JPS63193923A - High molecular weight polyphenylene oxide, its production and use - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides polyphenylene oxide (P) having a high molecular weight.
PO) and its production method by reacting a polybasic aromatic carboxylic acid or its derivative with polyphenylene oxide,
and their use for the modification of plastics.

Polyphenylene oxides and their preparation are known (e.g., U.S. Pat. No. 3,491,058.3,50).
Nos. 7,832 and 3,455.736).

It is also known to react certain polyphenylene oxides to form acyl-linked polymers (for example, German Patent Application Nos. 2,822° 859 and 2,82
No. 2,856). However, the applicable range and properties of these polymers do not necessarily satisfy all requirements.

It has now been found that high molecular weight polyphenylene oxides obtained from polybasic aromatic carboxylic acids and polyphenylene oxides have improved properties.

The present invention provides an optionally substituted aromatic group having the following formula (I) Ar (C0R)-(I) where m represents 2.3 or 4 and Ar has 6 to 20 carbon atoms. R represents the following formula (n), where X represents a halogen such as C1 or Br, and n is 10 to 10,000, preferably 100 to 5000
represents a polyphenylene oxide chain corresponding to an integer having the value of .

The polyphenylene oxide according to the present invention has a molecular weight of about 2°000 to
3,500,000, preferably 20°000 to 1,8
00,000 molecular weight, and 0.3 to 3.0 del,
Preferably, it has an inherent viscosity of 0.3 to 0.5 dl/g (measured in N-methylpyrrolidone at 30°C).

In the formula (I), Ar preferably represents an aromatic group having 6 to 10 carbon atoms, most preferably an aromatic group having 6 carbon atoms, but groups corresponding to the following formula (Ia>) are particularly preferred. In the above formula, m has the meaning indicated for formula (I), and X is hydrogen (H
) or a substituent such as, for example, halogen (CI, Br) or an alkyl group having 1 to 4 carbon atoms, and R has the meaning given for formula (I).

The present invention further provides polybasic aromatic carboxylic acids or derivatives thereof corresponding to formula (I[[) and corresponding carboxylic acid anhydrides Ar(COY)-(I
II) in which Ar and m have the meanings given for formula (I) and X represents the number 1 or 2 and Y is a halogen, such as for example Ct or Br, an OH group or a C, to C2゜-Aryloxy group or C3-C7゜-
representing an alkoxy group is reacted with a polyphenylene oxide formula corresponding to the following formula (IV), in which X and n have the meanings given for formula (n), -(-〇OR) In the formula, m represents the number 2.3 or 4, Ar represents an aromatic group having 6 to 20 carbon atoms, R is the formula (II), and X is, for example, Ct or Br. represents a halogen such as and n is 10 to 10,000, preferably 100 to 5000
The present invention relates to a method for producing polyphenylene oxide, in which the polyphenylene oxide chain is represented by an integer having the value of .

In formula (III), Y preferably represents CI, OH or 0-7znyl (phenolate).

Carboxylic acids or derivatives thereof corresponding to formula (I[[) or anhydrides thereof corresponding to formula (I[a)] include free acids, acid halides, esters, semi-esters, etc.
For example, terephthalic acid, terephthalic acid dichloride, terephthalic acid diphenyl ester, benzene-1,3,5
-1-dicarboxylic acid, benzene-1,3,5-tricarboxylic acid triphenyl ester, benzene-1,2,4,
5-tetracarboxylic acid, benzene-1,2,3,5-tetracarboxylic acid, phthalic acid, phthalic anhydride, naphthalene 1,2-dicarboxylic acid, anthracene-9°10-dicarboxylic acid, etc. can be used. can.

The polyphenylene oxide of formula (IV) can be a known polyphenylene oxide prepared by known methods (eg, British Patent No. 1.053,053 or US Pat. No. 3,491,058).

A carboxylic acid or a derivative thereof corresponding to formula (III), or an anhydride thereof corresponding to formula (lla) and formula (IV)
The reaction with the corresponding polyphenylene oxide can be carried out in the presence or absence of a solvent. In both cases, the reaction is carried out at 150-300°C in the absence of oxygen.
, preferably at a temperature of 180 DEG to 220 DEG C., optionally at a pressure of 1 to 10 bar and in the absence of water.

The solvent used is an organic solvent that is inert under the reaction conditions, such as diphenyl ether, hydroquinone dimethyl ether, diethylene glycol dimethyl ether, etc.
, lactams such as N-methylpyrrolidone, chlorinated hydrocarbons such as 1,2,4-)lichlorobenzene, sulfones such as diphenylsulfone, and the like.

Additives may be added to the reaction mixture, for example customary transesterification catalysts, bases such as alkali metal carbonates or heterocyclic nitrogen compounds. The selection of additives is based on the formula (III
) or a derivative thereof or a carboxylic acid of the formula (I [[a)
should depend on the choice of anhydride. For example, the formula (I
When using acid chlorides as derivatives of [[), it is advantageous to use bases. When using an ester as a derivative of the acid of the formula <l1t), a transesterification catalyst,
For example, it may be advantageous to add Lewis acids such as metal salts (eg 5nC1□).

