JPH0477553A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition having a combination of heat resistance, mechanical strength, dimensional accuracy, electrical properties and solvent resistance, comprising a saturated polyester and a terminal group- modified polyphenylene ether produced by reaction of an alkoxysilane compound with a polyphenylene ether. CONSTITUTION:The objective composition comprising (A) 10 - 90wt.% of a terminal group-modified polyphenylene ether of formula III produced by reaction, in the presence of a basic catalyst in an organic solvent, of (1) a polyphenylene ether of formula I (Q<1> is halogen, primary or secondary alkyl, etc.; Q<2> is H, halogen, etc.; (n) is >=10) with (2) a compound having, in an identical molecule, both alkoxysilyl and glycidyl groups of formula II (X is O or N; R<1> is 1-12C alkylene; R<2> and R<3> are each 1-6C hydrocarbon group; S is 1 or 2 when X is O or N, respectively; (t) is 1 - 3) and (B) 90 - 10wt.% of a saturated polyester (pref. polyester with liquid crystal nature).

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention provides a method for obtaining a resin composition of polyphenylene ether and saturated polyester using terminal-modified polyphenylene ether produced by reacting polyphenylene ether with an alkoxysilane compound. By blending saturated polyester, we have created a high-performance thermoplastic resin composition that combines the heat resistance, mechanical strength, and dimensional accuracy that are characteristic of polyphenylene ether, as well as the mechanical properties, electrical properties, and antidiathermia properties of saturated polyester. relating to things. This resin composition is
It is useful as a material for application in the automotive electrical and electronic fields, which are becoming increasingly diverse and sophisticated.

(Prior art) Polyphenylene ether having an unsubstituted or substituent group on the phenylene ring, particularly poly(2,6-dimethyl-1,4-phenylene ether), has excellent heat resistance and mechanical strength, and is useful as a so-called engineering plastic. However, it is well known that it has an undesirable property of being difficult to mold by injection molding or the like because of its high melt viscosity. Furthermore, the impact strength and solvent resistance of the same resin are insufficient in many fields of use as engineering plastics. The idea of supplementing the insufficient properties by mixing other resin materials is well known as one of the attempts when desired properties cannot be fully satisfied with a single resin material. Materials in which the moldability of polyphenylene ether is improved by blending polystyrene, which has good compatibility with polyphenylene ether and has good moldability, are widely used. But in this case,
Both of the same components do not have good solvent resistance, and the mixed composition also does not have sufficient solvent resistance.

Saturated polyester is a typical engineering plastic with excellent mechanical properties, electrical properties, and solvent resistance, and is widely used in applications such as automobile parts and electrical and electronic parts. However, this resin has the drawbacks of high molding shrinkage and linear expansion coefficient, and poor rolling stability under high loads, so its uses are limited. For this reason, a method of filling reinforcing agents such as glass fibers has been proposed, but this has the problem that the molded product's deterioration deteriorates, which limits its use depending on the required fields. Therefore, it combines the good properties of polyphenylene ether and saturated polyester,
If a composition that compensates for undesirable properties can be obtained, it will be possible to provide an excellent resin material that can be used in a wide range of fields, and it can be said to have great industrial significance. Therefore, in order to provide a molding material that compensates for the disadvantages without compromising the advantages of both,
For example, compositions in which the same resin is melt-mixed with sheep pure are disclosed in Japanese Patent Publication No. 51-21664, Japanese Patent Application Publication No. 49-50050,
It is disclosed in Publications No. 9-75662 and No. 59-159847. However, in such a simple blend system, bophenylene ether and saturated polyester are essentially incompatible, so the adhesion at the interface of this two-phase structure is not good, and this two-phase structure is uniform and fine. When subjected to shear stress during molding processes such as injection molding, delamination is likely to occur, resulting in deterioration of the appearance of the resulting molded product and the formation of defects at the two-phase interface. However, it is not possible to obtain a composition that has excellent mechanical properties such as dimensional accuracy, heat resistance, and rigidity, and physical properties such as solvent resistance.

