JPH0488018A - Stabilized polyphenylene ether resin, its composition and production thereof - Google Patents

Abstract

PURPOSE:To readily obtain the subject resin, having high resistance to thermal oxidative deterioration and excellent in moldability by heating a specific phenylene ether resin and a specified compound in a state of no radical former added. CONSTITUTION:The objective resin, containing terminal groups expressed by formula I [R1 to R5 are H, (substituted) alkvl, etc.; R6 and R7 and R8 and R9 together form the shape of a spiro rind; X is ester] and formula II in a number of respective average >=0.05 based on 100 phenylene ether units constructing the resin and terminal groups expressed by formula III in a number of <=0.05 based on 100 aforementioned units and having 1000-100000 number-average molecular weight is obtained as follows. (A) A polyphenylene ether resin, containing terminal groups expressed by formulas II and IV [R10 and R11 are H or (substituted) alkyl] in a number of average >=0.05 based on 100 above-mentioned units and the terminal groups expressed by formula III in a number of average <=0.05 based on 100 above-mentioned units and having 1000-100000 number-average molecular weight and (B) a compound having C=C double bonds expressed by formula V are heated in the absence of a radical former added to the glass transition temperature or above.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel polyphenylene ether resin, a composition thereof, and a method for producing the same.

More specifically, in the present invention, the polyphenylene ether chains constituting the polyphenylene ether resin have a total of 6-
The present invention relates to a novel polyphenylene ether resin that has a specific amount of cyclized end groups such as chroman end groups and esterified end groups, and which suppresses thermal oxidative deterioration during processing and use, and a method for producing the same.

The present invention also relates to a composition containing the polyphenylene ether resin and polystyrene resin.

(Prior Art and Problems) Polyphenylene ether has excellent mechanical properties, electrical properties, heat resistance, etc., and is widely used as a thermoplastic molding material. However, since these advantages are combined with the drawback of being susceptible to thermal oxidative deterioration, there is a problem in that its use is restricted for applications that are susceptible to thermal oxidative deterioration. In order to avoid this problem, many proposals have been made to use a combination of various stabilizers such as amines and organic phosphorus compounds. Apart from this, a method for modifying polyphenylene ether itself is also disclosed. For example, special public relations
Japanese Patent Publications No. 17679, Japanese Patent Publication No. 49-48197, Japanese Patent Publication No. 12556-1987, etc. disclose improvements in thermal oxidative deterioration resistance by blocking the phenolic end groups of polyphenylene ether by methods such as esterification and etherification. This is what I did. However, although polyphenylene ether resins modified by these methods have a certain degree of stabilization effect in films made by cast molding, when evaluated with melt-molded test pieces and films, they do not show sufficient stabilization. There is a problem that the effect is not recognized.

For example, poly[oxy(
In the case of 2,6-dimethyl-1,4-phenylene), the heat of melt molding generates a partial structure represented by the f1 formula, which, like the unblocked phenolic end group, is susceptible to thermal oxidative degradation. It is presumed that this may be the cause.

As a method to improve this, a method has recently been proposed in which a hydroxyl group-blocking agent such as a salicylic acid ester is co-present during melting (US Pat. No. 4,760,118, JP-A No. 63-295,632).

In this method, the hydroxyl group of the general formula (f) is blocked, as shown in the general formula (g); Because the activated methylene group, which is highly oxidizable, remains as it is,
Thermal oxidation resistance is still insufficient. In addition, this method produces various by-products that plasticize the polyphenylene ether resin, and the melt-molded product becomes plasticized due to the by-products and unreacted capping agent remaining therein.

In order to remove these by-products and unreacted substances, a new problem arises in that the resin must be dissolved and reprecipitated.

(Means for solving the problem) Under these circumstances, the inventors of the present invention have conducted intensive research and found that when the terminal structure of polyphenylene ether resin is changed to a so-called 6-chroman skeleton and cyclized, it is surprising to find that In particular, polyphenylene ether resin has extremely high stability during melt molding, and has the general formula (h) represented by the above formula (f), which causes thermal oxidative deterioration (wherein R'-R' are each independently It was discovered that a partial structure represented by hydrogen, an alkyl group, a substituted alkyl group, a halogen group, an aryl group, or a substituted aryl group is hardly formed in the polyphenylene ether chain.

In the present invention, the term "6-chroman skeleton or group" means unsubstituted or substituted 6-chroman.

Furthermore, by esterifying the phenolic end groups that have not been cyclized with 6-chroman, the polyphenylene ether resin, whose amount is controlled below a certain level, shows a remarkable stabilizing effect against thermal oxidative deterioration after melt molding. heading,
The invention has been completed.

