JPH06200015A - Production of alkoxysilylated polyphenylene ether - Google Patents

Abstract

PURPOSE:To obtain an alkoxysilyated polyphenylene ether simply at good efficiency by reacting a specified polyphenylene ether with a specified organosilicon compound in a specified ratio by melting in the absence of any solvent. CONSTITUTION:100 pts.wt. polyphenylene ether containing at least 0.01, per 100 phenylene ether units, phenylene ether unit having at least one substituent of formula I wherein R1 and R2 are each H, alkyl, substituted alkyl, halogen, aryl or substituted aryl; and R3 and R3' are each H, alkyl or substituted alkyl is reacted with 0.1-5 pts.wt. compound of formula II wherein Q is a group of formula III, IV, VI, VII or VIII; X1 and X2 are each H, halogen or the like; n is 0-10; W is a direct bond or 1-12C alkylene; Ra and Rb are each a 1-6C hydrocarbon group; and m is 1-3 by melting in the absence of any solvent. The obtained alkoxysilylated polyphenylene ether has good compatibility with a resin such as a polyamide.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an alkoxysilylated polyphenylene ether (hereinafter referred to as PPE).

[0002]

2. Description of the Related Art PPE is a thermoplastic resin having excellent heat resistance, mechanical properties, electrical properties, water resistance, acid resistance, alkali resistance, self-extinguishing property, etc., and is widely used as engineering plastics. . However PPE
Has a high melt viscosity in connection with a high glass transition temperature, and therefore has poor moldability and poor engineering impact resistance.

In order to improve such a drawback of PPE, blending with various resins such as polyolefin, polyester and polyamide has been attempted, but the composition obtained is poor in compatibility with these resins. The product is fragile and is inferior in mechanical strength and impact resistance and is not suitable for practical use.
Therefore, a compatibilizing agent is used, but most of the compatibilizing agent is a graft or block copolymer of both resins. When synthesizing these copolymers, it is possible to react the terminal phenolic hydroxyl group of PPE with a functional group in another polymer. However, the types of functional groups of other polymers capable of reacting with the terminal phenolic hydroxyl group of PPE are limited, and the range of utilization thereof is naturally limited.

Therefore, for the purpose of increasing the reactivity of PPE,
Many functionalized PPEs have been proposed. For example, special table Sho 63
JP-A-503392 discloses a method of graft-polymerizing vinyltrimethoxysilane in chlorobenzene in the presence of a radical initiator as a method of introducing an alkoxysilyl group into the molecular skeleton of PPE. In addition, Japanese Patent Laid-Open No. 4-3392
Japanese Patent Publication No. 3 discloses a method of reacting a halogenated alkoxysilane and PPE in a solvent.

However, all of the methods are reactions in a solvent, so that separation and recovery operations are required and the operations are complicated, and the number of steps is large, which is industrially unsuitable.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an extremely easy method for producing an alkoxysilylated PPE which is industrially useful.

[0007]

The present invention provides a phenylene ether unit of (A) polyphenylene ether,
The following formula (Formula 4):

[0008]

[Chemical 4] (In the above formula, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, an aryl group or a substituted aryl group, and R ₃ and R ₃
'Independently represent a hydrogen atom, an alkyl group, or a substituted alkyl group, but R ₃ and R ₃ ' cannot be hydrogen atoms at the same time). , 100 parts by weight of polyphenylene ether present in an amount of 0.01 or more per 100 phenylene ether units, and (B) the following formula (Formula 5):

[0009]

[Chemical 5] [In the above formula, Q is the following formula (Formula 6):

[0010]

[Chemical 6] (In the above formula, X ₁ and X ₂ each independently represent a hydrogen atom, a halogen atom or an alkyl group, and n is 0 to
Represents an integer of 10), W represents a direct bond or an alkylene group having 1 to 12 carbon atoms, R
_a and R _b each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and m represents an integer of 1 to 3], and 0.1 to 5 parts by weight of a compound represented by The present invention provides a method for producing an alkoxysilylated polyphenylene ether, which comprises melting and reacting.

