JPH05117386A - Production of terminal aminated polyphenylene ether - Google Patents

Abstract

(57) [Summary] [Structure] Polyphenylene ether and halogenated amino heterocyclic compound (for example, 2-chloro-4,6-diamino-
1,3,5-triazine) is reacted to produce a terminal aminated polyphenylene ether. As shown in the examples, according to the present invention, amino group-functionalized polyphenylene ether can be produced in high yield. This product can be easily copolymerized with polypropylene having a polar group as shown in Application Examples 1 and 2.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an amino group-modified polyphenylene ether by functionalizing a terminal phenolic hydroxyl group of polyphenylene ether. The terminal-modified polyphenylene ether of the present invention reacts with a functional group of a blended resin when blended with another resin, for example, polybutylene terephthalate, nylon, maleic anhydride grafted polypropylene, etc., as compared with the unfunctionalized polyphenylene ether, and It improves the compatibility of and gives a resin product with high impact strength. Therefore, this terminal amino group-modified polyphenylene ether is useful as a modifier for the polyphenylene ether and as a compatibilizer for the polyphenylene ether and other resins. In addition, this compound is useful as a precursor for polyphenylene ether graft or block copolymers.

[0002]

2. Description of the Related Art Polyphenylene ether is an extremely useful thermoplastic resin having excellent heat resistance, mechanical properties, electrical properties, water resistance, acid resistance, alkali resistance, and self-extinguishing property. , Many applications are being developed.

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. For the purpose of improving these drawbacks, polyolefins and other engineering plastics such as polybutylene terephthalate,
Blending with nylon etc. is carried out. However, in these blends, both polymers are inherently poorly compatible. As a result, the obtained resin product becomes brittle, and its mechanical strength and impact strength are reduced, and it cannot be put to practical use.

A compatibilizer is used to solve this problem. Compatibilizers are often graft or block copolymers of both polymers. It is expected that the terminal phenolic hydroxyl group of the polyphenylene ether will react with the functional groups in other polymers during the synthesis of these copolymers. However, the functional group species of the compound capable of reacting with the phenolic hydroxyl group is limited, and the utilization range thereof is naturally limited. Therefore, many functionalized polyphenylene ethers have been proposed for the purpose of increasing the reactivity of the polyphenylene ether. Many of them introduce an acid anhydride group, a hydroxyl group or the like into polyphenylene ether, and it was difficult to introduce an amino group into polyphenylene ether due to its high reactivity.

Tokusho 63-503391, Tokusho 63
JP-A-500803 discloses several examples of amino-functionalized polyphenylene ether, but the method requires multi-step reaction, gelation of polyphenylene ether occurs during the reaction, or high temperature. There are some problems to be solved such as the need for the melting reaction of

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a technique for producing a terminal amino group-functionalized polyphenylene ether capable of enhancing compatibility when blended with a resin such as polyolefin, polyester, polyamide, etc., by an extremely easy method. For the purpose of provision.

[0007]

The present inventors have made it possible to easily functionalize polyphenylene ether by functionalizing the terminal phenolic hydroxyl group of polyphenylene ether with a halogenated aminoheterocyclic compound, as compared with conventional methods. The present invention has been completed by finding that ether can be obtained. That is, the present invention has the general formula (I)

[0008]

[Chemical 4]

(Wherein Q ₁ is a halogen atom, a primary or secondary alkyl group having 1 to 12 carbon atoms, and a carbon number of 6 respectively.
To C12 phenyl group, C1 to C12 aminoalkyl group, C1 to C12 hydrocarbon oxy group, or C1
~ 12 halohydrocarbonoxy groups are represented. Q ₂ is a hydrogen atom, a halogen atom, a C 1-12 first or second C 2 respectively.
Grade alkyl group, phenyl group having 6 to 12 carbon atoms, 1 carbon atom
Represents a haloalkyl group having 1 to 12 carbon atoms, a hydrocarbon oxy group having 1 to 12 carbon atoms, and a halohydrocarbon oxy group having 1 to 12 carbon atoms. n represents a number of 10 to 500. ) And a polyphenylene ether represented by the general formula (II)

[0010]

[Chemical 5]

(Here, R represents a hydrocarbon having 1 to 12 carbon atoms, a hydrocarbon / aromatic having 6 to 12 carbon atoms, a halogen atom, a hydroxyl group, or an amino group. X represents a halogen atom. Y represents a carbon atom or a nitrogen atom), and a halogenated aminoheterocyclic compound represented by the formula (III) is reacted.