Accordingly, one object of the present invention is to provide stabilized polyphenylene ether resins that have high resistance to thermal oxidative degradation.

Another object of the present invention is to provide an easily implemented method for producing polyphenylene ether resin having the above characteristics.

Furthermore, another object of the present invention is to provide a composition containing the above-mentioned polyphenylene ether resin and polystyrene resin, which has excellent moldability as well as resistance to thermal oxidative deterioration.

That is, the present invention has; or more, contains an average of 0.50 or less terminal groups represented by the general formula (C) per 100 phenylene ether nitrates constituting the resin, and has a number average molecular weight of 1,000.
It is a polyphenylene ether resin characterized by having a molecular weight in the range of 0 to 100,000.

(In the formula, R1-R5 are each independently hydrogen, an alkyl group, a substituted alkyl group, a halogen group, an aryl group, or a substituted aryl group, and R6-R7 are each independently hydrogen, an alkyl group, a substituted alkyl group. , alkenyl group, substituted alkenyl group, halogen group, aryl group, substituted aryl group, hydroxyl group, alkoxy group, N-lactam group, carboxylic acid group,
They are a carboxylic anhydride group, a carboxylic ester group, a carboxylic acid amide group, a nitrile group, an acyloxy group, or an acyl group.

Note that R6 and R7, and R6 and R1 may be independently bonded to each other to form a ring of a spirocyclic structure.

Moreover, X represents an ester group of formula 1i1,000. ) Also, ■ the above polyphenylene ether resins 1 to 99
This is a resin composition containing 99 to 1 part by weight of a polystyrene resin.

■ The terminal group represented by the general formula (+)) and the general formula (
The terminal groups represented by dl are each on average 0.
05 or more, an average of 0.50 or less terminal groups represented by the general formula (C) per 100 phenylene ether units constituting the resin, and a number average molecular weight of 1.
A polyphenylene ether resin having a molecular weight of 0.000 to 100,000 and a compound having a carbon-carbon double bond represented by the general formula (e) are used without the addition of a radical generator to induce the glass transition of the polyphenylene ether. This is a method for producing the polyphenylene ether resin described above, in which the polyphenylene ether resin is heated to a temperature higher than the above temperature.

(In the formula, R4゜ and RI+ each independently represent hydrogen, an alkyl group, or a substituted alkyl group, but are not hydrogen at the same time.) (In the formula, R6-R7 are defined by the formula (al) (The same as that for general formula (C). Formula (d)
A polyphenylene ether resin containing an average of 0.05 or more terminal groups per 100 phenylene ether units constituting the resin and having a number average molecular weight in the range of 1000 to 100,000, and a polyphenylene ether resin having the general formula ( A compound having a carbon-carbon double bond represented by e), an esterifying agent, and, if necessary, a catalyst are heated to a temperature equal to or higher than the glass transition temperature of polyphenylene ether without the addition of a radical generator. , a method for producing the polyphenylene ether resin described above.

In the stabilized polyphenylene ether resin of the present invention, the terminal group represented by the general formula (a) and the terminal group represented by the general formula (b) are added to 100 of the phenylene ether units constituting the resin. Each contains an average of 0.05 or more, and the phenolic hydroxyl s represented by the general formula (C) is 0.0 per 100 phenylene ether units.
Must be 5 or less. If the number of terminal groups represented by the general formula (a) and the terminal group represented by the general formula (b) is less than this, sufficient molding stability cannot be obtained, and the final group represented by the general formula (C) A: If the number of nol terminal groups is greater than this, sufficient thermal oxidative deterioration resistance cannot be obtained.

Number average molecule N used as engineering resin
(approximately 10,000 to 50,000), the total number of cyclized end groups and esterified end groups is preferably 0.15 or more per 100 phenylene ether units. More preferably, the average number is 0.2 or more. Further, the number of phenolic terminal groups is preferably 0.2 or less per 100 phenylene ether units. More preferably, the average number is 0.10 or less. There is no particular lower limit, and the lower it is, the more preferable it is in terms of resistance to thermal oxidation deterioration. Note that the ratio of the cyclized end groups to the esterified end groups is not particularly limited, but a larger number of cyclized end groups is preferable in terms of hydrolysis resistance and the like.

