JPH05320332A - Production of hydroxyalkylated polyphenylene ether - Google Patents

Abstract

PURPOSE:To readily obtain a hydroxyalkylated polyphenylene ether having excellent compatibility with resins such as polyolefin or polyester by reacting a polyphenylene ether with a halogenated polyhydric alcohol. CONSTITUTION:A polyphenylene ether (hereinafter referred to as PPE) is reacted with a halogenated polyhydric alcohol of the formula X-R-(OH)m (R is 3-8C tri-to hexafunctional hydrocarbon; X is halogen; m is 2-5) (preferably 3-chloro-1,2- propanediol, etc.) to give the objective polymer. To be concrete, for example, PPE is dissolved in an organic solvent such as benzene to give a solution, to which an aqueous solution of an inorganic basic compound and a phase transfer catalyst such as benzyltrimethylammonium chloride are added, then the halogenated polyhydric alcohol is added to the solution and reaction is carried out at room temperature to a temperature not exceeding the boiling point of the organic solvent. Poly(2,6-dimethyl-1,4-phenylene ether) is preferable as the PPE.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a hydroxyalkylated PPE by modifying a terminal phenolic hydroxyl group of polyphenylene ether (hereinafter referred to as "PPE").

The hydroxyalkylated PPE of the present invention is
When blended with other resins, such as polybutylene terephthalate, nylon, maleic anhydride grafted polypropylene, etc., compared to unmodified PPE, it reacts with the functional groups of the blended resin to enhance compatibility between the resins and improve impact resistance. Gives high resin products. Therefore, this hydroxyalkylated PPE is useful as a modifier for PPE and as a compatibilizer for PPE and other resins. Furthermore, this compound is PP
It is useful as a precursor of a graft or block copolymer of E.

[0003]

2. Description of the Related Art PPE has excellent heat resistance, mechanical properties,
It is an extremely useful thermoplastic resin that has electrical properties, water resistance, acid resistance, alkali resistance, and self-extinguishing properties, and has been widely applied as an engineering plastic material.

However, since this resin has a high glass transition temperature, it has a high melt viscosity, is poor in moldability, and has poor impact resistance as an engineering plastic.

Blending with polyolefins or other engineering plastics such as polybutylene terephthalate, nylon and the like has been carried out with the aim of remedying these drawbacks. However, in these blends, both polymers are essentially poor in compatibility, and as a result, the resulting resin composition is brittle, and its mechanical strength and impact strength are lowered, making it unusable for practical use.

A compatibilizer is used to solve this problem. Most compatibilizers are graft or block copolymers of both polymers. It is conceivable to react the terminal phenolic hydroxyl group of PPE with a functional group in another polymer during the synthesis of these copolymers.

However, the functional group species of other polymers capable of reacting with the phenolic hydroxyl group are limited, and the range of utilization thereof is naturally limited. Therefore, many modified PPEs have been proposed for the purpose of increasing the reactivity of PPE.

Japanese Unexamined Patent Publication (Kokai) No. 3-292326 discloses a method for producing a hydroxyalkylated PPE by reacting a halogenated alcohol with PPE. The hydroxyalkylated PPE produced by this method is a PPE.
The content of hydroxyalkyl groups per molecule is 1 or less, and it is desired to introduce 2 or more hydroxyalkyl groups per molecule of PPE in order to improve the reactivity with the functional groups of other resins.

[0009]

In order to solve the above problems, the present invention has extremely excellent miscibility with resins such as polyolefins, polyesters and polyamides, and contains two or more hydroxyalkyl groups in one molecule. An object of the present invention is to provide a method for producing PPE.

[0010]

Means for Solving the Problems The present inventors can easily obtain excellent performance by modifying a terminal phenolic hydroxyl group of PPE with a halogenated polyhydric alcohol having two or more hydroxyl groups. Hydroxyalkylated PP
It was found that E was obtained, and the present invention was completed.