[0012]

[Chemical 6]

(Wherein Q ₁ , Q ₂ , R, Y and n are the same as those in the above formulas (I) and (II)) and a method for producing a polyphenylene ether modified with an end group. It is about. <Polyphenylene ether> Formula (I) used in the present invention
The polyphenylene ether represented by is represented by the general formula (I)

[0014]

[Chemical 7]

The homopolymers and copolymers represented by Here, Q ₁ is a halogen atom or a carbon number of 1 to 1, respectively.
2 primary or secondary alkyl groups, C 6-12 phenyl groups, C 1-12 aminoalkyl groups, C 1-12 hydrocarbon oxy groups, or C 1-12 halo. Represents a hydrocarbon oxy group. Q ₂ is a hydrogen atom, a halogen atom, a primary or secondary alkyl group having 1 to 12 carbon atoms, a phenyl group having 6 to 12 carbon atoms, or a carbon atom having 1 to 1 carbon atoms.
2 represents a haloalkyl group having 2 carbon atoms, a hydrocarbon oxy group having 1 to 12 carbon atoms, or a halohydrocarbon oxy group having 1 to 12 carbon atoms. n represents a number of 10 to 500.

In the compound of the formula (I), examples of the first lower alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, isoamyl group, 2
-Methylbutyl group, n-hexyl group, 2,3-dimethylbutyl group, 2-, 3- or 4-methylpentyl group and the corresponding heptyl group. Examples of the secondary lower alkyl group are isopropyl group, sec-butyl group and 1-methylpentyl group. Most often, each Q ₁ is an alkyl or phenyl group, especially an alkyl group having 1 to 4 carbon atoms, and each Q ₂ is a hydrogen atom. Suitable homopolymer and copolymer polyphenylene ethers include, for example, poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethyl-1,4-phenylene ether and 2,3,3. It is a random copolymer with 6-trimethyl-1,4-phenylene ether.

Many suitable random copolymers and homopolymers have been described in the patents and literature. Polyphenylene ethers containing moieties that improve properties such as molecular weight, melt viscosity and / or impact strength can also be used.
For example, it is a resin obtained by grafting a vinyl monomer such as acrylonitrile and a vinyl aromatic compound such as styrene or a polymer such as polystyrene and an elastomer onto polyphenylene ether.

The molecular weight of polyphenylene ether is usually such that the intrinsic viscosity at 30 ° C. is 0.2 to 0.8 dl in chloroform.
/ G. Polyphenylene ethers are usually prepared by the oxidative coupling of the abovementioned monomers, for example 2,6-dimethylphenol. Numerous catalyst systems are known for the oxidative coupling polymerization of polyphenylene ethers. There is no particular limitation on the selection of the catalyst, and any known catalyst can be used. For example, it usually contains at least one heavy metal compound such as copper, manganese, or cobalt in combination with various other substances. <Halogenated Amino Heterocyclic Compound> The halogenated amino heterocyclic compound represented by the general formula (II) used for functionalizing the polyphenylene ether is substituted with a hydrocarbon group or a hydrocarbon group of a hydrocarbon / aromatic group. It is a compound that has both a halogen atom and an amino group. Where X is
It represents a halogen atom, specifically, fluorine, chlorine, bromine, iodine or the like.

Specific preferred examples of the halogenated aminoheterocyclic compound represented by the general formula (II) include 2-chloro-
4,6-diamino-1,3,5-triazine, 6-chloro-2,4-diaminopyrimidine, 2-amino-4-chloro-6-hydroxypyrimidine, 2-amino-4-chloro-6-methylpyrimidine , 2-amino-4,6-dichloropyrimidine and the like. <Amination polyphenylene ether> The aminated polyphenylene ether represented by the general formula (III) includes the polyphenylene ether represented by the general formula (I) and the general formula (I
The halogenated aminoheterocyclic compound represented by I) is halogenated with polyphenylene ether in a mixed solvent of an organic solvent in which polyphenylene ether can be dissolved and a water-soluble inorganic basic compound in the presence of a phase transfer catalyst. It can be easily produced by reacting an amino heterocyclic compound.