The polyphenylene ether resin of the present invention is defined as containing a phenylene ether unit generally represented by as a repeating unit, excluding its terminal group, and is not particularly limited. A typical example is the following formula (i); (wherein R5-R6 are each independently selected from hydrogen, an alkyl group, a substituted alkyl group, a halogen group, an aryl group, or a substituted aryl group). It is composed of at least one type of phenylene ether unit shown below, and may further include monomers such as uni-nod of formulas (j), ((a), and (1) described below).

In the above definition of R1-R5, the alkyl group has 1 carbon number
-20, preferably alkyl having 1 to 10 carbon atoms.

Examples of the substituent of the substituted alkyl include halogens such as fluorine, chlorine, and bromine; hydroxyl groups; amino groups; and lower alkoxy groups. Aryl has 6 to 2 carbon atoms
It is an aryl of 0. As substituents of substituent Ryl,
Lower alkyl groups; halogens such as fluorine, chlorine, and bromine;
Examples include hydroxyl group; amino group; and lower alkoxy group.

When producing the polyphenylene ether polymer as the basic skeleton of the polyphenylene ether resin of the present invention by the industrially advantageous oxidative coupling polymerization of phenols,
R, is methyl, ethyl, propyl, isopropyl, n-
A lower alkyl group such as butyl, phenyl, naphthyl, etc. is preferred, and R2-R1 is preferably hydrogen or a lower alkyl group. The most preferred combinations are when R1 is a methyl group or phenyl group and R2-R1 are hydrogen, and when R3 and R2 are methyl groups and R3-R5 are hydrogen. In particular, R1 is a methyl group and R2-
It is preferable that R5 is hydrogen and the phenylene ether units account for 90 to 100% of the total units.

Monomers corresponding to the phenylene ether unit having the most preferable RI""' Rs satisfying these conditions include (i) 26-dimethylphenol, (ii)
2-methyl-6-phenylphenol, (iii) 2
．． 3. 6-) Limethylphenol and the like.

a homopolymer of monomer (1) or monomer (ii),
Alternatively, a copolymer of monomer (i) and monomer (11) and/or monomer (iii) is preferably used as the polyphenylene ether polymer as the basic resin skeleton of the present invention.

In addition, the polyphenylene ether resin of the present invention may contain various other phenylene ether units that have been proposed to be present in the polyphenylene ether resin as long as they do not go against the purpose of improving thermal stability. It may be included as a substructure. As an example of what is proposed to coexist in small amounts, there is
2-(dialkylaminomethyl)6-methylphenylene ether unit (j)ya,2(N-alkyl-N-phenylaminomethyl)6-methyl described in No. 2698 and JP-A No. 63-301222 Examples include phenylene ether unit (k), etc. fJ<.

It is possible to include such multivalent ether units.

(In the formula, R and R' are each independently di(c+"C2o) alkyl group, (01~Czo)hydroxyalkyl L
(C2-C2□) alkoxylalkyl, (03-C2
□) An acyloxyalkyl group or a (04-C) polyalkylene ether group. ) (wherein R is (C+ ~Cz
o) Alkyl group, (c+~C2o) hydroxyargyl group, (02~c2□) alkoxyalkyl group, (0
3-c2□) acyloxyalkyl group or (C4-C2o
) is a polyalkylene ether group. ) Furthermore, in order to have one or more terminal groups such as 6-chroman terminal group (a) per molecule of the polyphenylene ether chain, for example, as the molecular weight of the polyphenylene ether resin of the present invention represented by the - format (]), is 1.000 to 100000 in number average molecular weight. Its preferred range is about 6,000 to 60,000. In particular, preferred applications for engineering resins are approximately LO,
It is from OOO to 30,000. The number average molecular weight of the present invention is a polystyrene equivalent number average molecular weight determined by gel permeation chromatography using a standard polystyrene calibration curve.

As mentioned above, in the present invention, the average number of cyclized terminal groups such as 6-chroman terminal groups represented by general formula (a) is 0.05 per 100 phenylene ether units in the resin. It is necessary to include the above.

This cyclized terminal group (a) will be explained in detail.

In (a) 2, R8-R9 are each hydrogen, an alkyl group, a substituted alkyl group, a halogen group, an aryl group, or a substituted aryl group.

R6-R7 each independently represent hydrogen, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, a halogen group, an aryl group, a substituted aryl group, an alkoxy group, N-
Lactam group, carboxylic acid group, carboxylic anhydride group, carboxylic acid ester group, carboxylic acid amide group, nitrile group,
It is an acyl group or an acyloxy group. In addition, R1, R7
, R8 and R7 may each independently have free ends, or R6 and R7, and R8 and R9 may each independently bond to form a ring such as a spirocyclic structure.

