JPH03250027A - Production of hydroxyalkylated polyphenylene ether - Google Patents

Abstract

PURPOSE:To obtain very easily a hydroxyalkylated polyphenylene ether easily reactive with the functional group of another resin or the like by reacting a polyphenylene ether with a specified functionalizing agent. CONSTITUTION:A hydroxyalkylated polyphenylene ether of formula III (wherein Q1, Q2, (m) and R are as defined below) is produced by reacting a polyphenylene ether of formula I (wherein Q1 is halogen, prim. or sec. alkyl, phenyl, aminoalkyl, hydrocarbonoxy or halohydrocarbonoxy; Q2 is H, halogen, prim. or sec. alkyl, phenyl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy; and m>=10) with a compound of formula II (wherein R is H or 1-8C alkyl). According to the above process, the resin can be produced very easily and is one easily reactive with the functional group of another resin or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing hydroxyalkylated polyphenylene ethers by functionalizing terminal phenolic hydroxyl groups of polyphenylene ethers.

Specifically, the hydroxyalkylated polyphenylene ether produced by the production method of the present invention has a lower level of oxidation when blended with other resins, etc., than unfunctionalized polyphenylene ether.
It is thought to have the effect of reacting with the functional groups of blend resins, increasing the compatibility between resins, and increasing the strength of a single composition, and is also useful as a precursor for graft or block copolymers. .

[Conventional technology]

Polyphenylene ether is an extremely useful thermoplastic resin with excellent heat resistance, mechanical properties, electrical properties, water resistance, acid resistance, alkali resistance, and self-extinguishing properties, and has many applications as an engineering plastic material. is planned. However, this resin has a high melt viscosity associated with a high glass transition temperature, and therefore has disadvantages such as poor moldability and poor impact resistance as an engineering plastic.

Blending with polyolefins or engineering plastics has been carried out with the aim of improving these drawbacks, but they are essentially incompatible with these polymers, and the resulting compositions are brittle and have poor mechanical strength. Impact strength etc. are reduced and it cannot be put to practical use. Compatibilizers have been used to solve this problem, and most compatibilizers are graft or block copolymers of both polymers. When synthesizing these copolymers, it is conceivable to react the terminal phenolic hydroxyl group of polyphenylene ether with a functional group in another polymer.

However, the types of functional groups of other polymers that can react with the terminal phenolic hydroxyl group are limited, and the scope of their use is naturally limited. Therefore, many functionalized polyphenylene ethers have been proposed for the purpose of increasing the reactivity of polyphenylene ethers. Special edition Showa 62-500456
No., Special Publication No. 63-500803, Special Publication No. 63-503
No. 391 lists several examples of hydroxyalkyl group-functionalized polyphenylene ethers, but the production method requires multi-stage reactions and also requires the use of high-temperature melt reactions. Furthermore, even when modification can be performed under relatively mild reaction conditions, expensive acid chloride must be used. Furthermore, JP-A-63-128021 discloses a method of reacting polyphenylene ether with ethylene oxide or propylene oxide to hydroxyalkylate the terminal group of polyphenylene ether, but the reaction requires high pressure. There are several problems to be solved, such as the difficulty in controlling the number of ethylene oxide or propylene oxide added, and the inability to obtain a uniform product.

[Problems to be Solved by the Invention] An object of the present invention is to provide an extremely easy method for producing a hydroxyalkylated polyphenylene ether that can react with functional groups such as other resins.

[Means for Solving the Problem] The present inventors have discovered that modified polyphenylene ether can be produced extremely easily by functionalizing the terminal phenolic hydroxyl group of polyphenylene ether with a hydroxyalkyl group with an alkylene carbonate compound. The invention has been completed.

That is, the present invention provides the following formula: each represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, a phenyl group, a haloalkyl group, a hydrocarbonoxy group or an eight-headed hydrocarbonoxy group.

m is a number of 10 or more, and is characterized by reacting a polyphenylene ether shown in the table with a compound represented by the formula - (in the formula, R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). This is a method for producing a hydroxyalkylated polyphenylene ether represented by the general formula (wherein Ql, Q2, m, and R are the same as above).

The polyphenylene ether used in the present invention is.

- It is a homopolymer or copolymer having a structural unit of the formula. Q
Suitable examples of primary alkyl groups for l and Q2 include 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, 5ec-butyl or 1-ethylpropyl. In many cases, Ql
is an alkyl group or a phenyl group, especially an alkyl group having 1 to 4 carbon atoms, and Q2 is a hydrogen atom.

Suitable polyphenylene ether homopolymers include:
An example is one consisting of 2,6-dimethyl-1,4-phinidine ether units. Suitable copolymers include:
This is a random copolymer consisting of a combination of the above units and 2,3,6-drimethyl-1,4-phinidine ether units. A number of suitable homopolymers or random copolymers are described in the patent literature.6 Polyphenylene ethers containing molecular moieties that improve properties such as, for example, molecular weight, melt viscosity and/or impact strength, may also be used. Also suitable are, for example, polyphenylene ethers in which a polymer such as a vinyl chloride such as a vinyl aromatic compound such as acrylonitrile or styrene, or a polymer such as polystyrene or an elastomer thereof is grafted onto polyphenylene ether.

The molecular weight of polyphenylene ether is usually 0.2 to 0.8 d in intrinsic viscosity at 30°C in chloroform! /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.