It is desirable that the organic solvent used here be able to dissolve the polyphenylene ether as a raw material. Specific examples thereof include aromatic solvents such as benzene, toluene and xylene, halogenated aromatic solvents such as chlorobenzene and dichlorobenzene, and halogenated hydrocarbon solvents such as chloroform, trichloroethylene and carbon tetrachloride. 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, and the like.

Examples of the phase transfer catalyst 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 hydrogensulfate and trioctylmethylammonium chloride. Etc.

The reaction of the present invention is carried out according to the general formula (I) with respect to 1 mol of the phenolic hydroxyl group at the terminal group of polyphenylene ether.
I) halogenated amino heterocyclic compounds 1 to 30
A molar amount, preferably 2 to 20 mol, is used. The organic solvent is
300 to 100 parts by weight of polyphenylene ether
Use up to 1000 parts by weight. The inorganic basic compound is used in an amount of 1 to 10 equivalents per equivalent of the 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.

The conditions for producing the aminated polyphenylene ether represented by the general formula (III) will be specifically described. The polyphenylene ether represented by the formula (I) is heated and dissolved in an organic solvent, and the inorganic basic compound is added thereto. Solution and a phase transfer catalyst, and the reaction is carried out at the same temperature by adding the halogenated aminoheterocyclic compound at a temperature not exceeding the boiling point of the organic solvent used from room temperature, and stirring with heating until the reaction is complete. Manufactured by.

[0024]

EXAMPLES The present invention will be described in detail below with reference to examples. The polyphenylene ether used in these examples is poly (2,6-dimethyl-1,4-phenylene ether) (abbreviated as PPE in the table. Intrinsic viscosity measured at 30 ° C. in chloroform is 0.30 dl / g, Polystyrene-equivalent molecular weight: Mn 9,200, Mw 31,100)
belongs to.

Terminal group of polyphenylene ether The reaction rate of the phenolic hydroxyl group and the amino group were confirmed by the infrared absorption spectrum of 2.0 wt% carbon disulfide solution of modified polyphenylene ether using a quartz cell with an optical path length of 10 mm. Was carried out by measuring That is, the reaction rate is
It was calculated from the absorbance (3610 cm ⁻¹ ) of the terminal phenolic hydroxyl group of the polyphenylene ether before and after the reaction.

Examples 1-3 Polyphenylene ether 20.0 g and toluene 200
Milliliter was charged into the reactor and heated and stirred at 80 ° C. to dissolve the polyphenylene ether. Then 50
7.0% by weight aqueous sodium hydroxide solution, trioctylmethylammonium chloride as a phase transfer catalyst 2.
After adding 0 g, the temperature of the reaction mixture was raised to 90 ° C. and 3
Stirring was continued for 0 minutes.

Then, a functionalized reagent, a halogenated aminoheterocyclic compound shown in Table 1 (an aqueous solution of the amount shown in Table 1) was added over 15 minutes. After heating and stirring for 7 hours, the reaction solution was poured into 1.5 liters of methanol to precipitate the modified resin produced. This was separated by filtration, washed with 1 liter of water, and further washed with 1 liter of methanol. It was dried by heating under reduced pressure at 80 ° C. to obtain terminal aminated polyphenylene ether. The yield and the reaction rate of the polyphenylene ether terminal are shown in Table 1.

[0028]

[Table 1]

Application Example 1 5.0 g of a terminal amino group-functionalized polyphenylene ether obtained in Example 1 and maleic anhydride graft-modified polypropylene (number average molecular weight 43,400, weight average molecular weight 129000, maleic anhydride grafted The content is 1.
0% by weight) 5.0 g of o-dichlorobenzene 100 ml
And was heated to reflux at 172 ° C. for 8 hours under a nitrogen atmosphere.

After completion of the reaction, the reaction mixture was poured into 1 liter of methanol to precipitate the reacted polymer. After separation by filtration, washing with 1 liter of methanol and heating under reduced pressure at 80 ° C., 9.8 g of polymer was recovered. Next, 1.6556 g of the obtained polymer was subjected to Soxhlet extraction for 7 hours using 200 ml of chloroform as a solvent to remove ungrafted polyphenylene ether by extraction. As a result, it was found that the polyphenylene ether extracted and removed was 0.7641 g, and as a result, the content of polyphenylene ether in the grafted product was 7.2% by weight.

