JPH04103629A - Method for producing hydroxyl group-modified polyphenylene ether - Google Patents

Abstract

PURPOSE:To obtain the subject polymer, excellent in mechanical strength and impact resistance and useful as a compatibilizing agent, etc., by reacting a polyphenylene ether having carbon-carbon unsaturated bond in a substituent group with a specific mercaptan. CONSTITUTION:A polyphenylene ether, having carbon-carbon unsaturated bond in a substituent group and composed of, e.g. 2,6-diallylphenol is allowed to react with a mercaptan (e.g. 2-mercaptoethanol used in an amount of preferably 0.5-2 times based on the number of mol of the carbon-carbon unsaturated bond) expressed by the formula ((m) and (n) are respectively integers of 1-4; R<1> is 1-20C bi- to hexafunctional saturated hydrocarbon group, aromatic group or hydrocarbon group containing ether bond, amide bond or ester bond), preferably at 230-320 deg.C for 0.5-5min to afford the objective polymer.

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 be physically or chemically bonded to a different type of polymer.

Specifically, the present invention relates to a method for producing an aqueous group-modified polyphenylene ether useful for improving compatibility, which is obtained by reacting a polyphenylene ether having an arbitrary number of carbon-carbon unsaturated bonds with a mercaptan having a hydroxyl group.

(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. Therefore, when the two components are simply mixed, they exhibit an energetically stable phase-separated structure, but the adhesion at the interface of this two-phase structure is not good, resulting in a decrease in mechanical strength and impact resistance. , shows major problems such as easy delamination during molding.

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. To synthesize these, there are cases where a bifunctional small molecule such as maleic anhydride is used as a binder, and cases where polymers having functional groups that react with each other are bonded together. The type and number of functional groups in the molecule are important.

As an example of these methods, there are many methods in which unsaturated carboxylic acids, unsaturated imides, unsaturated epoxides, etc. are subjected to a crosstalk reaction, but there are restrictions on the control of the number and types of functional groups that can be introduced.

In addition, examples of introducing various functional groups using the terminal phenolic hydroxyl group of PPE as a reaction site have been proposed.
For example, JP-A-63-199754 or Japanese Patent Publication No. 1987-1997-
The terminal carboxylic anhydride modified products shown in each publication of No. 500456, the terminal alcoholic hydroxy modified products of U.S. Patent No. 4746708, and U.S. Patent No. 473293
There are terminal glycidyl-modified products described in No. 7 specification, but these have at most one reactive site or functional group per polymer molecule, and cannot be said to be satisfactory in terms of the optimum number of functional groups.

(Problems to be Solved by the Invention) One of the effective methods for introducing a functional group is the reaction of a mercaptan having a hydroxyl group. Mercaptans having hydroxyl groups are known to efficiently add to carbon-carbon unsaturated bonds mainly through radical reactions, and by applying this to polymers having carbon-carbon unsaturated bonds, it is possible to functionalize polymers. It's possible to yell.

However, the reaction of mercaptans having hydroxyl groups with known PPEs having unsaturated bonds (for example, resins obtained by oxidative copolymerization of 2-allyl-6-methylphenol and 2,6-dimethylphenol (U.S. Pat. No. 3,422)
062 specification)) is not known to date.

An object of the present invention is to provide a method for producing hydroxyl-modified PPE having an arbitrary number of hydroxyl groups in one polymer molecule, which are reactive functional groups for improving the compatibility of polymer blends.

(Means for Solving the Problems) The present invention relates to a polyphenylene ether having a carbon-carbon unsaturated bond in a substituent.

General formula % Formula % () (In the formula, m and n each represent an integer of 1 to 4, and R'
is a divalent to hexavalent saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic group, or a hydrocarbon group containing an ether bond, an amide bond, or an ester bond). This is a characteristic method for producing hydroxyl group-modified polyphenylene ether.

The present invention will be specifically explained below.

PPE having a carbon-carbon unsaturated bond as a substituent used in the present invention is defined by the general formula (wherein p represents an integer of 1 to 4, R independently represents a halogen atom, a carbon atom having 1 to 20 carbon atoms, -class or secondary alkyl group, aryl group, haloalkyl group, aminoalkyl group,
It represents a hydrocarbonoxy group or a halohydrocarbonoxy group in which a halogen atom and an oxygen atom are bonded via at least two carbon atoms, and at least one R is a carbon-carbon double bond or/or a carbon-carbon triple bond. This is PPE obtained by oxidative polymerization of one or more phenols represented by the following (representing a substituent having a bond). Specific examples of this phenol include 2-allylphenol, 2゜6-diallylphenol, 2-allyl-6-methylphenol, 2-allyl-5-chlorophenol, 2-allyl-3-methoxyphenol, and 2-allylphenol. -3-isobutyl-6-methylphenol or 2-allyl-6-ethylphenol, preferably 2,6-diallylphenol,
2-allyl-6-methylphenol, 2-allyl-6-
These include ethylphenol or 2-geranyl-6-methylphenol.

