JPH0476051A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. suitable as a molding material excellent in mechanical properties, moldability, dimensional accuracy, solvent resistance, etc., by compounding a terminal-modified polyphenylene ether with a modified olefin resin. CONSTITUTION:10-90wt.% terminal-moldified polyphenylene ether of formula 1 (wherein each Q<1> is halogen, primary or secondary alkyl, phenyl, aminoalkyl, or an oxyhydrocarbon or halooxyhydrocarbon group; each Q<2> is H, halogen, primary or secondary alkyl, phenyl, haloalkyl, or an oxyhydrocarbon or halooxyhydrocarbon group; (n) is 10 or higher; X is oxygen or nitrogen; R<1> is 1-12C alkylene; R<2> and R<3> are each a 1-6C hydrocarbon group; (s) is 1 when X is oxygen and (s) is 2 when X is nitrogen; and (t) is an integer of 1-3) is compounded with 90-10wt.% modified olefin resin contg. a substd. silyl group of the general formula: SiRnY3-n (wherein R is an aliph. hydrocarbon group; Y is a hydrolyzable org. or hydroxyl group; and (n) is 0, 1, or 2).

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides a method for obtaining a resin composition of polyphenylene ether and an olefin resin by using terminal-modified polyphenylene ether produced by reacting polyphenylene ether with an alkoxysilane compound. General formula -3iRnY3-n
By blending an olefin resin containing the substituted silyl group represented by the formula, a high-performance product that combines the heat resistance, mechanical strength, and dimensional accuracy that are characteristic of polyphenylene ether, as well as the moldability and organic solvent resistance of an olefin resin. The present invention relates to a thermoplastic resin composition. The present resin composition is useful as a material for applications in the automobile, 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, especially 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 components do not have good solvent resistance, and the mixed composition also does not have sufficient solvent resistance.

Olefin resins have excellent moldability, resistance to organic solvents, low specific gravity, and low cost, so they are widely used in the production of molded products, but their heat resistance is not so high, making them difficult to use for engineering plastics. has become an obstacle. Therefore, if a composition that combines the good properties of polyphenylene ether and olefin resin and compensates for the undesirable properties can be obtained, it will be possible to provide an excellent rat fat material that can be used in a wide range of fields, and its industrial significance will be great. I can say that. Therefore, in order to provide a molding material that compensates for the drawbacks of both resins without impairing their advantages, for example, Japanese Patent Publication No. 42706 discloses a composition in which both resins are simply melt-mixed. However, in such a simple blend system, polyphenylene ether and olefin resin are incompatible and have no affinity, so the adhesion at the interface of this two-phase structure is not good, and the two-phase structure It is difficult to form a uniform and finely dispersed form, and when subjected to shear stress during molding processes such as injection molding, delamination occurs.
This tends to cause defects in the two-phase interface of the obtained molded product, resulting in a decrease in mechanical strength and impact resistance.

One possible way to solve the above problems in a polymer blend that is incompatible with each other is to add functionalities that are thought to react with each other to improve the mutual affinity of the two components. This is a method of obtaining a block or graft copolymer via covalent bonds by modifying the polymer with a group and performing a melt reaction at high temperature. From this point of view, in order to increase the reactivity of polyphenylene ether,
Many functionalized polyphenylene ethers have been proposed. For example, examples of such functionalization include methods using carboxyl group- or carboxylic anhydride-functionalized polyphenylene ethers (
Special Publication No. 1988-500456, JP-A-63-10656
No. 6354427, No. 63-128056, etc.), a method using epoxy group-functionalized polyphenylene ether (Japanese Unexamined Patent Application Publication No. 62-257957, Japanese Patent Publication No. 1983-1983)
503388, etc.), a method using amide group- or imide group-functionalized polyphenylene ether (Japanese Patent Publication No. 63-5
No. 00803, No. 63-50339], JP-A-61-
16963, etc.), a method using alkoxysilyl group-functionalized polyphenylene ether (Japanese Patent Publication No. 63503)
No. 392) etc. are disclosed, and these functionalized polyphenylene ethers are used as precursors, and resins having a structure having functional groups, such as boaamide, saturated polyester, and the like are disclosed.
Alternatively, many resin compositions with functionalized polyolefins have been proposed. However, none of these discloses a resin composition of an alkoxysilyl group-functionalized polyphenylene ether and a functionalized polyolefin.