In the definition of R6-R7, the alkyl group has 1 to 2 carbon atoms.
0, preferably 1 to 10 alkyl, more preferably lower alkyl. Examples of the substituent of the substituted alkyl include halogens such as fluorine, chlorine, and bromine; hydroxyl groups, amino groups; and lower alkoxy groups. The alkenyl is preferably a lower alkenyl such as ethylenyl or 3-propenyl. A representative example of substituted alkenyl is 1-hydroxy-3-propenyl.

Aryl is an aryl of 6 to 20 carbons. Examples of the substituent of the substituted aryl include a lower alkyl group; a lower alkoxy group; a halogen such as fluorine, chlorine, and bromine; a hydroxyl group; an amino group; and an aminoalkyl group such as an amizmedel group. Aryl group means an aromatic ring group in a broad sense, and in addition to aryl in a narrow sense, it includes pyridyl group,
Also included are heteroaromatic ring groups such as triazyl groups. Representative examples of N-lactams include N-2-pyrrolidonyl, N-ε-caprolactamoyl, and the like. Representative examples of carboxylic acid amides include carbamoyl, phenylcarbamoyl, seryl, and the like. Preferred examples of carboxylic acid anhydrides are:
Acetoxycarbonyl, henzoyloxycarbonyl. Representative examples of carboxylic acid esters include methoxycarbonyl, ethoxycarbonyl, and allyloxycarbonyl. Typical examples of acyl groups include acetyl and hendyloxy, and preferred examples of acyloxy include acetoxy and hendyloxy.

From the viewpoint of stability, it is preferable that 2 to 3, especially 3 of R6-R7 are hydrogen. At this time, other groups include an aryl group, a substituted aryl group, a carboxylic acid group, a carboxylic acid anhydride group, a carboxylic acid ester group, a carboxylic acid amine F group,
It is preferable to select from nitrile group and N-lactam group.

In particular, it is preferable that at least one of R8 and R7 is an aryl group or a substituted aryl group from the viewpoint of stability against thermal oxidative deterioration and the production method described below.

Representative examples of aryl or substituted aryl groups in the definition of R6-R7 include phenyl, tolyl, chlorophenyl, naphthyl, 4-pyridyl, 3゜5-diamino-(s
)-4 lyadyl group, etc.

Including chill, sulfate ester, sulfite ester, phosphate ester, phosphite, etc. Many methods are known for capping the phenol terminals of polyphenylene ether with these esters. (For example, Special Publication No. 41-4277
Japanese Patent Publication No. 49-48197 describes a blocking method using phosphoric acid esterification and carbonic acid esterification; The publication describes a blocking method using sulfuric acid esterification.

Any of the esterified end groups produced by these methods can be used in the present invention.

Specifically, one or more terminal groups represented by the following formulas (n1 to (S)) can be used in combination.

The esterified terminal group (b) will be explained in detail.

The esterified terminal group in the present invention is an ester in a broad sense, and in addition to carboxylic acid esters, the method for producing the polyphenylene ether resin of the present invention is not particularly limited, but it can be suitably produced by the following method. I can do it.

In the first method, the terminal group represented by the general formula (b) and the terminal group represented by the general formula (d) are each added on an average of 0 to 100 phenylene ether units constituting the resin.
．． 05 or more, and the terminal group represented by the general formula (C) is on average 0.05 or more per 100 phenylene ether units constituting the resin. A polyphenylene ether resin containing 50 (flit or less) and having a number average molecular weight in the range of i, ooo to 100,000 and a compound having a carbon-carbon double bond represented by the general formula (el) without the addition of a radical generator. This is a method of heating to a temperature equal to or higher than the glass transition temperature of polyphenylene ether.

The raw material polyphenylene ether resin in this case contains an average of 0.05 to 0.50 terminal groups represented by the -format (C) per 100 phenylene ether units constituting the resin, and has a general formula of The terminal group represented by (d) is 100% of the phenylene ether unit constituting the resin.
It is prepared by esterifying a polyphenylene ether resin containing an average of 0.05 or more per polyphenylene ether resin and having a number average molecular weight in the range of 1,000 to 10,000 by any known method.

The second method is to contain an average of 0.05 to 0.50 terminal groups represented by the general formula (C) per 100 phenylene ether units constituting the resin; d) contains an average of 0.05 or more terminal groups per 100 phenylene ether units constituting the resin, and has a number average molecular weight of 1.000 to 100. '000
Polyphenylene ether resin in the range of and the general formula (
e) A compound having a carbon-carbon double bond represented by
This is a method in which an esterifying agent and, if necessary, a catalyst are heated to a temperature equal to or higher than the glass transition temperature of polyphenylene ether without the addition of a radical generator.