In addition, if necessary, the substituent of phenol or phenol may include a halogen atom, a secondary or secondary alkyl group, an aryl group, a haloalkyl group, an aminoalkyl group,
A phenol having a hydrocarbon oxy group or a halohydrocarbon oxy group in which a halogen atom and an oxygen atom are bonded via at least two carbon atoms is oxidatively copolymerized with the above-mentioned maximum (H) phenol. Typical examples of this phenol include 0-lm- or p-cresol: 2.6-12.5-.

2,4- or 3,5-dimethylphenol.

2.6-diphenylphenol: 2.6-dinitylphenol: 2.3.5- or 2.3.6-dolimethylphenol or 2-methyl-6-butylphenol, etc., preferably 2- 〇-Dimethylphenol, a major part of 2,6-dimethylphenol and a minor part of 2
．． 3.6-drimethylphenol and 〇- or p-
It is a mixture of one or more phenols selected from cresols.

Furthermore, the main components are the above-mentioned phenols, bisphenol A, tetrabromobisphenol A, resorcinol, hydroquinone, 2,2-bis(3°, 5′-dimethyl-
4”-hydroxy-phenyl)propane, bis(3,5
-dimethyl-4-hydroxy-phenyl)methane, 3.
3°.

It is also possible to use a polymer containing a polyvalent hydroxy aromatic compound such as 5.5°-tetramethyl-4,4°-dihydroxybiphenyl or 4.4°-dihydroxybiphenyl as a copolymer component.

Further, the production of the polymer can be carried out in the same manner as ordinary oxidative polymerization of PPE, for example, US Pat. No. 3,422,062
No. 3306874, No. 3306875, No. 3257257, or No. 3257358.

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

Many catalyst systems are known in the art, such as cuprous salt-amine, cupric salt-amine-alkali metal hydroxide, manganese salt-primary amine, and the like. Furthermore, there are no particular limitations on the range of the degree of polymerization, in which some of the polymer components can be modified with catalyst components, polymerization solvent components, etc., or modified with heat, oxygen, etc. in the manufacturing process and molding process. However, if the degree of polymerization is too low, a decrease in compatibilization ability becomes a problem, so the intrinsic viscosity of the chloroform solution at 30°C is O,ldf! /g is the practical lower limit, preferably 0.2dI/g or more, more preferably 0.3a! /g
That's all.

Specific examples of the mercaptan having a hydroxyl group of formula (I) used in the present invention include compounds shown in Group A.

Group A 2-mercaptoethanol, 3-mercaptopropatur, 2-mercaptopropatur, 2-mercapto-1
-Methylethanol, 4-mercaptobutanol, 3-
Mercapto-2-butanol, 1-mercapto-2-butanol, 2-mercaptobutanol, 3-mercapto-2-methylpropanol, 2-mercapto-1,1-
Dimethylethanol, 2-mercapto-2,2-dimethylethanol, 3-mercapto-1,2-propanediol, 2-mercaptophenol, 3-mercaptophenol, 4-mercaptophenol, 2-mercaptoethyl-2"-hydroxyethyl Ether, mercaptoacetic acid-2-hydroxyethyl ester, mercaptoacetic acid-
2-hydroxyethylamide, etc., preferably 2-
Mercaptoethanol, 3-mercaptopropertool,
These include 2-mercapto-1-methylethanol, 2-mercapto-1,1-dimethylethanol, 4-mercaptophenol, and more preferably 2-mercaptoethanol.

The hydroxyl-modified PPE produced in the present invention has carbon-carbon substituents.
It is obtained by adding a thiol moiety of a mercaptan having a hydroxyl group of formula (I) to PPE having a carbon unsaturated bond.

Here, the rate of modification of PPH with hydroxyl groups can be arbitrarily controlled by the content of alkenyl or alkynyl groups in PPE, but as a compatibilizer, the content of hydroxyl groups should be at least one per molecule of PPE. The number is preferably at least 30, and preferably at most 30.

PPE having carbon-carbon unsaturated bonds of the present invention and formula CI
) with a mercaptan having a hydroxyl group is carried out in an aromatic hydrocarbon solvent such as benzene, toluene, xylene, chlorobenzene, trichlorobenzene, etc. or a halogenated hydrocarbon solvent such as chloroform, dichloromethane, dichloroethane, trichloroethane, tetrachloroethane, etc. be able to.