That is, according to the present invention, polyphenylene ether has the formula (I) X-R- (OH) _m (I) (wherein R represents a C 3-8 trivalent hydrocarbon group). , X represents a halogen atom, and m represents an integer of 2 to 5), and a method for producing a hydroxyalkylated polyphenylene ether is characterized by reacting a halogenated polyhydric alcohol represented by the formula:

<PPE> The PPE used in the present invention has the general formula (II)

[0013]

[Chemical 1]

Homopolymers and copolymers having the structure shown by

Here, Q ¹ is each a halogen atom, a primary or secondary alkyl group having 1 to 12 carbon atoms, and 6 carbon atoms.
To 12 aryl groups, C1 to C12 aminoalkyl groups, C1 to C12 haloalkyl groups, C1 to C12
Or a halohydrocarbonoxy group having 1 to 12 carbon atoms, Q ² is a hydrogen atom, a halogen atom, or
A primary or secondary alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a haloalkyl group having 1 to 12 carbon atoms, a hydrocarbon oxy group having 1 to 12 carbon atoms, or 1 to 12 carbon atoms Represents a halohydrocarbonoxy group. n is 10-5
Represents an integer of 00.

Examples of suitable primary alkyl groups for Q ¹ and Q ² include methyl, ethyl, n-propyl, n-butyl, n.
-Amyl, isoamyl, 2-methylbutyl, n-hexyl, 2,3-dimethylbutyl, 2-, 3- or 4-
Methylpentyl or the corresponding heptyl. Similarly, examples of secondary alkyl groups are isopropyl, sec-butyl or 1-methylpentyl. In many cases, each Q ¹ is an alkyl group or a phenyl group, especially an alkyl group having 1 to 4 carbon atoms, and each Q ² is a hydrogen atom. Suitable PP
Examples of the homopolymer or copolymer of E include poly (2,6-dimethyl-1,4-phenylene ether) or 2,6-dimethyl-1,4-phenylene ether and 2,3,6-trimethyl. It is a random copolymer with -1,4-phenylene ether. Many suitable homopolymers and random copolymers are described in the patent literature.

For example, a PPE containing a molecular structure portion that improves properties such as molecular weight, melt viscosity and / or impact strength.
Are also suitable. That is, it is a resin or the like obtained by graft-reacting a vinyl monomer such as acrylonitrile or a vinyl aromatic compound such as styrene or a polymer such as polystyrene or an elastomer on PPE.

The molecular weight of PPE (II) is such that the intrinsic viscosity measured at 30 ° C. in chloroform is usually about 0.2 to 0.8 dl / g.

PPE is usually produced by oxidative coupling of the above-mentioned monomers. Numerous catalyst systems are known for the oxidative coupling polymerization of PPE. There is no particular limitation on the selection of the catalyst, and any known catalyst can be used. For example, those containing at least one heavy metal compound such as copper, manganese, and cobalt, usually in combination with various other substances, and the like.

<Halogenated polyhydric alcohol> The halogenated polyhydric alcohol represented by the general formula (I) used as a modifier for PPE has a halogen atom substituted with a hydrocarbon group and two or more hydroxyalkyl groups. It is a compound that has both. Here, X represents a halogen atom, and specifically represents fluorine, chlorine, bromine, iodine atoms or the like.

Specific preferred examples of the halogenated polyhydric alcohol represented by the general formula (I) include 3-chloro-1,2.
-Propanediol, 3-bromo-1,2-propanediol, 3-iodo-1,2-propanediol, 3-
Fluoro-1,2-propanediol, 3-chloro-2
-Methyl-1,2-propanediol, 3-bromo-2
-Methyl-1,2-propanediol, 3-chloro-
1,2-butanediol, 1-chloro-2,3-butanediol, 3-chloro-1,2,4-butanetriol, monochloropentaerythritol, monobromopentaerythritol, 1-chloro-2,3-pentanediol , 3-chloro-1,6-hexanediol, 1-chloro-2,2-dimethyl-3,5-hexanediol and the like.

Among these, 3-chloro-1,2-propanediol, 3-bromo-1,2-propanediol, 3-chloro-2-methyl-1,2-propanediol, monobromopentaerythritol, etc. Is particularly preferable.

<Hydroxyalkylated PPE> The hydroxyalkylated PPE produced by the present invention has the general formula (I
II)

[0024]

[Chemical 2]

(Wherein Q ¹ , Q ² , R, m and n are the same as above)

In a mixed solvent of PPE (II) and halogenated polyalcohol (I), an organic solvent in which PPE (II) can be dissolved and water in which a water-soluble inorganic basic compound is dissolved. , Can be easily produced by reacting in the presence of a phase transfer catalyst.

The organic solvent used here is P as a raw material.
It is desirable to be able to dissolve PE. Specific examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; halogenated aliphatic hydrocarbons such as chloroform, trichloroethylene and carbon tetrachloride. Can be mentioned. Examples of the water-soluble inorganic basic compound include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate.