PPE-based resins are also known as polyphenylene oxide-based resins, and are represented by the general formula (Chemical Formula 7):

[0012]

[Chemical 7] A large number of phenylene ether structural units having Here, each Q ₁ is independently a hydrogen atom, a halogen atom, a primary or secondary lower (that is, containing 7 or less carbon atoms) alkyl group, a phenyl group, a haloalkyl group, an aminoalkyl group, A hydrocarbon oxy group or a halohydrocarbonoxy group having a structure in which a halogen atom and an oxygen atom are separated by at least two carbon atoms, and each Q ₂ is independently a hydrogen atom, a halogen atom, a group It is a primary or secondary lower alkyl group, a phenyl group, a haloalkyl group, a hydrocarbon oxy group or a halohydrocarbonoxy group as defined for Q ₁ . Suitable primary lower alkyl groups include, for example, methyl, ethyl, propyl, butyl, isobutyl, amyl, isoamyl, 2-methylbutyl, hexyl, 2,3-dimethylbutyl, 2-, 3- or 4-methylpentyl. , Corresponding heptyl groups and the like. Examples of the secondary lower alkyl group include isopropyl, sec-butyl, 3-pentyl group and the like. The alkyl group is preferably a straight chain rather than a branched chain. Often, each Q ₁ is an alkyl or phenyl, especially a C _1-4 alkyl group, and each Q ₂ is a hydrogen atom. Suitable PPE are disclosed in numerous patent documents.

Both homopolymeric and copolymeric PPE can be used in the present invention. Suitable homopolymers are, for example, those containing 2,6-dimethyl-1,4-phenylene ether units. Suitable copolymers include 2,6-dimethyl-1,4-phenylene ether units such as 2,3,6
Including random copolymers containing in combination with -trimethyl-1,4-phenylene ether units. A number of suitable random copolymers as well as homopolymers are disclosed in numerous patents.

PPE containing molecular moieties that improve properties such as molecular weight, melt viscosity and / or impact strength may also be used in the present invention. Such polymers have been disclosed in a number of patent documents, in which vinyl monomers such as acrylonitrile and vinyl aromatic compounds (eg styrene) or polymers such as polystyrene and elastomers are grafted onto PPE by known methods. Can be manufactured. Such products typically include both grafted and non-grafted molecular moieties. Other suitable polymers are coupled PP
E, a higher molecular weight polymer containing the reaction product of a coupling agent with a hydroxyl group formed by reacting the coupling agent with the hydroxyl groups of two polyphenylene ether chains in a known manner. Examples of coupling agents are low molecular weight polycarbonates, quinones, heterocyclic compounds and formals.

The PPE generally has a number average molecular weight in the range of about 3,000 to 40,000 and a weight average molecular weight in the range of about 20,000 to 80,000, as determined by gel filtration chromatography. Its intrinsic viscosity is often measured in chloroform at 25 ° C., often in the range of about 0.15-0.6 dl / g,
It is preferably 0.25 to 0.55 dl / g.

PPE is typically prepared by oxidative coupling of at least one corresponding monohydroxyaromatic compound. Particularly useful and readily available monohydroxyaromatic compounds are 2,6-xylenol (wherein each Q ₁ is methyl and each Q ₂ is a hydrogen atom) and 2,
3,6-trimethylphenol (each Q ₁ and one Q ₂ is methyl and the other Q ₂ is a hydrogen atom), and the resulting polymers are each poly (2,6-dimethyl-
1,4-phenylene ether) and poly (2,3,6-trimethyl-1,4-phenylene ether).

Various catalyst systems are known for the production of PPE by oxidative coupling. There is no particular restriction on the choice of catalyst and any of the known catalysts may be used. In most cases, the catalyst contains at least one heavy metal compound such as a copper, manganese or cobalt compound, usually in combination with various other materials.

The first group of preferred catalyst systems consists of catalyst systems containing copper compounds. Such catalysts are described, for example, in U.S. Pat.
Nos. 306,874, 3,306,875, 3,914,266, and 4,028,341. These are usually combinations of cuprous or cupric ions, halide (eg halide, bromide, iodide, etc.) ions and at least one amine.

The second preferred catalyst system is a manganese compound-containing catalyst system. These are generally alkaline systems in which divalent manganese is combined with anions such as halides, alkoxides or phenoxides. In many cases manganese is used in dialkylamines, alkanolamines, alkylenediamines, o-hydroxyaromatic aldehydes, o-hydroxyazo compounds, w-hydroxyoximes (monomeric and polymeric), o-hydroxyaryloximes and β. -Is present as a complex with one or more complexing agents and / or chelating agents such as diketones. Further known cobalt-containing catalyst systems are also useful. Suitable manganese- and cobalt-containing catalyst systems for the production of PPE are described in numerous patents and other publications and are known to those skilled in the art.

