JPH04126718A - Production of end aminated polyphenylene ether - Google Patents

Abstract

PURPOSE:To obtain the title compound having improved compatibility with resins such as polyolefin, polyester and polyamide by reacting a specific polyphenylene ether with a halogenated primary amine. CONSTITUTION:A polyphenylene ether shown by formula I [Q<1> is halogen, primary, secondary alkyl, phenyl, aminoalkyl or (halo)hydrocarbon oxy; Q<2> is H, halogen, primary, secondary alkyl, phenyl, haloalkyl or (halo) hydrocarbonoxy; n is >=10] is reacted with a halogenated primary amine (e.g. 2-chloroethylamine) shown by the formula X-R-NH2 (R is 1-32C aliphatic hydrocarbon, aromatic hydrocarbon or araliphatic hydrocarbon; X is halogen) to give the objective compound shown by formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a process for producing terminally aminated polyphenylene ethers by functionalizing terminal phenolic hydroxyl groups of polyphenylene ethers.

Compared to unfunctionalized polyphenylene ether, the terminally aminated polyphenylene ether produced by the production method of the present invention, when blended with other resins, reacts with the functional groups of the blended resin to increase the compatibility between the resins. This is thought to have the effect of increasing the impact strength of the composition,
Furthermore, utilization as a precursor of a graft or block copolymer is also considered.

(Prior art) 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 is used as an engineering plastic material. , many applications are being developed. However, this resin has disadvantages related to its high glass transition temperature, such as high melt viscosity, poor moldability, and poor impact resistance as an engineering plastic.

Blends with polyolefins or other engineering plastics have been carried out with the aim of improving these drawbacks, but they are inherently incompatible with these polymers, and the resulting compositions are brittle and have poor mechanical properties. Strength,
The impact strength is reduced and it cannot be put to practical use. Compatibilizing agents have been used to solve this problem, but most of the compatibilizing agents 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, but most of them introduce acid anhydrides, hydroxyl groups, etc. into polyphenylene ethers, and polyphenylene ethers with amine groups It was difficult to introduce it into the world due to its high reactivity.

Special Publication No. 63-503391 and No. 63-500803
Each publication lists several examples of amine group-functionalized polyphenylene ethers, but the manufacturing method requires multiple reactions, and gelation of the polyphenylene ether occurs during the reaction. There are a number of problems that need to be solved, such as the need for high-temperature melting reactions.

(Problems to be Solved by the Invention) An object of the present invention is to provide an extremely easy method for producing terminally aminated polyphenylene ether that can significantly improve compatibility with resins such as polyolefins, polyesters, and polyamides. do.

(Means for Solving the Problems) The present inventors have discovered that by functionalizing the terminal phenolic hydroxyl group of polyphenylene ether with a halogenated primary amine, the terminal amino acid The present invention was completed based on the discovery that polyphenylene ether can be obtained.

The present invention is based on the general formula (wherein Ql each represents a halogen atom, a secondary or secondary alkyl group, a phenyl group, an aminoalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group, and Q2 each represents hydrogen atom, a halogen atom, a primary or secondary alkyl group, a phenyl group, a haloalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group, and n represents a number of 10 or more. General formula % formula %) (wherein, R represents an aliphatic hydrocarbon group, aromatic hydrocarbon group, or araliphatic hydrocarbon group having 1 to 32 carbon atoms, and X represents a halogen atom) This is a method for producing a terminally aminated polyphenylene ether represented by the general formula (wherein Ql, Q2, R and n are the same as above), which is characterized by reacting a chemical primary amine.

The polyphenylene ether used in the present invention is a homopolymer or copolymer having the following structure.

Suitable examples of primary alkyl groups for Ql and Q2 are methyl, ethyl, n-propyl, n-butyl, n-amyl, isoamyl, 2-methylbutyl, n-hexyl, 2.3-
Dimethylbutyl, 2-13- or 4-methylpentyl or heptyl. Suitable examples of secondary alkyl groups are isopropyl, 5ec-butyl or 1-methylpentyl. In most 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. A suitable polyphenylene ether homopolymer is, for example, one consisting of 2°6-dimethyl-1,4-phenylene ether units. Suitable copolymers include the above units and 2,3,6-drimethyl-1.
It is a random copolymer consisting of a combination of 4-phenylene ether units. Many suitable homopolymers or random copolymers are described in the patent literature. Polyphenylene ethers containing molecular moieties that improve properties such as molecular weight, melt viscosity and/or impact strength are also suitable. For example, polyphenylene ether is obtained by graft copolymerizing 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 0.2-0.8 dl 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.

General formula (I) used as a functionalizing agent for polyphenylene ether
The halogenated primary amine represented by II) is a compound having both a halogen atom substituted on a hydrocarbon group of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an aromatic aliphatic hydrocarbon group, and an amino group. Here, specific examples of X include fluorine, chlorine, bromine, and iodine.

Preferred specific examples of halogenated primary amines include 2-
6 General formulas produced by the method of the present invention, including halogenated primary amines such as chloroethylamine, 2-bromoethylamine, 3-chloropropylamine, 3-bromopropylamine, or their hydrochloride, hydrobromide salts, etc. The terminally aminated polyphenylene ether of (1) has the general formula (II)
A polyphenylene ether represented by the general formula (nB) is mixed with a halogenated primary amine represented by the general formula (nB) in a mixed solvent of an organic solvent in which the polyphenylene ether is dissolved and water in which a water-soluble inorganic basic catalyst is dissolved, in the presence of a phase transfer catalyst. , can be easily produced by reacting polyphenylene ether with a halogenated primary amine.