The amount of the mercaptan having a hydroxyl group of formula (I) to be used is preferably 1 to 40 times, more preferably 2 to 20 times the number of moles of carbon-carbon unsaturated bonds.

In order to speed up the modification reaction, organic peroxides such as dibenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, etc. or azobisisobenzoate are added to the reaction system. An effective method is the presence of a radical initiator typified by an azo compound such as butyronitrile (hereinafter abbreviated as AIBN), azobisisovaleronitrile, etc., or irradiation with ultraviolet rays.

The reaction temperature is preferably in the range of 30 to 200°C, more preferably 50 to 150°C. The reaction time depends on various conditions such as temperature, concentration, radical initiator, etc.
O hours are preferred, more preferably 2 to 6 hours.

Further, in the present invention, the reaction between the PPE having a carbon-carbon unsaturated bond as a substituent and the mercaptan having a hydroxyl group of formula 1 (I) can be carried out using an extruder, Panburi mixer, kneader, etc. in the presence of a radical initiator. This can also be carried out by a melt mixing method using a lab blast mill or the like. In this case, the PPE having a carbon-carbon unsaturated bond as a substituent, the mercaptan having a hydroxyl group of formula (I), and the radical initiator may be the same as those described above. In the melt crosstalk reaction, the amount of mercaptan having a hydroxyl group used is preferably in the range of 0.5 to 5 times, more preferably 0.5 to 2 times, the number of moles of carbon-carbon unsaturated bonds9.The reaction temperature is 150
It can be carried out in the range of ~380°C, but preferably 23°C.
One reaction time in the range of 0 to 320°C is 0.3 to 10 minutes, preferably 0.5 to 5 minutes.

(Example) In order to explain the present invention more specifically, Examples are shown below, but the present invention is not limited thereto. In the Examples, parts and % are parts by weight and weight%
shows.

The PPE used was a copolymerized P produced by oxidative coupling of 2,6-xylenol and 2-allyl-6-methylphenol in the presence of a manganese chloride/jetanolamine/dibutylamine/sodium hydroxide catalyst.
PE as shown in Table 1.

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

Table 1 If.

Example 1 No. I in Table 1 50 parts of PPE and 15.6 parts of 2-mercaptoethanol were dissolved in 430 parts of i-luene, the temperature was maintained at 85°C, and A was dissolved in 173 parts of toluene.
IBN4. 0 part was added dropwise over 15 hours. After the addition, the reaction was further carried out at 85° C. for 4 hours. The resin was precipitated with a large amount of acetonitrile to obtain the desired hydroxyl group-modified PPE. P
Table 2 shows the PE recovery rate and the allyl group reaction rate.

Examples 2-5 PPE, 2-mercaptoethanol and A shown in Table 2
The same procedure as in Example 1 was carried out except for the IBN and the amount used,
These were named Example 2, Example 3, Example 4, and Example 5, respectively. The results are shown in Table 2.

Example 6 No. I in Table 1 50 parts of PPE and 30.0 parts of 2-mercaptoethanol were dissolved in 430 parts of toluene,
AI dissolved in 173 parts of toluene while keeping the temperature at 70°C
After 0 parts of BNlo was added dropwise over 2.5 hours, the mold was reacted at 70°C for 5.5 hours.

The resin was precipitated with a large amount of acetonitrile to obtain the desired hydroxyl group-modified PPE. The results are shown in Table 2, and the infrared absorption spectrum of the hydroxyl group-modified PPE is shown in FIG.

(Effects of the Invention) By the production method of the present invention, a novel product in which an arbitrary number of hydroxyl groups are bonded in one polymer molecule, which becomes an effective compatibilizer for polymer blends of PPE resins, is produced by the characteristic reaction of the thiol compound. Hydroxyl-modified PPE can be provided.

[Brief explanation of the drawing]

FIG. 1 is an infrared absorption spectrum of the hydroxyl group-modified PPE obtained in Example 6.

Claims (1)

[Scope of Claims] A polyphenylene ether having a carbon-carbon unsaturated bond as a substituent has the general formula (HS)_m-R^1-(OH)_n(I) (in the formula,
m and n each represent an integer of 1 to 4, and R^1 is a divalent to hexavalent saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic group, or a hydrocarbon containing an ether bond, an amide bond, or an ester bond. A method for producing a hydroxyl group-modified polyphenylene ether, which comprises reacting a mercaptan having a hydroxyl group represented by the following formula.