JPH0472328A - Method for producing carbonyl group-modified polyphenylene ether - 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 (Industrial Application Field) The present invention provides the following methods for improving the compatibility of polymer blends:
The present invention relates to a method for producing polyphenylene ether having an arbitrary number of reactive functional groups in the molecule that can physically or chemically bond to a different type of polymer.

Specifically, by reacting a mercaptocarbonyl compound with a polyphenylene ether having an arbitrary proportion of carbon-carbon unsaturated bonds, a phase ? The present invention relates to a method for producing a carbonyl group-modified polyphenylene ether having an arbitrary number of carbonyl groups in the molecule useful for improving g properties.

(Prior art) When producing a polymer blend, polyphenylene ether (hereinafter abbreviated as PPE) is generally incompatible with other resins and has no affinity with them, except for specific resins. do not have. For this reason, when two components are simply mixed, they exhibit an energetically stable phase-separated structure, and the adhesion at the interface of this two-phase structure is poor, resulting in a decrease in mechanical strength and impact resistance, resulting in poor moldability. It presents major problems such as easy delamination during processing.

In order to solve the above problems, it is effective to use as a compatibilizer a block body or a graft body consisting of segments having affinity for each of the PPE and the polymer to be blended. There are two ways to synthesize these: using a bifunctional small molecule such as maleic anhydride as a binder, and combining polymers with functional groups that react with each other. The type and number of functional groups in the molecule are important.

In most of these examples, unsaturated carboxylic acids, unsaturated imides, unsaturated epoxides, etc. are subjected to crosstalk reactions, and there are restrictions on the control of the number or types of functional groups that can be introduced.

In addition, examples have been shown in which various functional groups are introduced using the terminal phenolic hydroxyl group of PPE as a reaction site. For example, JP-A No. 63-], No. 99754 or Special Publication No. 6
The terminal carboxylic anhydride-modified products shown in each publication of No. 2-500456, the terminal alcoholic hydroxy-modified products of Japanese Patent Publication No. 63503391, and U.S. Patent No. 473293
There are terminal glycidyl-modified products described in the specification of No. 7, but the number of reaction points and functional groups is at most one per polymer molecule, and the optimum number of functional groups cannot be said to be satisfactory.

One effective method for introducing a functional group is reaction with a mercaptocarbonyl compound. Mercaptocarbonyl compounds are known to efficiently add to carbon-carbon unsaturated bonds mainly through radical reactions, and by applying this to polymers with carbon-carbon unsaturated bonds, it is possible to functionalize polymers. Become.

However, the reaction of mercaptocarbonyl compounds with PPE having unsaturated bonds (e.g., 2-ano-6
-Resin obtained by oxidative copolymerization of methylphenol and 2,6-dimethylphenol (US Pat. No. 3,422,062)
No example has been shown so far of its application to

(Problems to be Solved by the Invention) The present invention aims to improve the compatibility of polymer blends by:
The present invention provides a method for producing carbonyl group-modified PPE having an arbitrary number of carbonyl groups in the molecule as reactive functional groups.

(Means for Solving the Problems) The present invention provides polyphenylene ether having a carbon-carbon unsaturated bond as a substituent, 89 formula% formula% (1) (wherein m and n are integers of 1 to 4, respectively). Defeated, R1
is a saturated aliphatic hydrocarbon group having a valence of 2 to s and having 1 to 20 carbon atoms,
It is an aromatic hydrocarbon group or a hydrocarbon group containing an amide bond or an ester bond, and R2 is an alkali metal oxy group, a hydrogen atom, a hydroxyl group, an aryl group, and carbon rr1.1 to 2.
This is a method for producing a carbonyl group-modified polyphenylene ether, which is characterized by reacting a mercaptocarbonyl compound represented by the following formula (which is an alkyl group, a halogenated alkyl group, or a hydrocarbon oxy group).

PPE having a carbon-carbon unsaturated bond used in the present invention
is a ship formula (in the formula, p is an integer from 1 to 4, and at least one R
is a substituent having a carbon-carbon double bond or/or a carbon-carbon triple bond, R is a halogen atom, a C1-C20 secondary or secondary alkyl group, an aryl group, haloalkyl group, aminoalkyl group, hydrocarbonoxy group, or halohydrocarbonoxy group in which a halogen atom and an oxygen atom are bonded via at least two carbon atoms] species or two species of monomer compounds represented by This is PPE obtained by oxidative polymerization of the above. Examples of this monomer compound include 2-allylphenol, 2,6-diallylphenol, 2-allyl-6methylphenol, 2-allyl-5-chlorophenol, 2-allyl-3-methoxyphenol, 2-allyl-3 -isobutyl-6-methylphenol or 2-allyl-6-ethylphenol, preferably 2,6-diallylphenol,
2-allyl-6-methylphenol, 2-allyl-6-
Ethylphenol or 2-geranyl-6-methylphenol.

