1,4-phenylene ether polymer powder shown in Reference Example 1 200 g% ethylene/glycidyl methacrylate copolymer (manufactured by Mitsubishi Yuka Co., Ltd., VFR
= 8, containing 4.7% by weight of glycidyl methacrylate) 10
0g was added, dissolved with llo'C, tri-n-butylamine 5 (LL) was added, and stirred at 110°C for 5 hours. After the reaction was completed, acetone was added to precipitate, and P was collected separately. Regarding the obtained polymer. The content of poly-2,6-dimethyl-1,4-phenylene ether in the xylene-insoluble matter determined by the same method as in Reference Example 2 was 75% by weight.

Reference Example 6 Production of Graftomer E Poly 2,6-dimethyl-1,4-phenylene ether polymer (manufactured by Mitsubishi Yuka Co., Ltd., in chloroform, manufactured by MFR
= 8, containing 4.7% by weight of glycidyl methacrylate) 50
After tri-blending the weight parts with a super mixer,
The graft reaction was allowed to proceed by kneading at 280° C. using a Danshaku extruder manufactured by Ikegai Tekko Co., Ltd. When the obtained composition was analyzed in the same manner as in Reference Example 2, the content of the poly-2,6-dimethyl-1,4-phenylene ether component in the xylene-insoluble matter was 48% by weight.

Example 1 Poly-2,6-dimethyl-1,4-phenylene ether polymer (manufactured by Mitsubishi Yuka Co., Ltd., intrinsic viscosity at 30°C in chloroform: 0.47 (lχ4) 50 parts by weight; polystyrene (manufactured by Mitsubishi Monsando Co., Ltd.) , HP-77) 50 parts by weight 5 Polyphenylene ether graft ethylene acrylic acid copolymer (graftomer A) produced in Reference Example 2: 1
After tri-blending 0 parts by weight using a super mixer, the mixture was kneaded and pelletized using a twin-screw extruder manufactured by Ikegai Tekko Co., Ltd. The obtained composition was molded into test pieces using an in-line injection molding machine manufactured by Taki Seisakusho, and various physical properties were measured. Furthermore, the wall thickness is 2.0
mm, using a mold with a width of 8 mm, the injection pressure was s o o kg.
/c++f, a spiral flow test was carried out at a temperature of 280"C. The results are shown in Table 1.

Comparative Examples 1 to 3 Graftomer A used in Example 1 was blended, and a resin composition (Comparative Example 1) and ethylene/acrylic acid copolymer (manufactured by Mitsubishi Yuka Co., Ltd., acrylic acid content 3.7 wt%, number average molecular weight 15000) (Comparative Examples 2 and 3) were prepared in Example 1.
The results obtained by injection molding and manufacturing in the same manner as above are also shown in Table 1.

From the results in Table 1, it is clear that the resin composition of the present invention is an excellent molding material that has excellent moldability and greatly improved impact strength while maintaining mechanical strength and thermal properties. It's empty.

Examples 2 to 5 Poly 4,6-
A resin composition was produced by changing the amount of v-A (graph used in Example 1) for a composition consisting of 50 parts by weight of dimethyl-1,4-phenylene ether and 50 parts by weight of polystyrene, and this was injected. Regarding the molded product, Example 1
Physical property measurements similar to those were carried out. The results are shown in Table 2.

Table 2 Example 6 Example 1 except that 10 parts by weight of polyphenylene ether graphite (graftomer B) produced by the method of Reference Example 3 was used in place of graftomer A used in Example 1. A resin composition was produced in the same manner as in Example 1, and the physical properties of the resin composition were measured in the same manner as in Example 1. The results are shown in Table 3.

Comparative Examples 4 to 5 Resin compositions (Comparative Examples 4 and 5) using polypropylene (Noblen TA-2, manufactured by Mitsubishi Yuka Co., Ltd.) in place of graftomer B were prepared in the same manner and under the same conditions as in Example 6, respectively. The physical properties were measured in the same manner as in Example 1 for the product manufactured by and injection molded. The results are shown in Table 3. In addition, the said Comparative Example 1 is also shown for comparison.

Example 7 In place of the graftomer A used in Example 1, 10 parts by weight of polyphenylene ether graft polyethylene (graftomer 〇) produced by the method of Reference Example 4 was used.
A resin composition was produced in the same manner as in Example 1, and its physical properties were measured in the same manner. The results are shown in Table 4.