In this case, as the esterifying agent and catalyst, any one known to esterify a phenolic hydroxyl group can be used, as described above. Among these, a combination of a carboxylic acid anhydride and a basic substance is preferred. Furthermore, surprisingly,
It has been found that with a combination of a compound having a specific carbon-carbon heavy bond and an esterifying agent, esterification proceeds in high yield even without the use of a catalyst, so a catalyst is not necessarily required.

Preferred specific examples of the unsaturated compound (e) include styrene, α-methylstyrene, chlorstyrene, methylstyrene, stilhene, cinnamic alcohol, benzalacetone, ethyl cinnamate, cinnamate nitrile, and 4-vinylpyridine. , 2-vinyl-35-diamino-(S)-triazine, and the like. Moreover, as the unsaturated compound (d), one that does not contain an aromatic ring can also be used. Specific examples of such unsaturated compounds (e) include acrylic acid; methyl, ethyl, propyl, butyl, isobutyl, t-butyl, 2-ethylhexyl, octyl, isodecyl, lauryl, lauryl-tridecyl, tridecyl acrylate; , cetyl-stearyl, stearyl, cyclohexyl, acrylic esters such as hensyl ester; acrylamide, acrylonitrile, methacrylic acid; methyl, ethyl, propyl, butyl, isobutyl, t-butyl, 2-ethylhexyl, octyl, isodecyl methacrylate, lauryl, lauryl-tridecyl, tridecyl, cetyl-stearyl, stearyl, cyclohexyl,
Methacrylic acid esters such as hensyl ester; methacrylamide, methacrylonitrile, itaconic acid; itaconic acid diesters such as dimethyl, diethyl diptyl, di2-ethylhexyl, dinoryl, and dioctyl esters of itaconic acid; monomethyl, monoethyl itaconic acid, Examples include monoesters of itaconic acid such as monobutyl, mono-2-ethylhexyl, mononolyl, and monooctyl ester; itaconic anhydride; N-vinyl compounds such as N-vinylpyrrolidone; and vinyl ethers such as butyl vinyl ether.

The polyphenylene ether resin of the present invention has high compatibility with polystyrene resins, and when blended with these resins, a resin composition with improved thermal oxidative deterioration resistance and good moldability can be obtained.

That is, according to the present invention, a resin composition containing 1 to 99 parts by weight of the stabilized polyphenylene ether resin of the present invention and 99 to 1 part by weight of a polystyrene resin is provided.

As the polystyrene resin, those commonly used together with polyphenylene ether resins and those known in the art can be used. For example, in addition to styrene homopolymers, those known in the art can be used. Copolymers with other ethylenically unsaturated monomers may be mentioned as long as they do not cause any damage.

Specific examples of comonomers include α-methylstyrene, acrylonitrile, methacrylonitrile, acrylic esters, methacrylic esters, maleic anhydride, N-alkylmaleimides, N-arylmaleimides, vinyloxaprine, etc. There is.

Furthermore, by blending and using a polystyrene polymer containing a rubber-like shell, the low impact resistance, which is another disadvantage of polyphenylene ether resins, can be improved. Specifically, high-impact polystyrene, ABS resin,
ABS resin, etc.

Also included are styrene-butadiene block copolymers, styrene-isoprene block copolymers, and the like. In this case as well, a composition can be obtained which has significantly improved stability against thermal oxidative deterioration compared to conventional similar compositions.

When a rubber component in which some or all of the unsaturated bonds are hydrogenated is used, a remarkable effect on the layer is observed. Furthermore, styrene-butadiene block copolymers, styrene-isoprene block copolymers, and hydrogenated products thereof modified with maleic anhydride or the like may also be used.

These rubbery block copolymers may also be in the form of crosslinked particles.

The stabilized polyphenylene ether resin of the present invention is
It may be blended with the polystyrene resin in any ratio (the former may be 1 to 99 parts by weight, preferably 99 to 99 parts by weight).
It is 50 parts by weight.

Further, the formation of a composition with a polystyrene resin may be performed during or after the production of the stabilized polyphenylene ether resin of the present invention. For example, after tri-blending a polyphenylene ether polymer having terminal groups (a) to (C) and/or (d), a polystyrene resin, and an unsaturated compound of formula (e), a roll mill, twin screw extruder, etc. A desired composition can be obtained by melt-kneading.