(Problems to be Solved by the Invention) The present invention has particularly excellent heat resistance, dimensional accuracy, moldability,
An object of the present invention is to provide a thermoplastic resin composition containing polyphenylene ether and an olefin resin, which has solvent resistance and a dispersed structure.

(Means for Solving the Problems) As a result of intensive studies to solve the above problems, the present inventors have discovered that polyphenylene ethers containing functionalized polyphenylene ethers and substituted silyl groups that are extremely easily modified by a specific method. The inventors have discovered that a thermoplastic resin composition blended with a modified olefin resin can achieve the above object, and have arrived at the present invention.

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

(A) -Salt (wherein, Ql each represents a halogen atom, a primary or secondary alkyl group, a phenyl group, an aminoalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group, and each Q2 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 (which is an integer of
B) - Modified olefin resin containing a substituted silyl group represented by the formula % (wherein R is an aliphatic hydrocarbon group, Y is a hydrolyzable organic group or hydroxyl group, and n is Oll or 2)
90 to 10% by weight of functionalized polyphenylene ether (hereinafter referred to as functionalized polyphenylene ether) (A) having the above structure of the present invention and functionalized olefin resin (hereinafter referred to as functionalized olefin resin) (B).
) is extremely useful as a molding material that has excellent mechanical properties, moldability, dimensional accuracy, and solvent resistance, combining the characteristics of polyphenylene ether and olefin resin.

Hereinafter, the structure of the resin composition of the present invention will be explained.

Part A: Functionalized polyphenylene ether The functionalized polyphenylene ether used in the present invention is produced by the following method.The details are described below.

The polyphenylene ether represented by the general formula (II) (in the formula, Q', Q2 and n are the same as above) is added to the polyphenylene ether (I
Compound (III) having an alkoxysilyl group and a glycidyl group represented by formula (II) in the same molecule (wherein X, R', R2, R3, s and t are the same as above) is reacted to form the general formula (I ) A functionalized polyphenylene ether (A) is obtained.

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, D-butyl, n-amyl, isoamyl, 2-methylbutyl, n-hexyl, 2.3-
Dimethylbutyl, 2-13- or 4-methylbenzyl or heptyl. Examples of secondary alkyl groups are isopropyl, 5ec-butyl or 1-ethylpropyl. In many cases, each 01 is an alkyl group or a phenyl group,
In particular, it is an alkyl group having 1 to 4 carbon atoms, and each 02 is a hydrogen atom.

Suitable polyphenylene ether homopolymers include:
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 F units and 2.3.6 trimethyl-1.4-phenylene ether units. Many suitable homopolymers and random copolymers include
Described in patents and 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 02 to 08 tU/g.

Polyphenylene ethers are usually produced by oxidative coupling of the monomers described above. A number of catalyst systems are known for the oxidative coupling polymerization of polyphenylene ethers. 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 1
Amine, N-glycidyl-N, N-bis[3-(+-rimethoxysilyl)propyl 1 amine, 3-glycidyloxypropyl(methyl)dimethoxysilane, 3-glycidyloxypropyltrimethylhexysilane, 3- 2 siloxypropyl(methyl)jethoxysilane and the like. Particularly preferred are 3-glycidyloxypropyltrimethyl-l-oxysilane or 3-gnosicyloxypropyl(methyl)jethoxysilane.

The functionalized polyphenylene ether (A) represented by the -M formula (F) has an alkoxysilyl group and a glycidyl group represented by the general formula (Ill) in the same molecule as the polyphenylene ether represented by the -F19 formula (11). It can be easily produced by reacting a compound in an organic solvent in the presence of a basic catalyst.

It is desirable that the organic medium used here be capable of dissolving polyphenylene ether. Specifically, aromatic solvents such as benozene, toluene, and xylene, halogenated aromatic solvents such as chlorobenzene and dichlorobenzene, and halogenated hydrocarbon solvents such as chloroporm, trichlorethylene, and carbon tetrachloride. , N-methyl-2-pyrrolidone,
Examples include aprotic polar solvents such as 1.3 dimethyl-2-imidazolidinone. Examples of the basic catalyst include alcoholades such as sodium methoxide and sodium ethoxide; tertiary amines such as benzyldimethylamine 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 -11Q 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 the polyphenylene ether, and the pentabasic catalyst is used in an amount of 1 to 3 parts by weight per 100 parts by weight of the polyphenylene ether used.