- One possible way to solve the above problems in numerically incompatible polymer blends is to react the polyphenylene ether with the saturated polyester in order to improve the mutual affinity of the two components. This is a method of obtaining a block or graft copolymer through chemical bonding by modifying the polymer with a functional group, melt-kneading it at high temperature, and reacting it. In the case of a composition of polyphenylene ether and saturated polyester, it is necessary to add to bophenylene ether a functional group that can react with the hydroxyl group or carboxyl group present at the end of the saturated polyester, or the ester structural unit of the main chain.

From this point of view, many functionalized polyphenylene ethers have been proposed for the purpose of increasing the reactivity of polyphenylene ethers. For example, examples of the functionalization include a method using carboxyl group- or carboxylic anhydride-functionalized polyphenylene ether (JP-A-62-257958, JP-A-62-257958;
3-54427, Japanese Patent Publication No. 63-500803, etc.), method using epoxy group-functionalized polyphenylene ether (Japanese Patent Application Laid-Open No. 62-257958, Japanese Patent Publication No. 1983-500803, etc.)
03388 publications, etc.), a method using alkoxysilyl group-functionalized polyphenylene ether (Japanese Patent Publication No. 1983-50),
No. 3392, etc.), and resin compositions with various Shiwa polyesters have been proposed. However, even if these methods are used, it is often insufficient to improve the compatibility of both polyphenylene ether and saturated polyester, and the mechanical properties of the resulting compositions are still insufficient. , further improvements are desired.

(Problems to be Solved by the Invention) The present invention provides a thermoplastic resin composition blended with polyphenylene ether and saturated polyester, which has particularly excellent heat-resistant rigidity, dimensional bulk, moldability, solvent resistance, and dispersion structure. The purpose is to provide

(Means for Solving the Problems) As a result of intensive studies to solve the above problems, the present inventors have developed a blend of functionalized polyphenylene ether and saturated polyester that are extremely easily modified using a specific method. It has been discovered that a thermoplastic resin composition can achieve the above object, and the present invention has been achieved.

That is, the present invention is a thermoplastic resin composition characterized by comprising the following components (A) and (B).

(A) - Formula (wherein Ql each represents a halogen atom, a secondary or secondary alkyl group, a phenyl group, an aminoalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group, and Q2 each represents a hydrogen atom) , represents a halogen atom, a primary or secondary alkyl group, a phenyl group, a haloalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group, n represents a number of 10 or more, and X represents an oxygen atom or a nitrogen atom. R1 represents an alkylene group having 1 to 12 carbon atoms, R2 and R3 each represent a hydrocarbon group having 1 to 6 carbon atoms, S is 1 when X is an oxygen atom, and 1 when X is a nitrogen atom. 2, and t is 1 to 3
10 to 90% by weight of end group-modified polyphenylene ether represented by
(B) Saturated polyester 90-10% by weight The composition of the functionalized polyphenylene ether (hereinafter referred to as functionalized polyphenylene ether) having the above structure of the present invention (A) and the saturated polyester (B) has the characteristics of polyphenylene ether. It is extremely useful as a molding material that has excellent heat resistance, dimensional accuracy, moldability, solvent resistance, and a dispersion structure, all of which have the characteristics of saturated polyester.

The structure of the thermoplastic resin composition of the present invention will be explained below.

LAJO-Functionalized Polyphenylene Ether The functionalized polyphenylene ether used in the present invention is produced by the following method. The details are described below.

Polyphenylene ether represented by general formula (II) A compound (Ill) having an alkoxysilyl group and a glycidyl group represented by formula (III) in the same molecule (wherein, X, R', R2, R3, S and t are (same as above) is reacted to obtain the functionalized polyphenylene ether (A) represented by the general formula (I).

Polyphenylene ether is a homopolymer or copolymer having the structure of formula (II).

Suitable examples of primary alkyl groups for Ql and Q2 are methyl, ethyl, n-propyl, n-butyl, n-amyl, isoamyl, 2-methylbutyl, n-hexyl, 2.3-
Dimethylbutyl, 2-13- or 4-methylpentyl or heptyl. Examples of secondary alkyl groups are isopropyl, 5ee-butyl or 1-ethylpropyl. In many cases, each Q' is an alkyl group or a phenyl group,
In particular, it is an alkyl group having 1 to 4 carbon atoms, and each (in the formula, Q'
, Q'' and n are the same as above), and Q2 is a hydrogen atom.