Comparative Examples 6 to 7 Resin compositions (Comparative Examples 6 and 7) using polyethylene (Yukalon LM-30, manufactured by Mitsubishi Yuka Co., Ltd.) in place of graftomer 〇 were prepared in the same manner and under the same conditions as in Example 1, respectively. It was manufactured by injection molding and its physical properties were measured in the same manner. The obtained results are shown in Table 4 together with Comparative Example 1.

Examples 8 to 9 Examples 8 to 9 except that the polyphenylene ether grafted ethylene meta, glycidyl acrylate copolymer (graftomer D) log produced by the method of Reference Example 5 was used in place of the graftomer A used in Example 1. A resin composition was produced in the same manner as in Example 1, and its physical properties were measured in the same manner. The results are shown in Table 5. (Example 8) Excellent material properties similar to those of Example 1 were obtained.

A resin composition was produced by the same method as in Example 1, using 10 parts of polyphenylene ether grafted ethylene glycidyl methacrylate copolymer (graftomer E) produced by the method of Reference Example 6 in place of Glyphtomer D. The physical properties were measured in the same manner. The results are shown in Table 5. (Example 9) Example 1O Ethylene-glycidyl methacrylate-vinyl acetate copolymer (manufactured by Mitsubishi Yuka Co., Ltd., MI
PR-8, glycidyl methacrylate content 8.9% by weight
, vinyl acetate content: 4.5% by weight) were triblended using a super mixer, and then mixed into pellets using a rotary extruder manufactured by Ikegai Tekko Co., Ltd. to obtain a resin composition. When the composition of the xylene insoluble matter was analyzed by the method of Reference Example 2, it was found that the content of bolideenylene ether Ia was 21% by weight, and the ethylene/glycidyl methacrylate-vinyl acetate copolymer was 79% by weight, which was approximately 1% by weight of the added polyphenylene ether polymer. 5
Table 6 shows the physical properties of a test piece injection molded with a composition in which % by weight was grafted onto the ethylene/glycidyl methacrylate-vinyl acetate copolymer.

Applicant: Mitsubishi Yuka Co., Ltd. Agent: Patent attorney Katsura Atsuta Procedural amendment (1).

December 30, 1932 1. Indication of the case 1982 Patent Application No. 104513 2. Name of the invention Polyphenylene ether resin composition 3. Person making the amendment Relationship to the case Applicant Representative Director Masaki Yoshida 6. Amendment (1) On page 7, line 15 of the specification, delete J and add the following sentence.

"A polyolefin chain grafted with polyphenylene ether; generally a polyolefin random copolymer chain or a block copolymer chain grafted with polyphenylene ether, for example." (2) Ibid. 9 ``A polyolefin in which a polyphenylene ether is grafted to a random copolymer chain or a block copolymer chain'' in lines 5 to 8 of the page is used. -Corrected to 4.

(3) "This" in the 9th line of page 9 is corrected to "these."

(4) "175" on page 19, line 15 is corrected to "62".

Procedural amendment (voluntary) February 2, 1980 Haruki Shimada, Commissioner of the Patent Office1, Indication of the case 1982 Patent Application No. 10451'32, Title of the invention Polyphenylene ether resin composition 3, Make amendments Patent applicant 8, content of amendment 1 General formula on page 5, line 7 of the specification, and 10 from the bottom
"R11," R2 in the 9th, 5th and 4th rows
”, “R3” and “R4j, respectively [R'-1,
Corrected to "R2", "R3" and "R4".

2. In the general formula on the last line of page 6, "R4" is replaced with "R5", and "R
Correct 5-1 to "R6".

3. Correct "R4" in the first line of page 7 to "R5J."

4. Correct "R5" in the second line of the same page to "R6B."

5, page 8, in the general formula and in the 8th line from the bottom, rR6, J rR, J rR8J rR, J rR,
oJ and “R1, J to “R7, J-r R8” “R
9” “RIOJ [Corrected to R11J and [RI2 J.

6, "R8" and r R3 in Kio's structural formula on page 17
Correct J to rR'j and l''RIo'', respectively.

7. On page 18, line 17 and the last line, "Reference example 2" is corrected to "1 reference example 3."

that's all 38

Claims (1)

[Claims] (1) 80 to 20 parts by weight of polyphenylene ether,
20 to 80 parts by weight of styrenic polymer, and 0.1 to the total amount of polyphenylene ether and styrenic polymer.
A polyphenylene ether resin composition having improved processability and impact resistance, characterized in that it consists of ~50% by weight of polyphenylene ether-grafted polyolefin.