In addition, inorganic fillers such as glass fibers, various stabilizers, plasticizers, flame retardants, pigments, etc. may be appropriately added to the polyphenylene ether resin of the present invention or the composition containing the same according to known methods. can.

(Examples) Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

In addition, each measurement was performed under the following conditions.

■ The viscosity of the polymer is determined by adding 0.5% chloroform solution to 3
Measured using an Ubbelohde viscosity tube at 0°C, η
Expressed as sp/c.

(2) Δη/η is a value obtained by dividing the difference in ηSp/c before and after melt molding by ηSp/c before molding, and is an index of viscosity change during melt molding.

■ I) l-Nuclear magnetic resonance spectrum is G manufactured by JEOL ■
Measurements were made on X-270 and GX-400 using CDCl,l as a solvent, and tetramethylsilane was used as a standard.

■ The infrared absorption spectrum was obtained using FT/I manufactured by JASCO ■.
The film was measured in transmission using R-7000.

■ Gel permeation chromatography (hereinafter referred to as G
PC) was measured with HL-802RTS manufactured by Toyo Soda Kogyo ■ and calibrated with standard polystyrene.

■ Free phenolic OH groups in the polymer are EHU
D 5 HCHORI et al.'s method [Journal of Applied Polymer Science; Applied Polymer Symposium, 34. pp. 103-117, (197
8)].

■ To reduce the thermal weight of the polymer, prepare the molded body as a 5% by weight solution in toluene and precipitate it by adding the same amount of methanol.
Regarding the powder obtained by filtering, washing and drying, in the air 3
Measurement was carried out at 50°C for 160 minutes, and the amount of reduction was expressed as a weight % value.

■ The thermal oxidative deterioration resistance of polymers is determined by infrared spectroscopy after leaving a film produced by rolling a molded product or casting from a chloroform solution in an air circulation constant temperature bath at 150°C or 180°C for 7 hours. 1695 on photometer
cnr" absorption increment was measured and expressed as a relative value. This absorption corresponds to the aldehyde group or carboxyl group formed by oxidation of the methyl group of the main repeating unit represented by formula (1), It is an indicator of the degree of oxidative deterioration.

(i) Izot impact strength was measured on notched specimens according to ASTM D256.

Reference Example I The raw material polyphenylene ether is
According to the method described in No. 70, 2,6-xylenol was produced by oxidizing force/sampling polymerization in the presence of dibutylamine.

The viscosity of the obtained polyphenylene ether was 0°548, and as a result of analysis by IH-nuclear magnetic resonance spectroscopy, it was found that (
The terminal group of formula IJ) is 100 of the main repeating unit (1)
It was confirmed that there were 0.35 pieces per piece. Also,
The amount of free phenolic hydroxyl groups is determined by the main repeating unit (
It was confirmed that 0.20 out of 100 items of 1) were present.

Reference Example 2 100 parts by weight of the polyphenylene ether obtained in Reference Example 1 was made into a 5% by weight toluene solution, and 1 part by weight of acetic anhydride and 0.85 parts by weight of pyridine were added. Add this solution to 1
After maintaining the polymer at 40°C for 0 hours, the same amount of methanol as toluene was added to collect the polymer, which was then washed and dried. As a result of analyzing this polymer by infrared absorption spectrum, it was found that the terminal group structure of the formula (2) was 0.00% for every 100 main repeating units (1). It was confirmed from the absorption area value near 1766■1 that there were +8. Furthermore, it was confirmed that the amount of free phenolic hydroxyl groups was 0.03 per 100 of the main repeating units (1). Also, the viscosity is 0
．． 550, and the number average molecular weight was 25,000.

Example 1 10 of the polyphenylene ether resin obtained in Reference Example 2
After adding 10 parts by weight of styrene to 0 parts by weight and uniformly blending the mixture using a Henschel mixer, the mixture was melt-kneaded at 300°C in a 30 mmφ twin-screw extruder and pelletized through a water tank. As a result of analyzing the pellet thus obtained by IH-nuclear magnetic resonance spectroscopy, it was found that the terminal group structure of formula (b) was 0.31 per 100 of the main repeating units (1).
5. It is possible to generate From the area value of the O2ppm signal, it was also determined that the dislocation structure of formula (f) is the main repeating unit (
The fact that 0.03 pieces are generated per 100 pieces of 1) is 3.
．． This was confirmed from the area value of the signal at 86 ppm. Furthermore, the amount of free phenolic hydroxyl groups was 0.12 per 100 of the main repeating units (11), the viscosity was 0.552, and the molecular weight was 25,500.