As a homopolymer of polyphenylene ether with good J,
For example, it is composed of 2,6-dimethyl-1,4-phenylene ether units. Suitable copolymers include:
It is a random copolymer consisting of a combination of the above units and 2,3,6-drimethyl-1,4-phenylene ether units. Many suitable homopolymers and random copolymers are described in the patent literature. Also suitable are polyphenylene ethers containing molecular moieties that improve properties such as, for example, molecular weight, melt viscosity and/or impact strength.

For example, polyphenylene ether is obtained by graft polymerizing a vinyl monomer such as a vinyl aromatic compound such as acrylonitrile or styrene, or a polymer such as polystyrene or an elastomer thereof onto polyphenylene ether.

The molecular weight of polyphenylene ether is usually such that the intrinsic viscosity at 30° C. in chloroform is about 0.2 to 0.8 a/g.

Polyphenylene ethers are usually produced by oxidative coupling of the monomers described above. Regarding the oxidative coupling polymerization of polyphenylene ether, a large number of catalyst systems are known. There are no particular restrictions on the selection of the catalyst, and any known catalyst can be used. For example,
These include at least one heavy metal compound such as copper, manganese, cobalt, etc., usually in combination with various other substances.

General formula (II) used for functionalization of polyphenylene ethers
Specific examples of compounds having a glycidyl group and an alkoxysilyl group in the same molecule of I) include N-glycidyl-
N, N-bis[3-(methyldimethoxysilyl)propyl]amine, N-glycidyl-N, N-bis[3-(trimethoxysilyl)propyl]amine, 3-glycidyloxypropyl(methyl)dimethoxysilane, 3 -glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyl(methyl)jethoxysilane, and the like. Particularly preferred is 3-glycidyloxypropyltrimethoxysilane or 3-glycidyloxypropyl(methyl)jethoxysilane.

The functionalized polyphenylene ether (A) represented by the general formula (I) is a compound having a polyphenylene ether represented by the -M formula (II) and an alkoxysilyl group and a glycidyl group represented by the general formula (Ill) in the same molecule. It can be easily produced by reacting in an organic solvent in the presence of a basic catalyst.

The organic solvent used here is desirably capable of dissolving polyphenylene ether. Specifically, aromatic solvents such as benzene, toluene, and xylene: chlorobenzene,
Halogenated aromatic solvents such as dichlorobenzene; halogenated hydrocarbon solvents such as chloroform, trichloroethylene, carbon tetrachloride; N-methyl-2-pyrrolidone; 1.
Examples include aprotic polar solvents such as 3-dimethyl-2-imidazolidinone. Examples of the basic catalyst include alcoholades such as sodium methoxide and sodium ethoxide, tertiary amines such as pencil dimethylamine and tributylamine, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. .

In this reaction, 2 to 50 moles, preferably 5 to 20 moles of the functionalizing agent represented by the fQQ formula (III) are used per mole of the terminal phenolic hydroxyl group of polyphenylene ether. The organic solvent is used in an amount of 500 to 1000 parts by weight per 100 parts by weight of polyphenylene ether. The basic catalyst is used in an amount of 1 to 3 parts by weight per 100 parts by weight of the polyphenylene ether used.

The -IlΩ production procedure for functionalized polyphenylene ether (A) is to heat and dissolve polyphenylene ether (II) in a well-containing solvent, then add a basic catalyst dissolved in a small amount of ethanol or methanol, 20
The functionalizing agent (nB) was added at a temperature of 0° C. and further heated until the reaction was completed.

Saturated polyester Various polyesters can be used as the saturated polyester of component (B) used in the present invention.

For example, one example is a thermoplastic polyester produced by condensing dicarboxylic acid or its lower alkyl ester, acid halide, or acid anhydride derivative with glycol according to a conventional method.

Specific examples of aromatic or aliphatic dicarboxylic acids suitable for producing this polyester include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, superric acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, p,
p'-dicarboxydiphenyl sulfone, p-carboxyphenoxyacetic acid, p-carboxyphenoxypropionic acid, p-carboxyphenoxybutyric acid, p-carboxyphenoxyvaleric acid, 2.6-naphthalene dicarboxylic acid or 2.7-naphthalene dicarboxylic acid, etc. Alternatively, a mixture of these carboxylic acids may be used.