In addition, if necessary, among phenol or phenol derivatives, the substituent may include a halogen atom, a secondary or secondary alkyl group, an aryl group, a haloalkyl group, an aminoalkyl group, a hydrocarbon oxy group, or a halogen atom and an oxygen atom. is a monomer compound having a halohydrocarbonoxy group bonded via at least two carbon atoms to the above-mentioned bottom (
It may be oxidatively copolymerized with the monomer compound shown in II), and representative monomers of the latter derivative include, for example, 〇-1m- or p-cresol, 2.6
-12,5-22.4- or 3.5-dimethylphenol, 2.6-diphenylphenol, 2.6-diallylphenol, 2.3.5- or 2.3.6-)
Examples include dimethylphenol and 2-methyl-6-t-butylphenol. Among these, preferred are one or two selected from 2.6-dimethylphenol, a large amount of 2.6-dimethylphenol, a small amount of 2.36-trimethylphenol, and 0- or p-cresol. This is a combination of more than one type of monomer compound.

Furthermore, the main components are bisphenol A, tetrabromobisphenol A, resorcinol,
Hydroquinone, 2,2-bis(3°,5′-dimethyl-4°-hydroxyphenyl)propane, bis(3,5
-dimethyl-4hydroxyphenyl)methane, 3.3'
, 55°-tetramethyl-4,4′-dihydroxybiphenyl, or 4,4°-dihydroxybiphenyl may also be used as a copolymer containing a polyvalent hydroxy aromatic compound such as 4,4°-dihydroxybiphenyl.

Further, the production of the polymer can be carried out in the same manner as ordinary oxidative polymerization of PPH, for example, as described in U.S. Patent No. 3,422,062, U.S. Pat. It is described in.

The catalyst used for oxidative polymerization is not particularly limited, but any catalyst that can obtain a desired degree of polymerization may be used.

In this field, cuprous salts - amines, "secondary copper salts - amines"
Many catalyst systems are known consisting of alkali metal hydroxides, manganese salts-primary amines, etc.

Further, it is possible to use a polymer in which a part of the polymer constituents has been modified by a catalyst component, a polymerization solvent component, or by heat or oxygen during the manufacturing process or molding process. The range of the degree of polymerization is not particularly limited, but if the degree of polymerization is too low, the compatibilization ability will decrease, so
The practical lower limit is one with an intrinsic viscosity of about 0.1 #/g measured at 0°C, preferably 0.2 #/g or more, more preferably 0.3 df! /g or more.

Specific examples of mercaptocarbonyl compounds used in the present invention include compounds shown in Group A. Among these, mercaptoacetic acid, 2-mercaptopropionic acid, mercaptosuccinic acid, mercaptoacetic acid ethyl ester, etc. are preferred, and mercaptoacetic acid is particularly preferred.

Group A: mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thiosalicylic acid, 3-mercaptopropionic acid methyl ester,
Mercaptoacetic acid ethyl ester, 2-mercaptopropionic acid ethyl ester, N-(2-mercaptopropionyl)glycine, mercaptoacetic acid sodium salt, etc. Carbonyl group-modified PPE produced in the present invention includes the above-mentioned,
It is obtained by adding a thiol moiety of a mercaptocarbonyl compound to PPE having a carbon-carbon unsaturated bond as a substituent.

Here, the rate of modification by the carbonyl group of PPE is
The content of carbon-carbon unsaturated bonds in E can be arbitrarily controlled, but when considered as a compatibilizer, the content of carbonyl groups is preferably at least one per molecule of PPE, and Preferably 30 or less/1゜PPE having carbon-carbon unsaturated bonds in the present invention
The reaction between mercaptocarbonyl compound and benzene,
It can be carried out in an aromatic hydrocarbon solvent such as toluene, xylene, chlorobenzene, trichlorobenzene.

The amount of the mercaptocarbonyl compound used is preferably 2 to 30 times the amount of carbon-carbon unsaturated bonds, and 2 to 0.
More preferred is mole times.

In order to speed up the modification reaction, an organic peroxide such as dibenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide or t-butyl peroxybenzoate, or azobisisobutyronitrile is added to the reaction system. Alternatively, it is an effective method to use a radical initiator typified by an azo compound such as azobisisovaleronitrile or to irradiate with ultraviolet rays.

The reaction temperature is preferably in the range of 30 to 200°C, and more preferably 50 to 150°C.6 The reaction time is determined by the temperature,
It depends on various conditions such as concentration and radical initiator, but 0.5
~10 hours is preferred, and 2 to 6 hours is more preferred.

