JPH04117423A - Production of alkoxysilyl-modified polyphenylene ether - Google Patents

Abstract

PURPOSE:To obtain the title compound useful as a compatibilizer for producing a polymer blend of a polyphenylene ether resin by reacting a polyphenylene ether having a C-C unsaturated bond in the substituent with a specified mercaptan. CONSTITUTION:A polyphenylene ether having a C-C unsaturated bond in the substituent (e.g. a compound obtained by oxidatively coupling 2,6-xylenol with 2-allyl-6-methylphenol) is made to react with an alkoxysilylated mercaptan of the formula [wherein (m) and (n) are each 1-4; R<1> is a 1-20C bi- to hexa-valent saturated hydrocarbyl or aromatic group; (l) is 0-2; R<2> is H, an (SH-containing) 1-20C saturated hydrocarbyl or aromatic group; and R<3> is H or R<1>] (e.g. 3- mercaptopropyltrimethoxysilane).

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, polyphenylene ether having an arbitrary number of carbon-carbon unsaturated bonds is reacted with a mercaptan having an alkoxysilyl group, and the molecule contains an arbitrary number of alkoxysilyl groups useful for improving compatibility. The present invention relates to a method for producing an alkoxysilyl group-modified polyphenylene ether.

(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. . For this reason, when the two components are simply mixed, they exhibit an energetically stable phase-separated structure, and the adhesion at the interface of this two-phase bridge structure is poor, 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-mentioned 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 phenolic hydrogen group at the terminal of PPE as a reaction site have been proposed so far.

For example, JP-A-63-199754 or JP-A-62-
No. 500456, the terminal carboxylic anhydride-modified product shown in each publication, the terminal alcoholic hydroxyl-modified product shown in U.S. Patent No. 4,746,708, or U.S. Patent No. 4,732,937.
There are terminal glycidyl-modified products etc. in the specification, but,
In these, 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.

(Problems to be Solved by the Invention) One of the effective methods for introducing a functional group is the reaction of a mercaptan having an alkoxysilyl group. It is known that the mercaptan efficiently adds to carbon-carbon unsaturated bonds mainly through radical reactions, and by applying this to polymers having carbon-carbon unsaturated bonds, it becomes possible to functionalize polymers. .

However, the reaction of a mercaptan having an alkoxysilyl group with known PPE having an unsaturated bond (for example, a resin obtained by oxidative copolymerization of 2-allyl-6-methylphenol and 2,6-dimethylphenol (U.S. No example has been known to date of application to the patent specification (Japanese Patent No. 3422062).

The present invention adds alkoxysilyl groups, which are reactive functional groups, to polymer 1 to improve the compatibility of polymer blends.
Modified PP with alkoxysilyl groups having any number in the molecule
The purpose of this invention is to provide a method for manufacturing E.

(Means for Solving the Problems) The present invention provides polyphenylene ether having a carbon-carbon unsaturated bond as a substituent, with the general formula % formula % (1) (where m and n are each an integer of 1 to 4). represents R1
represents a divalent to hexavalent saturated hydrocarbon group or aromatic group having 1 to 20 carbon atoms, β represents 0.1 or 2, and Rz represents a hydrogen atom, a carbon number of 1 to 20 containing or not containing a mercapto group; 2
0 saturated hydrocarbon group or aromatic group. R3 represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic group. .

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,
Represents a hydrocarbon oxy group or an eight-headed hydrocarbon oxy 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/and carbon-carbon Examples include PPE obtained by oxidative polymerization of one or more phenols represented by the following (representing a substitution having a triple bond). Specific examples of this phenol include 2-allylphenol, 2,6-diallylphenol, 2-allyl-6-methylphenol,
-allyl-5-chlorophenol, 2-allyl-3-methoxyphenol, 2-allyl-3-isobutyl-6-
Examples include methylphenol and 2-allyl-6-nitylphenol, preferably 2,6-diallylphenol, 2-allyl-6-methylphenol, 2-allyl-6-nitylphenol or 2-geranyl-6- Methylphenol, etc.