Also, examples of aliphatic glycols suitable for producing polyester include linear alkylene glycols having 2 to 12 carbon atoms, such as ethylene glycol, 1,3-propylene glycol, 1,4-butene glycol, 1,6-hexene glycol, 112- Examples include dodecamethylene glycol. Examples of aromatic glycol compounds include p-xylylene glycol, pyrocatechol, resorcinol, hydroquinone, and alkyl-substituted derivatives of these compounds. Other suitable glycols include 1,4-cyclohexane dimetatool.

Other preferred polyesters include polyesters produced by ring-opening polymerization of lactones. For example, polyvivalolactone, poly(ε-caprolactone), and the like.

Still other preferable polyesters include polymers that form liquid crystals in a molten state (Therm).

tropic Liquid Crystal Pol
ymer; There is polyester as TLCPI.

Typical polyesters that fall into these categories include Eastman Kodak Company's X7G Datco's Xydar, Sumitomo Chemical Company's Econol, and Celanese Company's Vectra.

Among the polyesters mentioned above as component (B),
Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polynaphthalene terephthalate (PEN), poly1.4 cyclohexane dimethylene terephthalate (PCT), liquid crystalline polyester, etc. are suitable saturated polyesters for the thermoplastic resin composition of the present invention. It is polyester.

Formulation A and B The selection of the blending ratio of components (A) and (B) of the thermoplastic resin composition of the present invention is determined by the required performance of the intended use of the final molded product.

That is, although properties such as moldability, mechanical strength, solvent resistance, dimensional accuracy, and high-temperature rigidity can often be adjusted by the characteristics of each component and their blending ratio, for example, rigidity and impact strength, etc. The contradictory properties of expression mechanisms are often difficult to reconcile. For practical purposes, usually
This is done from the point of achieving an appropriate balance of various properties such as formability, mechanical strength, and high-temperature rigidity. Therefore, although there is essentially no limit to the blending ratio of each component in the composition of the present invention, it can be said that the following ranges are practically useful.

Component (A): Functionalized polyphenylene ether 90-10
Weight% Component (B) Saturated polyester 10 to 90% by weight Component (A) used in the present invention may be used alone or may be a mixture of functionalized polyphenylene ether and unfunctionalized polyphenylene ether. .

Other additional ingredients can be added to the resin composition according to the present invention. For example, well-known antioxidants, weather resistance improvers, plasticizers, fluidity improvers, mold release agents, nucleating agents, etc. for saturated polyester; well-known antioxidants, weather resistance improvers, plasticizers, etc. for polyphenylene ether. additives, styrenic resins, flow modifiers, etc. can be used as additional ingredients. Also, organic/inorganic fillers, reinforcing agents, especially glass fiber, mica, talc,
Wollastonite, potassium titanate, calcium carbonate,
Addition of silica etc. is effective in improving rigidity, heat resistance, dimensional accuracy, etc. For practical purposes, various known colorants and dispersants thereof can be used.

Furthermore, the addition of an impact strength improver, in particular the addition of a copolymer consisting of an unsaturated epoxy compound and ethylene or an unsaturated epoxy compound, a copolymer consisting of ethylene and an ethylenically unsaturated compound, styrene-butadiene copolymer rubber and Its hydrides, ethylene polymers and ethylene-propylene-(diene) copolymer rubbers, as well as their α, β-
Addition of an unsaturated carboxylic acid anhydride modified product and an unsaturated glycidyl ester or unsaturated glycidyl ether modified product is effective for improving the impact strength of the composition. The above impact strength improvers may be used alone, or in combination of two or more. The blending amount of the impact strength improver differs depending on the target physical property value, for example, the stiffness of the composition.
In order to improve the balance between raw strength and impact strength, the amount is 5 to 30 parts by weight per 100 parts by weight of the resin component of one composition.