Application Example 2 5.0 g of polyphenylene ether functionalized with terminal amino group obtained in Example 1 and glycidyl methacrylate graft polypropylene (number average molecular weight 109,000, weight average molecular weight 389,600, glycidyl methacrylate content 1.2 weight) %) 5.0 g of o-dichlorobenzene 10
It was dissolved in 0 ml and heated under reflux at 174 ° C. for 8 hours in a nitrogen atmosphere.

After completion of the reaction, the reaction mixture was poured into 1 liter of methanol to precipitate the reacted polymer. After separation by filtration, washing with 1 liter of methanol and heating under reduced pressure at 80 ° C., 9.8 g of polymer was recovered. Next, 1.6665 g of the obtained polymer was subjected to Soxhlet extraction for 7 hours using 200 ml of chloroform as a solvent to extract and remove ungrafted polyphenylene ether. As a result, it was found that the polyphenylene ether extracted and removed was 0.7745 g, and as a result, the content of polyphenylene ether in the graft body was 6.6% by weight.

Application Example 3 Terminal aminated polyphenylene ether 5 obtained in Example 1
0 part by weight and 50 parts by weight of the maleic acid graft-modified polypropylene used in Application Example 1 were placed in a plastomill manufactured by Toyo Seiki Co., Ltd. having an internal volume of 60 ml at 230 ° C. and a rotation speed of 18
Melt kneading was performed for 10 minutes under the condition of 0 rpm.

With respect to the obtained resin composition, a cross section of the resin composition was observed with an S-2400 scanning electron microscope manufactured by Hitachi Ltd. As a result, it was observed that the polyphenylene ether was spherically dispersed, and the dispersion diameter was 1 to
It was 5 microns or less.

Comparative Application Example A resin composition was obtained in the same manner as in Application Example 3, except that unmodified polyphenylene ether was used instead of terminal aminated polyphenylene ether. The dispersed diameter of this resin composition was as coarse as 20 to 50 microns.

[0036]

INDUSTRIAL APPLICABILITY As shown in the examples, according to the present invention, terminal amino group-terminated polyphenylene ether can be produced in high yield. This product can be easily copolymerized with polypropylene having a polar group as shown in Application Examples 1 and 2. Further, as shown in Application Example 3, when the terminal aminated polyphenylene ether and the polypropylene having a polar group are blended, a uniform dispersion of fine spherical polyphenylene ether is observed.

[Brief description of drawings]

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

FIG. 2 shows an infrared absorption spectrum of the terminal aminated polyphenylene ether obtained in Example 2 in a carbon disulfide solution. (Absorption by primary amine was observed near 3422 and 3541 cm ^-1 .)

Claims (1)

[Claims] 1. A compound represented by the general formula (I): (Here, each Q ₁ is a halogen atom, a primary or secondary alkyl group having 1 to 12 carbon atoms, a phenyl group having 6 to 12 carbon atoms, an aminoalkyl group having 1 to 12 carbon atoms, or 1 to 1 carbon atoms.
2 represents a hydrocarbon oxy group or a halohydrocarbon oxy group having 1 to 12 carbon atoms. Q ₂ is a hydrogen atom, a halogen atom, a primary or secondary alkyl group having 1 to 12 carbon atoms, a phenyl group having 6 to 12 carbon atoms, a haloalkyl group having 1 to 12 carbon atoms, or a 1 to 12 carbon atom. It represents a hydrocarbon oxy group or a halohydrocarbonoxy group having 1 to 12 carbon atoms. n
Represents a number from 10 to 500. ) And a polyphenylene ether represented by the general formula (II): (Here, R is a hydrocarbon having 1 to 12 carbons and 6 carbons.
~ 12 hydrocarbons / aromatics, halogen atoms, hydroxyl groups, or amino groups. X represents a halogen atom. Y
Represents a carbon atom or a nitrogen atom. ) Is reacted with a halogenated amino heterocyclic compound represented by the general formula (III) (Here, Q ₁ , Q ₂ , Y, R, and n are the same as those in the above formulas (I) and (II).) A method for producing a terminal aminated polyphenylene ether.