-Numerical preparation procedure for functionalized polyphenylene ether (A) is to heat and dissolve polyphenylene ether (II) in an organic solvent, then add a basic catalyst dissolved in a small amount of ehnol or methanol, °Cf
7)? The functionalizing agent (Ill) is added at M degree and further heated until the reaction is complete.

Formation 11L)--Functionalized olefin resin Olefin resin modified with a silyl group having a hydrolyzable substituent of component (B) used in the present invention (
B) can be produced, for example, by the following method.

That is, ethylenically unsaturated silane is added to an ethylene resin such as polyethylene or a copolymer mainly composed of ethylene, or a propylene resin such as polypropylene or a copolymer mainly composed of propylene in the presence of a radical generator. Graft copolymerization method (for example, Japanese Patent Publication No. 47
-1711 or JP-A-59-36115, etc.), or a method by high-pressure radical copolymerization of ethylene and ethylenically unsaturated silane, or optionally other radically polymerizable monomers (for example, JP-A-1983-1711) 237
77, etc.) is typically manufactured.

However, in the present invention, the method for producing the modified olefin resin of component (B) is not limited to the above-mentioned method. Various methods can be applied, such as methods for obtaining Furthermore, the silicon compound for modification is not limited to ethylenically unsaturated silane.

Examples of the silicon compound for modification include a silicon compound having a reactive group that can be graft-polymerized to an olefin resin, a silicon compound having a group that can react with a functional group introduced into an olefin resin, or a silicon compound that can be copolymerized with an olefin monomer. There are silicon compounds having a functional group, and -11Q includes compounds as shown in the following formula.

R'5iRnY3-n where R' is a carbon-carbon double bond-containing group such as vinyl, allyl, isopropenyl, butenyl, cyclohexenyl or γ-(meth)acryloyloxypropyl. R is a hydrocarbon group such as an alkyl group such as methyl, ethyl, propyl or decyl. Y represents a hydrolyzable organic group or a hydroxyl group, and n is Oll or 2.

Examples of Y include methoxy, ethoxy, formyloxy, acetoxy, propionyloxy, and an alkyl or arylamino group.

Particularly preferred silicon compounds for modification are compounds represented by the formula % (in the formula, A represents an alkyl group having 1 to 8 carbon atoms), specifically, vinyltrimethoxysilane. or vinyltriethoxysilane.

Examples of olefin resins modified with silicon compounds having hydrolyzable organic groups as described above include homopolymers of α-olefins such as ethylene, propylene, butene, and hexene, and copolymers of these α-olefins. It includes a combination or a copolymer of these α-olefins with other unsaturated monomers that can be copolymerized.

Specifically, (very) low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer or its ion. Crosslinked products, ethylene-(meth)acrylic acid ester copolymers, mixtures of these polymers, or graft copolymers of the above polymers with maleic anhydride, (meth)acrylic acid, (methacrylic esters, etc.) It includes.

The amount of modifier in component (B) is usually 5% by weight or less,
Preferably it is 3 to 0.1% by weight. If the amount of the modifier is more than this, the crosslinking reaction due to the silanol condensation reaction between the modified resins may progress during the resin mixing process, resulting in a decrease in moldability and mechanical strength of the resulting composition. .

A Ratio of 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 viewpoint 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 90-1
0% by weight Component (B) 10 to 90% by weight of functionalized olefin resin If the functionalized polyphenylene needle is less than 10% by weight,
The rigidity is not sufficient, and if it exceeds 90% by weight, the solvent resistance is undesirable. Furthermore, the functionalized polyphenylene ether used in the present invention may be used alone, or may be a mixture of unfunctionalized polyphenylene ether or polyphenylene ether and a styrenic resin typified by soluble polystyrene. Similarly, the functionalized olefin resin may be used alone or in a mixture with an unfunctionalized olefin resin.

Kaasahi Oisai De Other additional components can be added to the present invention.