The functionalizing agent of general formula (III) used in the present invention includes: 1.
It is a carbonate ester of 2-alkanediol. here,
R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and examples of preferred compounds include ethylene carbonate and propylene carbonate.

The hydroxyalkylated polyphenylene ether of general formula (1) produced by the method of the present invention has -1Kt formula (II)
Polyphenylene ether represented by general formula (III)
The functionalizing agent shown can be easily produced by reacting the functionalizing agent shown in the formula in an organic solvent that dissolves polyphenylene ether at a temperature of 100 to 200°C in the presence of a basic compound as a catalyst.

Examples of organic solvents used here include aromatic solvents such as toluene and xylene; chlorobenzene,
These include halogenated aromatic solvents such as dichlorobenzene.

Basic compounds for the catalyst include sodium methoxide,
Examples include alcoholades such as sodium ethoxide, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate.

The reaction amount ratio of the polyphenylene ether and the functionalizing agent used in this reaction is 1 to 40 mol of the functionalizing agent per 1 mol of the terminal phenolic hydroxyl group of the polyphenylene ether,
Preferably it is 10 to 20 moles.

The amount of basic catalyst used is polyphenylene ether 100
The amount is 0.5 to 5 parts by weight.

[Example] The present invention will be explained in detail below using examples.

The reaction rate of the terminal phenolic hydroxyl group of polyphenylene ether is reported in the Journal of Applied Polymer Science Applied Polymer Symposium (Journal of Applied Polymer Symposium).
er 5science: Applied Polyse
r 5yIlposiu+w).

The terminal phenolic hydroxyl groups before and after the reaction were determined and calculated according to the method described in Vol. 34 (1978), pages 103-117.

Example 1 Poly(2,6-dimethyl-1,4-phenylene ether) (intrinsic viscosity measured in chloroform at 30° C.: 0.4 (1/g) 40 g of chlorobenzene 400
wI, then 4.4 g of ethylene carbonate and 0.4 g of potassium carbonate were added, and stirring was continued at 120° C. for 8 hours.

After cooling the reaction solution, it was slowly poured into 1.5I2 methanol to precipitate the functionalized polyphenylene ether formed. After separating the precipitated polymer, it was washed with 1.52 ml of pure water, and then twice with 1.52 ml of methanol. 80
The mixture was dried by heating under reduced pressure at ℃ to obtain 38.5 g of hydroxyethylated polyphenylene ether.

The infrared absorption spectrum of this hydroxyethylated polyphenylene ether is shown in FIG.

Absorption considered to be derived from hydroxyl groups is shown near 3600 cm-'. Furthermore, quantification of the phenolic hydroxyl groups in the terminal groups before and after the reaction revealed that 50% of the terminal groups had reacted.

Example 2 20 g of poly(2,6-dimethyl-1,4-phenylene ether) (intrinsic viscosity measured in chloroform at 30° C. + 0.30 dl/g) are dissolved in 200 g of xylene, followed by 20 g of propylene carbonate. Add 0g of potassium carbonate and 0.3g of potassium carbonate, continue stirring at 132°C for 7 hours, and slowly pour the reaction mixture into methanol lβ.
The resulting functionalized polyphenylene ether was precipitated.

After separating the precipitated polymer, it was washed with pure water IQ and then twice with methanol lβ. Drying was carried out under reduced pressure at 80°C to obtain 19.0 g of 2-hydroxypropylated polyphenylene ether, which exhibited an absorption thought to be derived from hydroxyl groups near 3600 CI m-' in its infrared absorption spectrum. ing. Furthermore, quantification of the phenolic hydroxyl groups in the terminal groups before and after the reaction revealed that 49% of the terminal groups had reacted.

Application example 1: Synthesis of polyphenylene ether-polypropylene graft copolymer 17.1 g of hydroxyethylated polyphenylene ether obtained in Example 1 and polypropylene modified with maleic anhydride (maleic anhydride content 1.3% by weight, number Average molecular weight Vin=43.200. Weight average molecular weight Mw=125.
200 mt' of xylene was added to 5.0 g of 000) and reacted for 7 hours at 130° C. under a nitrogen atmosphere.The reaction mixture was poured into methanol lβ to precipitate the polymer, which was recovered by furnace. Furthermore, this polymer was mixed with methanol 1
．． Washed twice with 22. Dry under reduced pressure at 85°C to obtain 2
1.4 g of polymer was obtained.

Next, 2.54 g of the obtained polymer was added to 30 g of chloroform.
0- was used as a solvent, and extraction was performed using a Soxhlet extractor. As a result, 1.83 g of unreacted polyphenylene ether was extracted as a chloroform-soluble component. From this, the polyphenylene ether content in the obtained polyphenylene ether-boribropylene copolymer was 19.7% by weight.

〔Effect of the invention〕

As shown in the Examples, hydroxyalkylated polyphenylene ethers can be easily prepared by the process of the present invention, which can also be easily combined with treated polypropylene, as shown in Application Example 1. , could be copolymerized.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum of the hydroxyethylated polyphenylene ether (cast film prepared from a chloroform solution) obtained in Example 1.

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (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. (m represents a number of 10 or more) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (III) (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) ) Hydroxyalkyl represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (wherein Q_1, Q_2, m, and R are the same as above) A method for producing polyphenylene ether.