Examples of the phase transfer catalyst include quaternary ammonium salts, quaternary phosphonium salts and tertiary sulfonium salts. Preferred are quaternary ammonium salts, and specific examples thereof include benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogensulfate and trioctylmethylammonium chloride. Etc.

The hydroxyalkylated PPE of the present invention (II
I) can also be produced by the following method. That is, PP
It can be easily produced by reacting E (II) with a halogenated polyhydric alcohol (I) in a non-aqueous state in the presence of a basic compound in an organic solvent. In this case, a small amount of alcohols such as methanol and ethanol may be added to facilitate the dissolution of the basic compound in the organic solvent.

It is desirable that the organic solvent used here is capable of dissolving the raw material PPE. Specific examples include aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene; chloroform,
Halogenated aliphatic hydrocarbons such as trichloroethylene and carbon tetrachloride; N-methylpyrrolidone, 1,3-dimethyl-
An aprotic polar solvent such as 2-imidazolidinone and the like can be mentioned. Examples of the basic compound include alcoholates such as sodium methoxide and sodium ethoxide;
Tertiary amines such as triethylamine, benzyldimethylamine and tributylamine; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; sodium carbonate,
Examples thereof include alkali metal carbonates such as potassium carbonate; alkali metal hydrides such as sodium hydride, and the like.

The hydroxyalkylated PP of the present invention is described below.
The method for producing E (III) will be specifically described. PPE (II)
100 parts by weight of the organic solvent is heated to 300 to 1,000 parts by weight to dissolve it. Then, an inorganic basic compound (PPE
1 to 10 mol, preferably 1 to 5 mol) of an aqueous solution and 1 to 20 parts by weight of a phase transfer catalyst are added to 1 mol of the terminal phenolic hydroxyl group and the mixture is stirred for about 0.5 to 1 hour. Then, a halogenated polyhydric alcohol (I) as a modifier at a temperature not exceeding the boiling point of the organic solvent used from room temperature.
1 to 1 mol of the terminal phenolic hydroxyl group of PPE,
It is produced by adding 30 mol, preferably 2 to 20 mol, and reacting at the same temperature, and further stirring by heating for 1 to 10 hours until the reaction is completed.

Alternatively, instead of using an aqueous solution of an inorganic basic compound and a phase transfer catalyst in the above-mentioned production method, the hydroxyalkylated PPE (III) of the present invention contains the same amount of basic compound and, if necessary, an appropriate amount. It is also produced by reacting in the same manner as above except that alcohol is used.

[0033]

EXAMPLES The present invention will be described in detail below with reference to examples. In addition, the reaction rate of the terminal phenolic hydroxyl group of PPE and the confirmation of the hydroxyalkyl group are confirmed to be 2.0 for the modified PPE.
A wt% carbon disulfide solution was performed by measuring the infrared absorption spectrum using a quartz cell with an optical path length of 10 mm. That is, the reaction rate was calculated from the absorbance (3,610 cm ^-1 ) of the terminal phenolic hydroxyl group of PPE before and after the reaction.

Example 1 Poly (2,6-dimethyl-1,4-phenylene ether) as PPE (Intrinsic viscosity of 0.30 dl / g measured in chloroform at 30 ° C., polystyrene equivalent molecular weight: number average molecular weight 9, 200, weight average molecular weight 31,1
00) 20.0 g and toluene 200 ml were charged into a reactor and heated and stirred at 80 ° C. to dissolve PPE. Next, after adding 5.0 g of 50 wt% sodium hydroxide aqueous solution and 1.0 g of trioctylmethylammonium chloride as a phase transfer catalyst, the temperature of the reaction mixture was raised to 90 ° C. and stirring was continued for 30 minutes. Then 2.5 g of 3-chloro-1,2-propanediol was added over 15 minutes. Furthermore, after heating and stirring for 5 hours, the reaction solution was poured into 1.5 liters of methanol to precipitate the produced modified resin.

After this was filtered off, it was washed with 1 liter of water and further with 1 liter of methanol. It was dried under reduced pressure at 80 ° C. to obtain a hydroxyalkylated PPE. Yield 98%, reaction rate of terminal phenolic hydroxyl group is 75%
Met. The infrared absorption spectrum of the cast film prepared from the obtained chloroform solution of hydroxyalkylated PPE is shown in FIG. The same spectrum is 3,59
Absorption attributed to the hydroxyalkyl group was observed at 0 cm ^-1 .