For example, well-known antioxidants, weather resistance improvers, nucleating agents, flame retardants, slip agents, etc. for olefin resins, well-known antioxidants, weather resistance improvers, plasticizers, etc. for polyphenylene ethers,
Styrenic resins, flow improvers, etc. can be used as additional ingredients. Furthermore, the addition of organic and inorganic fillers and reinforcing agents, particularly glass fibers, mica, tartar, wollastonite, potassium titanate, calcium carbonate, silica, etc., is effective in improving rigidity, heat resistance, dimensional accuracy, etc. For practical use, each f
! ! Known coloring agents and dispersants thereof can also be used.

Furthermore, the addition of impact strength improvers, especially styrene-buxene copolymer rubber and its hydride, nigerene-propylene-(diene) copolymer rubber, and their α,β-unsaturated carboxylic acid anhydrides. Addition of modified products and modified products with unsaturated glycidyl esters or unsaturated glycidyl ethers, copolymers of unsaturated epoxy compounds and ethylene, unsaturated epoxy compounds, copolymers of ethylene and ethylenically unsaturated compounds, etc. is effective in 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 varies depending on the target physical property value, but for example, in the case of improving the balance between rigidity and impact strength of the composition, 5 parts by weight of the resin component of the composition.
~30 parts by weight.

Method for mixing the composition The method for mixing the thermoplastic resin composition of the present invention includes a method of kneading and mixing the above-mentioned components using various mixers, such as a screw extruder, a twin screw extruder, a Banbury mixer, etc. , any method can be used. Further, the order of mixing may be any possible order, but when mixing by melt kneading, 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 listed in Table 1, and 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 heated to 25°C.
~ into a rill to precipitate the resulting functionalized polyphenylene ether. After separating the furnace, use acetonitrile 2E12 again.
This was washed with water 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 1 to 3 Functionalized polyphenylene ether (a), (b), functionalized olefin resin [silane-modified polypropylene manufactured by Mitsubishi Yuka Co., Ltd. (trade name: Linkron XPM800HM, 230°C
12,16 kg load MFR 10 g/10 min)], unfunctionalized polyphenylene ether (manufactured by Nippon Polyether Co., Ltd.,
Chloroborm Intrinsic viscosity at 30°C 0.3 affl/g
), and U unfunctionalized olefin resin (propylene resin MA3.230″C12 manufactured by Mitsubishi Yuka Co., Ltd., MFRLog/10 minutes of 16 kg load) was used in a plastomill manufactured by Toyo Seiki Co., Ltd. with an internal volume of 60 cc. Table 2 With the composition shown in 2
The mixture was melt-kneaded for 6 minutes at 80° C. and 60 rpm. The physical properties of the obtained resin composition were evaluated as follows,
The results are shown in Table 2. As is clear from these results, when functionalized polyphenylene ether and functionalized olefin resin are blended, homogeneous dispersion of very fine, almost spherical polyphenylene ether is observed, as well as high impact strength and solvent resistance. A composition was obtained.

The measurement and analysis methods are 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) Izotsu impact strength The obtained resin composition was press-molded at 280°C to create a sheet with a thickness of 2 mm, and three test pieces with a thickness of 2mm were stacked in accordance with JIS K7110. The unnotched Izot impact strength at °C was measured.

(3) Organic solvent resistance Bergen's genus ellipse method [SPE Journal 667 (196
2)]. Specifically, a test piece with a thickness of 2 mm was fixed in a quarter-ellipse jig with a major axis of 24 cm and a minor axis of 8 cm, and was immersed in commercially available gasoline for 5 minutes to determine the minimum strain at which a crack would occur. was determined as the critical strain.

At this time, if no cracks occur, 0 (extremely good)
, those with a critical strain value of 15% or more are ○ (good), and those with a critical strain value of 15% or more are rated 1.0.
It was judged as ~1.5%△ (W pass, less than 10% × (defective).

(Effects of the Invention) As described above, the thermoplastic resin composition of the present invention containing functionalized polyphenylene gothyl and functionalized olefin resin has excellent impact strength and solvent resistance, as shown in Table 2. ,
It has a dispersed form.

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 to 90% by weight (B) Represented by the general formula -SiR_nY_3_-_n (wherein, R is an aliphatic hydrocarbon group, Y is a hydrolyzable organic group or hydroxyl group, and n represents 0, 1 or 2) Modified olefin resin 90 containing substituted silyl group
~10% by weight