As a method for mixing the thermoplastic resin composition of the present invention, the above-mentioned components are mixed in various mixers, such as a screw extruder, twin screw extruder, Banbury mixer, etc. Method, various ingredients? Any method can be used, such as removing the solvent after mixing the 8 liquid or suspension, or adding a common non-toxic medium to precipitate, separate and recover. Also, the order of mixing is
Any possible order may be used, but when mixing by melt cross-fertilization, a preferred method is to sequentially mix the components starting from the one with the highest viscosity.

(Examples) Hereinafter, the present invention will be explained in detail with reference to Examples, but the scope of the present invention is not particularly limited thereby.

Preparation example of functionalized polyphenylene ether: Polyphenylene ether and toluene were charged into a reactor in the amounts shown in Table 1, and the mixture was heated and stirred to dissolve the polyphenylene ether. After heating to the reaction temperature listed in the same table, sodium ethoxide was dissolved in ethanol and added, followed by a predetermined amount of the functionalizing agent listed in the table, and the mixture was heated and stirred to react. After the reaction was completed, the reaction mixture was poured into 2512 acetonitrile to precipitate the functionalized polyphenylene ether formed. After being separated, it was washed again with acetonitrile 25I2 and dried under reduced pressure at 80°C to obtain a functionalized polyphenylene ether. These obtained resins were designated as functionalized polyphenylene ethers (a) and (b), and the results are shown in Table 1.

Example 1.2 and Comparative Examples Functionalized polyphenylene ether (a) (b), saturated polyester (polybutylene terephthalate manufactured by Mitsubishi Kasei Co., Ltd., trade name: Tubadol 5010) and unfunctionalized polyphenylene ether (manufactured by Nippon Polyether Co., Ltd., chloroform). Intrinsic viscosity at 30°C 0.3dI/g
) with the composition shown in Table 2 in a blast mill manufactured by Toyo Seiki Co., Ltd. with an internal volume of 60 cc, at 260°C and at a rotation speed of 6 Orp.
The mixture was melt-kneaded for 6 minutes under the conditions of m. The obtained resin composition was analyzed and evaluated.

The results are shown in Table 2. As is clear from the present results, when functionalized polyphenylene ether and saturated polyester were blended, very fine, almost spherical polyphenylene ether dispersion was observed, as well as graft copolymerized polyphenylene ether.

The analysis and evaluation method is as follows.

(1) Dispersion Form In order to examine the two-phase dispersion state of the obtained resin composition, a cross section was observed using a scanning electron microscope model S-2400 manufactured by Hitachi, Ltd.

(2) Analysis of Resin Composition A portion of the obtained resin composition was taken out and dissolved in a 3:2 (volume ratio) mixed solution of 0-chlorophenol and tetrachlorethylene. This solution was poured into chloroform to remove insoluble matter, taken out and dried. The amount of polyphenylene ether in the insoluble matter was determined as the ratio of the amount of polyphenylene ether grafted to the resin composition, and as the modification rate expressed as a percentage of the polybutylene terephthalate used. In addition, the chloroform solution obtained earlier was poured into a large amount of methanol, and the precipitated resin was dried and analyzed by infrared spectroscopy.

(Effects of the Invention) As shown in Table 2, the thermoplastic resin composition of the present invention containing functionalized polyphenylene ether and saturated polyester has an excellent dispersion structure in which the same resin is copolymerized. ing.

Continuation of the 100th part 1 Tohocho, City Mitsubishi Yuka Co., Ltd. Yokkaichiso Inside Gokenkosho

Claims (1)

[Scope of Claims] A thermoplastic resin composition comprising the following components (A) and (B). (A) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, Q^1 is each a halogen atom, a primary or secondary alkyl group, a phenyl group, an aminoalkyl group, a hydrocarbon oxy group or halohydrocarbonoxy group, Q^2
each represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, a phenyl group, a haloalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group, n represents a number of 10 or more, and X is an oxygen atom Or represents a nitrogen atom, R^1
represents an alkylene group having 1 to 12 carbon atoms, R^2 and R
^3 each represents a hydrocarbon group having 1 to 6 carbon atoms. s is 1 when X is an oxygen atom, 2 when X is a nitrogen atom,
t is an integer of 1 to 3) Terminal group-modified polyphenylene ether 1
0-90% by weight (B) Saturated polyester 90-10% by weight