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,
Even if 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 oxidized and copolymerized with the phenol of general formula (II). Representative examples of these phenols 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-trimethylphenol or 2-methyl-6-
Examples include t-butylphenol, preferably 2.
6-dimethylphenol, a mixture of one or more phenols selected from a large amount of 2.6-dimethylphenol and a small amount of 2.3.6-1-dimethylphenol and 〇- or p-cresol. It is.

Furthermore, the main ingredients include the above-mentioned phenols, such as 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
．． It is also possible to use a polymer containing a polyvalent hydroxy aromatic compound such as 3'5,5'-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 PPH, for example, US Pat. No. 3,422,062
No. 3306874, No. 3306875, No. 3257257, or No. 3257358. The catalyst used in the oxidative polymerization is not particularly limited, but any catalyst that can obtain a desired degree of polymerization may be used. Many catalyst systems are known, including primary amines. Further, a part of the polymer constituents may be modified with a catalyst component, a polymerization solvent component, etc., or modified with heat, oxygen, etc. in the manufacturing process and molding process. The range of the degree of polymerization is not particularly limited, but if the degree of polymerization is too low, a reduction in compatibilization ability becomes a problem, so the practical lower limit is preferably about 0.1 dl/g, which is the intrinsic viscosity of the chloroform solution at 30°C. is 0.2 dl/g or more, more preferably 0.3 dl
/g or more.

The mercaptan having an alkoxysilyl group of formula (I) used in the present invention is not particularly limited as long as it is a compound having both a mercapto group and an alkoxysilyl group, but specific examples include compounds shown in the EA group below. .

Group A (mercaptomethyl)trimethoxysilane, (mercaptomethyl)triethoxysilane, (mercaptomethyl)
Tripropoxysilane, (mercaptomethyl)triphenoxysilane, (mercaptomethyl)dimethoxysilane, mercaptomethyl(methyl)dimethoxysilane, (mercaptomethyl)methoxysilane, mercaptomethyl(
dimethyl)methoxysilane, (2-mercabutethyl)
Trimethoxysilane, (2-mercaptoethyl)dimethoxysilane, 2-mercaptoethyl(methyl)dimethoxysilane, (2-mercaptoethyl)methoxysilane,
2-mercaptoethyl(methyl)methoxysilane, 2-
Mercaptoethyl(dimethyl)methoxysilane, (3-
Mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)dimethoxysilane, (3-mercaptopropyl)methoxysilane, 3-mercaptopropyl(dimethyl)methoxysilane, (4-mercaptobutyl)trimethoxysilane, (10-mercaptopropyl)trimethoxysilane decanyl)
Trimethoxysilane, (15-mercaptopentadecanyl)trimethoxysilane, (20-mercaptoeicosanyl)trimethoxysilane, (3,3-dimercaptopropyl)trimethoxysilane, (2,3-dimercaptopropyl) Trimethoxysilane, (1,1-dimercaptopropyl)trimethoxysilane, (1,2-dimercaptopropyl)trimethoxysilane, (1,2,3
-trimercaptopropyl)trimethoxysilane, (4
-mercaptophenyl)trimethoxysilane, (2-mercaptophenyl)trimethoxysilane, (3-mercaptophenyl)trimethoxysilane, (2,4-dimercaptophenyl)trimethoxysilane, (2,3-dimercaptophenyl) Trimethoxysilane, (2,6-dimercaptophenyl)trimethoxysilane, (2,4
, 6-trimercabutophenyl)trimethoxysilane, and preferably (3-mercaptopropyl)trimethoxysilane.

The alkoxysilyl group-modified PPE produced in the present invention has the formula (I
) can be obtained by adding a thiol moiety to a mercaptan having an alkoxysilyl group.

Here, the rate of modification of PPH with alkoxysilyl groups can be arbitrarily controlled by the content of alkenyl or alkynyl groups in PPE, but as a compatibilizer, the content of alkoxysilyl groups per molecule of PPE can be controlled as desired. It is preferable that there be at least 1 or more, and 3
It is preferable that the number is 0 or less.

The PPE having a carbon-carbon unsaturated bond of the present invention and the formula (1
) with a mercaptan having an alkoxysilyl group can react with benzene, toluene, xylene, chlorobenzene,
The reaction can be carried out in an aromatic hydrocarbon solvent such as trichlorobenzene or a halogenated hydrocarbon solvent such as dichloromethane, chloroform, dichloroethane, trichloroethane, or hexachloroethane.