For the reaction of acids of formulas <III) and (II[a) with polyphenylene oxides of formula (■), all components of the reaction are added together and an inert gas is passed through the reaction mixture or a vacuum is applied. After that, oxygen is removed by flowing inert gas. The mixture is then heated to reaction temperature. The inert gas used can be, for example, a noble gas such as N2 or Ar.

When using a carboxylic acid halide as the derivative of formula (III), the carboxylic acid halide may be dissolved in a small amount of a suitable solvent, such as tetrahydrofuran, and then added to the polyphenylene ether of formula (IY). is advantageous.

The reaction of the carboxylic acid or derivative of formula (Iff) with the polyphenylene ether of formula (IIV) can be carried out by pouring the reactants into a mixture of alcohol-niteryl aqueous acid (e.g. methanol-diethyl ether-concentrated hydrochloric acid). , or by adding the mixture to the reaction. The novel polyphenylene ether precipitates and can be separated, for example, by filtration.

It can then be further purified by conventional reprecipitation methods (eg, dissolution in N-methylpyrrolidone and precipitation with methanol concentrated HCl).

Conventional fillers, modifiers, pigments, stabilizers, flame retardants, etc. can be added to the polyphenylene oxide of the present invention. Their properties, such as processability, are improved by their high molecular weight. They can be processed into molded parts, for example by injection molding or extrusion. They can also be mixed and processed with other plastics.

They are particularly suitable for the production of high melting point thermoplastics. Moreover, the new polyphenylene ethers can also be reacted with other polymers to form various block copolymers.

The polyphenylene ether of the one-portion formula (II) can be prepared, for example, by alkali metal 4 with exclusion of oxygen and water (protons).
- Halogenophenolates can be prepared by known methods as follows: 50 ml of anhydrous hydroquinone dimethyl ether are prepared and dried under nitrogen to 15.63 f of potassium 4-bromophenolate. Add and heat the mixture. Polymerization is initiated by the addition of a catalyst solution prepared from 50,111 g of CuCl and anhydrous pyridine from three companies. The reaction temperature ranges from 100 to 250 °C, although a temperature of 200 °C has been found to be most effective. ing. The reaction solution was mixed with methanol, diethyl ether and fiHcl.
Stop the condensation by injecting it into the mixture.

The product precipitated from N-methylpyrrolidone is 0.4d
It has an inherent viscosity of 1/y (N-methylpyrrolidone/30C).

0.52 polyphenylene ether with an inherent viscosity of 0.299 dl/g at 200°C is dissolved in 10 ml of hydroquinone dimethyl ether and 0.2n+1
of anhydrous quinoline. After gradual addition of 15B terephthalic acid dichloride dissolved in anhydrous tetrahydrofuran from Company 75, the THF is immediately distilled off. The precipitated polyphenylene ether has a significantly increased inherent viscosity of 0.42 dl/g in CNMP at 30° C. and improved heat resistance as measured by thermogravimetric testing.

11? with an inherent viscosity of 0.299 dl/y.
of polyphenylene ether and 1'7+9 of terephthalic acid diphenyl ether are dissolved in 2 On+/anhydrous hydroquinone at 200° C. under inert gas and 0.14 mg of magnesium activated with iodine are added. The reaction temperature is maintained at 200°C for 8 hours.

precipitated from a mixture of methanol and diethyl ether;
Washed and dried polyphenylene ether is 0.35
It is found to have an inherent viscosity of 1 dl/g (NMP/30°C).

Claims (1)

[Claims] 1. The following formula (I) Ar-(-COR)_m(I) In the formula, m represents a number of 2, 3 or 4, and Ar is an aromatic group having 6 to 20 carbon atoms. R represents a group, and R is a formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) In the formula, X represents a halogen such as Cl or Br, and n is 10 to 10,000, preferably 100-5000
A polyphenylene oxide having a high molecular weight corresponding to , representing an integer having the value of , representing a polyphenylene oxide chain of . 2. The following formula (I) Ar-(-COR)_m(I) In the formula, m represents a number of 2, 3 or 4, and Ar is an optionally substituted aromatic having 6 to 20 carbon atoms. R represents a group group, and R is the following formula (II) ▲ Numerical formula, chemical formula, table, etc. ▼ (II) In the formula, X represents a halogen such as Cl or Br, and n is 10 to 10,000, preferably is 100-5000
A method for producing polyphenylene oxide corresponding to , which represents an integer of
Polybasic aromatic carboxylic acid or its derivative corresponding to formula (III) or corresponding carboxylic acid anhydride Ar(COY)_m(III) corresponding to formula (IIIa), ▲Mathematical formula, chemical formula, table, etc. are available. ▼(IIIa) In the formula, Ar and m have the meanings described for formula (I), X represents the number 1 or 2, and Y is a halogen such as Cl or Br, an OH group or C_6~ C_1_0-aryloxy group or C_1~
C_1_0-represents an alkoxy group, is the following formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) In the formula, X and n have the meanings described for formula (II). Polyphenylene corresponding to The production method, which comprises reacting with an oxide. 3. Use of polyphenylene oxide according to claim 1 for modifying plastics.