The PPE resin used in the present invention is represented by the above formula (Formula 4) at the position of Q ₁ or Q ₂ in the phenylene ether structural unit of the above PPE resin (Formula (Formula 7)). The number of units having at least one substituent having a structure represented by 0.01 or more, and preferably 0.05 or more, per 100 phenylene ether structural units. When it is less than 0.01, the number of bonds with the polysiloxane is too small, and it is difficult to obtain a copolymer having desirable properties. Further, it is particularly preferable that the unit having a substituent of the structure represented by the formula (Formula 4) is at the terminal. At that time, the substituent of the structure represented by the formula (Formula 4) is preferably at a position adjacent to the hydroxyl group, that is, at Q ₁ .

In the above formula (Formula 4), R ₁ and R ₂
When is an alkyl group, it represents a lower alkyl group such as methyl, ethyl, propyl and butyl, and in the case of a substituted alkyl group, the substituent includes a halogen atom and the like. In the case of a halogen atom, F, Cl, Br
In the case of an aryl group, examples thereof include a phenyl group and a naphthyl group, and in the case of a substituted aryl group, examples of the substituent include a lower alkyl group, a halogen atom, and a nitro group. As for R ₃ and R ₃ ′, the alkyl group and the substituted alkyl group include the same alkyl groups and substituted alkyl groups as described above.

Of the above structures, the preferred one is R ₁
= In R ₂ = H, and R ₃ = R ₃ '= butyl group.

PPE having such a specific structural unit
The resin based can be obtained by incorporating a corresponding primary or secondary monoamine as one of the components of the oxidative coupling reaction mixture when using a copper- or manganese-containing catalyst. Such amines, especially dialkylamines, preferably dibutylamine and dimethylamine, are often chemically linked to the PPE, which is often an α-on one or more Q ₁ groups.
This is achieved by replacing one of the hydrogen atoms. The main site of this reaction is the Q ₁ group adjacent to the hydroxyl group on the terminal unit of the polymer chain. For details of the manufacturing method of such PPE, for example, Macromolecules (M
acromolecules), Vol. 23, pp. 1318-1329 (1990) and the like.

Next, the compound (B) used in the present invention is
It is a known compound having a structure represented by the above formula (Formula 5). In the above formula, X ₁ and X ₂ are F, Cl, Br or I in the case of a halogen atom, and are linear or branched such as methyl, ethyl, propyl, butyl in the case of an alkyl group. And lower alkyl groups. When W represents an alkylene group, it may be linear or branched. When R _a or R _b is a hydrocarbon group, specific examples thereof include alkyl groups such as methyl, ethyl, propyl and butyl. Such a compound can be obtained by reacting an amino compound having a corresponding alkoxysilyl group with a corresponding acid anhydride or dicarboxylic acid. Specific examples of the compound having an alkoxysilyl group include 3-aminopropyl (methyl) diethoxysilane, 3-aminopropyl (methyl) dimethoxysilane, and 3-aminopropyl (methyl) dimethoxysilane.
Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, etc. To be Further, as the acid anhydride or dicarboxylic acid to be reacted with this, maleic anhydride, nadic acid anhydride,
Itaconic anhydride, fumaric acid, maleic acid, itaconic acid,
Examples thereof include nadic acid. This reaction can be carried out, for example, in a solvent such as acetone or ether under reflux. Furthermore, the dehydration cyclization from an amic acid to an imide can be performed by a known method using acetic anhydride or the like.

In the method of the present invention, the above-mentioned PPE is used.
The compound (B) is used in an amount of 0.1 to 5 parts by weight, preferably 0.2 to 3.0 parts by weight, based on 100 parts by weight of the system resin. If the amount of the compound (B) is less than 0.1 parts by weight, highly reactive PPE cannot be obtained, and if it is more than 5 parts by weight, the heat resistance of the PPE is significantly reduced.

In the present invention, the above PPE resin and the compound (B) are melted and reacted in the absence of a solvent. Specifically, the mixture is heated and mixed at a temperature of 200 to 350 ° C. The mixing means is not particularly limited, but for example, a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder or the like can be used.

The alkoxysilylated PPE obtained by the method of the present invention can be compatibilized with various polymers by utilizing the reactivity of the alkoxysilyl group. Other resins,
For example, when blended with polyamide, polyphenylene sulfide, polyolefin, polyester, etc., PP
The alkoxysilyl group of E reacts with the functional group of the blended resin to enhance the compatibility between the two resins and exert the effects such as improving the impact strength of the composition. Further, such alkoxysilylated PPE is useful as a precursor for graft or block copolymers. Further, it is possible to increase the molecular weight of PPE by the coupling reaction of the alkoxysilyl group. In addition, the effect of improving the adhesiveness with various resins and inorganic fillers, fiber reinforcing agents, etc. can be expected.