The amount of the mercaptan having an alkoxysilyl group of formula (1) to be used is preferably 1 to 30 times, more preferably 2 to 10 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 generator 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 25 to 200°C, more preferably 40 to 150°C. The reaction time depends on various conditions such as temperature, concentration, radical generator, etc., but it is 0.5~
15 hours is preferable, and 2 to 10 hours is more preferable.

In addition, in the present invention, the reaction between PPE having a carbon-carbon unsaturated bond as a substituent and a mercaptan having an alkoxysilyl group of formula (1) can be carried out using a press in the presence of a radical generator.
It can also be carried out by a melt mixing method using a Pan Bali mixer, a kneader, a lab blast mill, or the like. In this case, PPE having a carbon-carbon unsaturated bond in the substituent and the formula (I)
As the mercaptan having an alkoxysilyl group and the radical generator, those equivalent to those mentioned above can be used. In the melt crosstalk reaction, the amount of mercabutane having an alkoxysilyl group to be used is preferably in the range of 0.5 to 5 times, more preferably 0.5 to 2 times, the number of 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 0.3 to 10 minutes, preferably 0.3 to 10 minutes.
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 the examples, parts and % indicate parts by weight and % by weight, respectively.

The PPE used was a copolymerized PPE prepared by oxidative coupling of 26-xylenol and 2-allyl-6-methylphenol in the presence of a manganese chloride/jetanolamine/dibutylamine catalyst, as shown in Table 1. .

In addition, the allyl group content and reaction rate were calculated by LH-NMR. The content of trimethoxysilyl group is also the same.
'H-NMR was calculated, and the ratio of trimethoxysilyl groups to benzene rings in PPE was expressed in mol%.

Table 1 Example 1 50 parts of No. I P P B in Table 1 and 831 parts of 3-mercaptopropyltrimethoxysilane (hereinafter abbreviated as MPS) were dissolved in 430 parts of toluene, and the temperature was raised to 8.
AIBN5. maintained at 5°C and dissolved in 258 parts of toluene.
0 part was added dropwise and reacted for 5 hours. Precipitate the resin with a large amount of acetonitrile to obtain the desired alkoxyl group-modified PP.
I got an E. Table 2 shows the PPE recovery rate, trimethoxysilyl group content, and allyl group reaction rate.

Incidentally, an H-NMR chart of the alkoxysilyl group-modified PPE is shown in FIG.

Examples 2 to 7 The same procedure as Example 1 was carried out except for the usage amounts of PPE, MPS, and AIBN shown in Table 2, and Examples 2 to 7 were obtained, respectively.
And so.

The results are shown in Table 2.

Example 8 Under a nitrogen atmosphere, 50 parts of No.l P PE in Table 1 and 341.6 parts of MP were dissolved in 430 parts of toluene, and the mixture was reacted for 9 hours while maintaining the temperature at 50'C and irradiating with ultraviolet rays. . The resin was precipitated with a large amount of acetonitrile to obtain the desired alkoxysilyl group-modified PPE.

The results are shown in Table 2.

(Effects of the Invention) By the method of the present invention, a novel polymer in which an arbitrary number of alkoxysilyl 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 mercaptan. Alkoxysilyl group-modified PPE
can be provided.

[Brief explanation of the drawing]

Figure 1 shows the alkoxysilyl group-modified P obtained in Example 1.
It is a 'H-NMR chart of PE.

Claims (1)

[Claims] Polyphenylene ether having a carbon-carbon unsaturated bond as a substituent has the general formula (HS)_m-R^1-[Si(R^2)_l(OR^
3)_3_-_l]_n(I) (where m and n each represent an integer of 1 to 4, and R^1 is a divalent to hexavalent saturated hydrocarbon group or aromatic group having 1 to 20 carbon atoms , where l is 0
, 1 or 2. R^2 represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms containing or not containing a mercapto group, or an aromatic group. R^3 is a hydrogen atom, carbon number 1~
A method for producing an alkoxysilyl group-modified polyphenylene ether, which comprises reacting a mercaptan having an alkoxysilyl group represented by the formula (representing a saturated hydrocarbon group or an aromatic group of 20).