Reference Example 3 100 parts by weight of the polyphenylene ether obtained in Reference Example 1 was made into a 5% by weight toluene solution, and 1 part by weight of benzoic acid chloride and 0.85 part by weight of triethylamine were added. This solution was maintained at 80°C for 10 hours, then allowed to cool to room temperature, and the same amount of methanol as toluene was added to collect the polymer, which was washed and dried. As a result of analyzing this polymer by IH-nuclear magnetic resonance spectrum and infrared absorption spectrum,
The terminal group structure of formula (0) is 1 of the main repeating unit (1)
It was confirmed from the signal around 8.22 ppm and the area value of absorption around 1740 cm-' that there were 0.35 out of 00.

Furthermore, it was confirmed that the amount of free phenolic hydroxyl groups was 0.02 per 100 of the main repeating units (1). Moreover, the viscosity was 0.547.

Example 2 A pellet and a test piece were obtained in the same manner as in Example 1 except that the polyphenylene ether resin obtained in Reference Example 3 was used.

As a result of analyzing the pellet by IH-nuclear magnetic resonance spectroscopy, it was found that the terminal group structure of (b) 2 is formed in 0.26 units per 100 of the main repeating units. O2
This was confirmed from the area value of the signal around ppm. Also,
It was confirmed that 0.03 dislocation structures of the formula (g) were formed for every 100 main repeating units (1). Furthermore, the amount of free phenolic hydroxyl groups was 0.07 per 100 of the main repeating units (1), the viscosity was 0.560, and the number average molecular weight was 26,500.

Example 3 10 parts by weight of styrene and 0.5 parts by weight of acetic anhydride were added to 100 parts by weight of the polyphenylene ether of Reference Example 1, mixed well with a Henschel mixer, and extruded and injection molded in the same manner as in Example 1. I did it.

As a result of Beret analysis, 0.26 end group structures of formula (b) are formed for every 100 main repeating units (1), and the rearrangement structure of formula (f) is formed in the main repeating unit (1). The amount of free phenolic hydroxyl groups was 0.09 per 100 main repeating units (1), and the viscosity was 0.558. , the number average molecular weight was 26,000.

Comparative Example 1 The polyphenylene ether obtained in Reference Example 1 was extruded alone under the same conditions as in Example 1 to obtain a pellet.

In this pellet, 0.48 (f) two dislocation structures were generated for every 100 main repeating units (1). Further, the amount of free phenolic hydroxyl groups was 0.72 per 100 main repeating units (t), the viscosity was 0.685, and the number average molecular weight was 36.500.

Test pieces were obtained by injection molding the berets of Examples 1 to 3 and Comparative Example 1. Further, this test piece was made into a chloroform solution and cast to obtain a film.

Analysis result evaluation result of test piece and 18 of cast film
The results of aging at 0°C for 17 hours are shown in Table 1.

As is clear from Table 1, the resin of Example 1 shows significantly less change in viscosity, molecular weight, and chemical structure during injection molding than the resin of Comparative Example, and has excellent processing stability. I understand. Furthermore, it is a stable resin that exhibits extremely little deterioration when exposed to high-temperature air.

Example 4 75 parts by weight of the stabilized polyphenylene ether resin pellet produced in Example 2 and 25 parts by weight of impact-resistant polystyrene (manufactured by Asahi Kasei Corporation, trade name: Styron 492) were mixed well, and the mixture was heated at 300°C in a twin-screw extruder. The mixture was melt-blended under the conditions of

The resulting pellet was pressed at 300'C for 3 minutes to form a rolled film. The obtained film was exposed to heat at 150°C for 7 hours, and the degree of oxidative deterioration was measured at 1695 cm-'
It was investigated by absorption of In addition, a test piece was prepared by injection molding the same pellet at 300°C, exposed to heat under the same conditions, and the retention of Izod impact value was measured. The results are listed in Table-2.

Comparative Example 2 A rolled film and a test piece were obtained in the same manner as in Example 4, except that the polyphenylene ether resin pellets produced in Comparative Example 1 were used. The obtained films and test pieces were subjected to heat exposure at 150'C for 7 hours, and the degree of progress of oxidative deterioration and retention of Izot impact values were investigated. The results are listed in Table-2.

Table 2 Reference Example 4 100 parts by weight of the polyphenylene ether obtained in Reference Example 1 was made into a 5% by weight toluene solution, and 2 parts by weight of dienyl chloride phosphate and 0.62 parts by weight of pyridine were added. After this solution was kept at 40°C for 10 hours, the same amount of methanol as toluene was added to recover the polymer, which was washed and dried.