[0028]

The mechanism of the reaction in the method of the present invention is described in, for example, P
The case where the amine-containing structural portion contained in PE is at the end will be described. When PPE and the compound (B) are heated,
First, the amine is eliminated from the amine-containing structural portion contained in PPE, and, for example, the following formula (Formula 8):

[0029]

[Chemical 8] (Wherein Q ₁ , Q ₂ , R ₁ and R ₂ have the same meanings as described above), a reactive intermediate as shown by the formula (6) attached to the compound (B) is formed. It is presumed that the carbon-carbon double bond in the selected structure is bonded by a Diels-Alder type reaction.

[0030]

Example 1 (1) Preparation of amine-functionalized PPE resin Dibutylamine and 2,6-xylenol were subjected to oxidative coupling polymerization according to a known method to give poly (2,6-dimethyl-1). , 4-phenylene) ether (weight average molecular weight 64,000, number average molecular weight 22,000) was obtained. H ¹ -N
Analysis of φ-CH ₂ —NR ₂ (where φ represents a phenyl group and R represents a butyl group) using MR showed that this PPE had 0.83% by weight of dibutylamine residues. It was (2) Preparation of Imide Compound 3-Aminopropyltriethoxysilane and maleic anhydride (molar ratio 1: 1) were reacted in ether at 0 ° C. to obtain an imide compound. (3) Production of alkoxysilylated PPE 80 parts by weight of amine-functionalized PPE obtained in (1) and homopolystyrene (manufactured by Dainippon Ink and Chemicals, Inc.,
1 part by weight of the compound prepared in (2) was added to 20 parts by weight of CR-3500 and melt-kneaded with a twin-screw extruder set at 300 ° C. to react PPE with an imide compound. In addition, since homopolystyrene efficiently performs melt-kneading,
It is added for the purpose of lowering the viscosity.

The modification amount of the obtained alkoxysilylated PPE was determined by quantifying the terminal phenolic hydroxyl groups before and after the reaction. The yield was 100% and the reaction rate was 95%. The obtained alkoxysilylated PPE was analyzed by FTIR, and as a result, the following formula (Formula 9):

[0032]

[Chemical 9] It was found to contain a structure of (OEt = ethoxy group). Application Examples 1 to 2 40 parts by weight of alkoxysilylated PPE (containing homopolystyrene) obtained in Example 1 and polyamide (P
A) (A1025, manufactured by Unitika Ltd.) or polyphenylene sulfide (PPS) (Toprene T-4,
60 parts by weight (manufactured by Topren Co., Ltd.) were melt-kneaded by a twin-screw extruder set at 300 ° C. The appearance of the obtained strand was observed, and the dispersion diameter of PPE was measured using a scanning electron microscope (SEM). The results are shown in Table 1. Application Comparative Examples 1-2 Unmodified PPE instead of alkoxysilylated PPE
(Intrinsic viscosity 0.48 dl / g (in chloroform, 25 ° C),
Strands were prepared in the same manner as in Application Examples 1 to 2 except that General Electric Co. was used, the appearance was evaluated, and the dispersion diameter of PPE was measured by SEM. The results are shown in Table 1.
Also described in.

[0033]

[Table 1]

It can be seen from Table 1 that the alkoxysilylated PPE produced in the examples has excellent compatibility with resins such as PA and PPS.

[0035]

According to the present invention, alkoxysilylated P
PE can be efficiently and easily manufactured. Since the method of the present invention is carried out without a solvent, steps such as solvent removal, drying, and granulation are unnecessary, and the steps are simplified. Further, the alkoxysilylated PPE obtained by the present invention includes PA, P
Excellent compatibility with other resins such as PS. Therefore, the method of the present invention is industrially very useful.

Claims (1)

[Claims] 1. In the phenylene ether unit of the polyphenylene ether (A), the following formula (Formula 1): (In the above formula, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, an aryl group or a substituted aryl group, and R ₃ and R ₃
'Independently represent a hydrogen atom, an alkyl group, or a substituted alkyl group, but R ₃ and R ₃ ' cannot be hydrogen atoms at the same time). , 100 parts by weight of polyphenylene ether present in an amount of 0.01 or more per 100 phenylene ether units, and (B) the following formula (Formula 2): [In the above formula, Q is the following formula (Formula 3): (In the above formula, X ₁ and X ₂ each independently represent a hydrogen atom, a halogen atom or an alkyl group, and n is 0 to
Represents an integer of 10), W represents a direct bond or an alkylene group having 1 to 12 carbon atoms, R
_a and R _b each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and m represents an integer of 1 to 3], and 0.1 to 5 parts by weight of a compound represented by A method for producing an alkoxysilylated polyphenylene ether, which comprises melting and reacting.