In addition, in the present invention, the reaction between PPE having a carbon-carbon unsaturated bond in the main chain aromatic ring substituent and a mercaptocarbonyl compound is carried out using an extruder, a Panbury mixer, a kneader, a lab blast mill, etc. in the presence of a radical initiator. It can also be carried out by the melt cross-wire method using . In this case, the PPE having a carbon-carbon unsaturated bond, the mercaptocarbonyl compound, and the radical initiator may be the same as those described above. In this melt-kneading reaction, the amount of the mercaptocarbonyl compound used is preferably in the range of 05 to 5 moles, more preferably 05 to 2 moles, of the carbon-carbon unsaturated bond. The reaction temperature can be carried out in the range of 150 to 380°C, but preferably in the range of 230 to 320″C.

The reaction time is 3 to 10 minutes, preferably 5 to 5 minutes (
Examples) In order to explain the present invention more specifically, Examples are shown below, but the present invention is not limited thereto. In addition, in the examples, parts and % are weight M parts and weight ■%, respectively.
shows.

The PPE used was a copolymerized PPE prepared by oxidative coupling of 2.6=xylenol and 2-allyl-6-methylphenol in the presence of a manganese chloride/jetanolamine/dibutylamine catalyst as shown in Table 1. Ta.

The infrared absorption spectrum of IPPE No. in the same table is shown in FIG.

The content and reaction rate of allyl groups were calculated by 'H-NMR from the integrated intensity of signals originating from furyl groups around 3.20 ppm and 4.95 ppm.

Table 1 a) Ratio of the number of moles of allyl group to the constituent monomer units of PPE, calculated from the integrated intensity of 'H-#MR (allyl group hydrogen/aromatic hydrogen) Example 1 No. in Table 1, I 50 parts of PPE and 193 parts of mercaptoacetic acid were dissolved in 430 parts of toluene. temperature to 85
℃, add 34 parts of azobisisobutyronitrile (hereinafter abbreviated as AIBN) to 87 parts of toluene.
The mixture was added dropwise over 5 hours. After dropping, the mold was allowed to react at 85° C. for 4 hours. The resin was precipitated with a large amount of acetonitrile to obtain the desired carbonyl group-modified PPE. Table 2 shows the yield and the reaction rate of allyl group.

Examples 2 to 5 The same procedure as in Example 1 was conducted except for the amounts of PPE, mercaptoacetic acid, and AIBN shown in Table 2. The results are shown in Table 2.

Incidentally, the infrared absorption spectrum of the carbonyl group-modified PPE obtained in Example 3 is shown in FIG.

Example 6 No. I in Table 1 50 parts of PPE and 193 parts of mercaptoacetic acid were dissolved in 550 parts of chlorobenzene. Benzoyl peroxide (hereinafter abbreviated as BPO) 5 was added to 11 parts of chlorobenzene while keeping the temperature at 95°C.
．． One part was added dropwise over 1.5 hours. 95° to the page after dripping
The reaction was carried out at C for 4 hours.

The resin was precipitated with a large amount of acetonitrile to obtain the desired carbonyl group-modified PPE. The results are shown in Table 3.

Examples 7 to 9 Example 6 except for the amount of mercaptoacetic acid shown in Table 3.
The reaction was carried out in the same manner. The results are shown in Table 3.

Example 10 Under a nitrogen atmosphere, 50 parts of IPPE shown in Table 1 and 199 parts of mercaptoacetic acid were dissolved in 733 parts of chlorobenzene. The reaction was carried out for 9 hours while maintaining the temperature at 50° C. and irradiating ultraviolet rays. Precipitate the resin with a large amount of acetonitrile,
The desired carbonyl group-modified PPE was obtained.

The results are shown in Table 3.

(Effect of the invention) A novel PPE having an arbitrary number of units in which a carbonyl group is bonded to a substituent, which becomes an extremely effective compatibilizer for polymer blends of PPE resins, is provided by the reaction of a known characteristic thiol compound. We were able to.

[Brief explanation of drawings]

FIG. 1 shows the infrared absorption spectra of No., I.PPH in Table 1. FIG. 2 is an infrared absorption spectrum of the carbonyl group-modified PPE obtained in Example 3.

Claims (1)

[Claims] A polyphenylene ether having a carbon-carbon unsaturated bond as a substituent has the general formula (HS)_m-R^1-(COR^2)_n(I)(
In the formula, m and n are each an integer of 1 to 4, and R^1
is a divalent to hexavalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms,
It is an aromatic hydrocarbon group or a hydrocarbon group containing an amide bond or an ester bond, and R^2 is an alkali metal oxy group, a hydrogen atom, a hydroxyl group, an aryl group, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group, or 1. A method for producing a carbonyl group-modified polyphenylene ether, which comprises reacting a mercaptocarbonyl compound represented by (which is a hydrocarbon oxy group).