As a result of analyzing this polymer with 'H and 31p magnetic resonance spectra, it was confirmed that 0.31 terminal groups of the (r1 formula) were formed for every 100 main repeating units (1). , the terminal group (Ll) was mostly unreacted.

The amount of free phenolic hydroxyl groups is determined by the main repeating unit (
11 is 0.05 per 100, and the viscosity is 0.5
It was 52.

Example 5 5 g of the polyphenylene ether resin obtained in Reference Example 4 was impregnated with 0.5 g of styrene, and heat compression molded at 320° C. for 3 minutes. As a result of analyzing the obtained test piece, (
Repeating unit (1) whose main group is the terminal group of formula r) and formula (b)
0.00 for each 100 pieces. 28 pieces and 0.22
It was confirmed that there were. The amount of free phenolic hydroxyl groups was 0.08 per 100 main repeating units (1), and the viscosity was 0.556.

Example 6 A hydrogenated product of 97 parts by weight of the stabilized polyphenylene nityl resin produced in Example 2 and a styrene-butadiene block copolymer (manufactured by Asahi Kasei Corporation, trade name: Toughtic H-
1051) 3 parts by weight were mixed well and extruded using a twin screw extruder.
The mixture was melt-blended and pelletized at °C. The obtained pellet was injection molded at 330°C to prepare a test piece, and the Izod impact value was measured, and it was 16 kg-c.
+++/cm.

(Effects of the Invention) The stabilized polyphenylene ether resin of the present invention does not cause problems such as plasticization compared to conventional polyphenylene ether, has significantly improved deterioration and viscosity increase during melt molding, and has high resistance to heat oxidation and deterioration. It is a molding material that has excellent properties such that molded products with improved properties can be easily molded.

Procedural amendment September 10th, 1990

Claims (4)

[Claims] (1) Terminal group represented by general formula (a) and general formula (b)
A phenylene ether unit containing an average of 0.05 or more terminal groups represented by formula (c) per 100 phenylene ether units constituting the resin, and containing a terminal group represented by the general formula (c) Contains an average of 0.50 or less per 100, and has a number average molecular weight of 1,000
100,000. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(b) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(c) (Formula In the formula, R_1 to R_5 each independently represent hydrogen, an alkyl group, a substituted alkyl group, a halogen group, an aryl group, or a substituted aryl group, and R_6 to R_9 each independently represent hydrogen, an alkyl group, a substituted alkyl group, or an alkenyl group. group, substituted alkenyl group, halogen group, aryl group, substituted aryl group, hydroxyl group, alkoxy group, N-lactam group, carboxylic acid group, carboxylic acid anhydride group, carboxylic acid ester group, carboxylic acid amide group, nitrile group, acyloxy group or acyl group. Note that R_6, R_7, R_8, and R_9 may each be independently bonded to form a ring of a spirocyclic structure. represent. ) (2) A resin composition containing 1 to 99 parts by weight of the polyphenylene ether resin according to claim (1) and 99 to 1 part by weight of a polystyrene resin. (3) Contains an average of 0.05 or more terminal groups represented by the general formula (b) and terminal groups represented by the general formula (d) per 100 phenylene ether units constituting the resin. and contains an average of 0.50 or less terminal groups represented by the general formula (c) per 100 phenylene ether units constituting the resin, and has a number average molecular weight of 1,000.
~ 100,000 and a compound having a carbon-carbon double bond represented by the general formula (e) without the addition of a radical generator, at a temperature higher than the glass transition temperature of the polyphenylene ether. The method for producing polyphenylene ether resin according to claim (1), which comprises heating to a temperature. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(d) (In the formula, R_1_0 and R_1_1 each independently represent hydrogen, an alkyl group, or a substituted alkyl group, but they cannot be hydrogen at the same time.) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(e) (In the formula, R_6 to R_9 are the same as those defined in formula (a).) (4) The average number of terminal groups represented by formula (c) is 0 per 100 phenylene ether units constituting the resin.
．． 05 or more and 0.50 or less, and contains an average of 0.05 or more terminal groups represented by the general formula (d) per 100 phenylene ether units constituting the resin, and has a number average molecular weight of 1. ,000 to 100,000, a compound having a carbon-carbon double bond represented by the general formula (e), an esterifying agent, a catalyst if necessary, and a radical generator. 2. The method for producing a polyphenylene ether resin according to claim 1, wherein the polyphenylene ether resin is heated to a temperature higher than the glass transition temperature of the polyphenylene ether in the absence of additives.