The organic solvent used here is desirably capable of dissolving polyphenylene ether, which is a raw material. Specifically, aromatic hydrocarbon solvents such as benzene, toluene, and xylene:
Halogenated aromatic hydrocarbon solvents such as chlorobenzene and dichlorobenzene: chloroform, trichloroethylene,
Examples include halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride. As the water-soluble basic catalyst, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide;
Examples include alkali metal carbonates such as sodium carbonate and potassium carbonate.

Examples of phase transfer catalysts include quaternary ammonium salt compounds, quaternary phosphonium salt compounds, and tertiary sulfonium salt compounds. Preferred are quaternary ammonium salt compounds, and specific examples thereof include benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, and trioctylmethylammonium chloride. In this reaction, 1 to 30 moles, preferably 2 to 20 moles of the functionalizing agent represented by the general formula (II+) are used per mole of the terminal phenolic hydroxyl group of the polyphenylene ether.

The organic solvent is used in an amount of 300 to 1000 parts by weight per 100 parts by weight of polyphenylene ether. The basic catalyst is
1 to 10 equivalents are used per equivalent of functionalizing agent used. Preferably 1 to 5 equivalents are used. The phase transfer catalyst is used in an amount of 1 to 20 parts by weight per 100 parts by weight of polyphenylene ether.

To specifically explain the manufacturing procedure of the terminally aminated polyphenylene ether of general formula (I) manufactured by the method of the present invention, the polyphenylene ether is heated and dissolved in an organic solvent, and then an aqueous solution of a basic catalyst and a phase transfer catalyst are added. is added, a functionalizing agent is added and reacted at a temperature ranging from room temperature to a temperature not exceeding the boiling point of the organic solvent used, and the reaction is further heated and stirred until the reaction is completed.

Under the present reaction conditions, one molecule of halogenated primary amine is added to the terminal of polyphenylene ether. However, there is a possibility that one or more molecules of halogenated primary amine reacts with the terminal amino group of the functionalized polyphenylene ether, but even in that case, the terminal of the polyphenylene ether is an amino group, and the present invention Within range.

(Example) The present invention will be explained in detail below using examples.

To confirm the reaction rate of the terminal phenolic hydroxyl group and the amino group of polyphenylene ether, a 1.5% by weight carbon tetrachloride solution of aminated polyphenylene ether was heated with an optical path length of 10 m.
The experiment was carried out by measuring infrared (IR) absorption spectra using a quartz cell with a quartz cell. That is, the reaction rate was calculated from the absorbance (3622 cm-') of the terminal phenolic hydroxyl group of the polyphenylene ether before and after the reaction.

Examples 1-3 Poly(2,6-dimethyl-1,4-phenylene ether) (PPE, intrinsic viscosity measured in chloroform at 30°C: 0.30 df!/g) 20, og and toluene 2001 nl were added to a reactor. The mixture was charged and heated and stirred at 80°C to dissolve the polyphenylene ether. Subsequently, 7.0 g of a 50% aqueous sodium hydroxide solution was added as a basic catalyst.
After adding 2.0 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. Subsequently, the functionalizing agent listed in Table 1 was added in the same amount as an aqueous solution over 15 minutes. Furthermore, after heating and stirring for 7 hours, the reaction mixture was poured into methanol 1,5β to precipitate the produced modified resin. After separating this, wash with water II2 and then methanol 1j
Washed with 2. The terminally aminated polyphenylene ether was obtained by heating and drying under reduced pressure at 80"C. The yield and the reaction rate of the polyphenylene ether terminal are shown in Table 1. The number of additions of the halogenated tertiary amine was determined by proton nuclear magnetic resonance absorption spectrum. was found to be one molecule.

Figure 1 shows the infrared absorption spectrum of a cast film prepared from a chloroform solution of terminally aminated polyphenylene ether obtained in Example 2, and that of a carbon tetrachloride solution of terminally aminated polyphenylene ether obtained in Example 2. The infrared absorption spectrum is shown in Figure 2. In the latter, absorption due to primary amines was observed around 3380 cm-'.

Application example 1 Terminal aminated polyphenylene ether 5 obtained in Example 1
．． 0 g and 5.0 g of maleic anhydride-modified polypropylene (number average molecular weight 13.600, weight average molecular weight 32,800, maleic anhydride content 8% by weight) and 100 g of xylene.
- and heated under reflux at 125°C for 7 hours under a nitrogen atmosphere.

After the reaction was completed, the reaction mixture was poured into 1 liter of methanol to precipitate the reacted polymer. After separation, the mold was washed with methanol II2 and dried under reduced pressure at 80°C.9
．． 77g of polymer was recovered.

Next, 1.553 g of the obtained polymer was added to chloroform 20
Waxley extraction was performed for 7 hours using 0- as a solvent to extract and remove ungrafted polyphenylene ether. As a result, the amount of polyphenylene ether extracted and removed was 0.365 g, and the content of polyphenylene ether in the graft body was found to be 34.6% by weight.

(Effects of the Invention) As shown in Examples, the method for producing terminally aminated polyphenylene ether of the present invention is extremely easy, and as shown in Application Example 1, this method can be easily combined with treated polypropylene. was able to be grafted to the

[Brief explanation of the drawing]

FIG. 1 shows the infrared absorption spectrum of the terminally aminated polyphenylene ether obtained in Example 2 (cast film prepared from a chloroform solution). FIG. 2 shows an infrared absorption spectrum of a carbon tetrachloride solution of the functionalized polyphenylene ether obtained in Example 2.

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, Represents a hydrocarbon oxy group or a halohydrocarbon oxy 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, and n represents a number of 10 or more) Ether has a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (III) (In the formula, R represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group having 1 to 32 carbon atoms. , X represents a halogen atom) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. 2, R and n are the same as above).