Example 2 The same PPE used in Example 1, 65.0 g of PPE and 200 ml of xylene were charged into a reactor and heated and stirred at 90 ° C. to dissolve PPE. Then 3.0 g sodium ethoxide was dissolved in 20 ml ethanol and added, after which the temperature of the reaction mixture was raised to 100 ° C. and stirring was continued for 30 minutes. Next, 4.5 g of 3-chloro-1,2-propanediol was added into the reaction system over 50 minutes. Furthermore,
The mixture was heated and stirred at the same temperature for 4 hours, and after completion of the reaction, the reaction solution was poured into 1.5 liters of methanol to precipitate the hydroxyalkylated PPE thus produced.

This was filtered off and post-treated in the same manner as in Example 1 except that it was dried under reduced pressure at 90 ° C. to obtain a hydroxyalkylated PPE. Yield 97%, terminal reaction rate 9
It was 4%. The infrared absorption spectrum of the obtained carbon dioxide disulfide solution of hydroxyalkylated PPE is shown in FIG. The same spectrum has 3,450 cm ^-1 and 3,590 cm ^-1
The absorption attributed to the hydroxyalkyl group was observed.

Example 3 The procedure of Example 2 was repeated, except that instead of 4.5 g of 3-chloro-1,2-propanediol, 6.3 g of 3-bromo-1,2-propanediol was used.

The yield was 96%, and the reaction rate at the terminal was 92%. The infrared absorption spectrum of this product is 3,59
Absorption attributed to the hydroxyalkyl group was observed at 0 cm ^-1 .

Application Example 1 50 parts by weight of the hydroxyalkylated PPE obtained in Example 1 and maleic anhydride graft-modified polypropylene (number average molecular weight 43,400, weight average molecular weight 129000,
50 parts by weight of maleic anhydride (graft content is 1.0% by weight) was melt-kneaded with a plastomill manufactured by Toyo Seiki Co., Ltd. at 230 ° C. and a rotation speed of 180 rpm for 5 minutes. About the obtained resin composition, Hitachi S-2400
The cross section of the resin composition was observed with a scanning electron microscope. As a result, it was observed that PPE was finely and uniformly dispersed in a spherical shape, and the dispersed particle size was about 1 to 5 μm.

Comparative Application Example 1 PPE (40.0 g) and 2-chloroethanol (400 ml) were charged in a reactor and heated and stirred at 80 ° C. to dissolve PPE. Then, after adding 3 g of sodium ethoxide,
Stirring was continued at 80 ° C. for 4 hours. Next, the reaction liquid was poured into 2 liters of methanol to precipitate the generated modified resin.

This was post-treated in the same manner as in Example 1 to obtain a hydroxyalkylated PPE. The yield was 95%, and the reaction rate of terminal phenolic hydroxyl groups was 43%. In the infrared absorption spectrum of this product, absorption attributable to the hydroxyalkyl group was observed at around 3,600 cm ^-1 .

Next, a resin composition was obtained in the same manner as in Application Example 1 by using the obtained terminal hydroxyalkylated PPE. The dispersed particle size of PPE of this resin composition is 10 to
It was about 20 μm.

[0044]

As shown in the examples, according to the present invention, a hydroxyalkylated PPE having two or more hydroxyl groups in one molecule can be produced in high yield. Also, application example 1
As shown in FIG. 3, when the hydroxyalkylated PPE and polypropylene having a polar group were blended, a uniform dispersion of PPE in a fine spherical shape was observed. It is considered that this is because the two resins react with each other in the molten state to form a graft polymer, which improves the compatibility.

[Brief description of drawings]

FIG. 1 Hydroxyalkylated P obtained in Example 1
It is an infrared absorption spectrum of PE (cast film prepared from a chloroform solution).

FIG. 2 Hydroxylalkylated P obtained in Example 2
It is an infrared absorption spectrum of a carbon disulfide solution of PE.

Claims (1)

[Claims] 1. A polyphenylene ether having the general formula (I) X—R— (OH) _m (I) (wherein, R represents a C 3-8 trivalent hydrocarbon group, and X represents Represents a halogen atom, m represents an integer of 2 to 5), and reacts with a halogenated polyhydric alcohol.