JPH05163344A - Method for producing polyphenylene ether having silyl group - Google Patents

Abstract

(57) [Summary] [Structure] A method for producing a silyl-modified polyphenylene ether by reacting a polyphenylene ether having an alkenyl group with a silane compound represented by the general formula I. Embedded image H-Si (Q ¹ ) _n (Q ² ) _3-n (I) (In the formula, n is an integer of 1 to 3, Q ¹ is an alkoxy group having 1 to 20 carbon atoms, an aromatic oxy group. .Q ² showing a group or a halogen group, a hydrogen atom, an aromatic group, an aromatic alkyl group of the alkyl group or C1-20 C20 .n or (3-n) is 2 or more At this time, Q ¹ and Q ² may be different from each other.) [Effect] According to the method of the present invention, a silyl-modified polyphenylene ether can be produced in an extremely high yield. The polyphenylene ether functionalized with the alkoxysilyl group, aryloxysilyl group or halogenated silyl group is useful as a compatibilizing agent for polymer alloys.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a silyl-modified polyphenylene ether having an arbitrary number of silyl groups having a hydrolyzable substituent by a hydrosilylation reaction. Polyphenylene ether having this functional group has coating properties, printability, adhesiveness, gas permeability,
It is a resin having excellent cross-linking properties, and is useful as a film, a gas separation membrane, a container, a vehicle member, an electric member, a compatibilizer for polymer alloys, and a modifier for polyphenylene ether.

[0002]

2. Description of the Related Art In recent years, demands for molding resins have been diversified and sophisticated. Therefore, development of a resin having a functional group is required, and polyphenylene ether is no exception. For example, polyphenylene ether and a resin incompatible with it, such as polyethylene terephthalate, polybutylene terephthalate,
In the blend with polypropylene, nylon 6, nylon 6,6, nylon 4,6, nylon 6,10, nylon 6,12, polyphenylene sulfide, etc., both are blended in order to exhibit a micro-dispersed form and to obtain a tough interfacial strength. It is effective to use, as a compatibilizer, a block body or a graft body composed of a segment having an affinity for each of the resins. One of the important methods for synthesizing these is the bonding of polymers with functional groups that react with each other. Further, it is considered that the yield of the compatibilizing agent synthesized depends largely on the concentration of the functional group in the polymer.

Examples of this functional group include an alkoxysilyl group, an aromatic oxy group and a halogenated silyl group. Among these, as a method of introducing an alkoxysilyl group into polyphenylene ether, JP-A-63-503392 discloses a method of graft-reacting vinyltrimethoxysilane with polyphenylene ether in the presence of a radical initiator in chlorobenzene. ing. However, this method has a drawback that the amount of alkoxysilyl groups introduced cannot be controlled.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a method for producing a silyl-modified polyphenylene ether having an alkoxysilyl group, an aromatic oxysilyl group or a silyl halide group, which is a reactive functional group, in an arbitrary number in a molecule. It is a thing.

[0005]

The present invention provides a method for producing a silylated modified polyphenylene ether by reacting a polyphenylene ether having an alkenyl group with a silane compound represented by the general formula I.

[0006]

Embedded image H-Si (Q ¹ ) _n (Q ² ) _3-n (I)

(In the formula, n is an integer of 1 to 3, Q ¹ is an alkoxy group having 1 to 20 carbon atoms, an aromatic oxy group or a halogen group. Q ² is a hydrogen atom, an aromatic group or a carbon atom. Number 1
Is a C20 alkyl group or a C1-20 aromatic alkyl group. When n or (3-n) is 2 or more, Q ¹ and Q ² may be different from each other. The alkenyl group-containing polyphenylene ether resin used in the present invention is a polyphenylene ether obtained by oxidative polymerization of one or more monomer compounds represented by the general formula II.

[0008]

[Chemical 4]

(Where m is an integer from 1 to 4,
At least one R is an alkenyl group, and the other R is independently a halogen atom, a primary or secondary alkyl having 1 to 20 carbon atoms, aryl, haloalkyl, aminoalkyl, hydrocarbon oxy, or halogen. It represents a halohydrocarbonoxy group in which an atom and an oxygen atom are bonded via at least two carbon atoms. ) Examples of the monomer compound represented by the formula II include 2-allylphenol, 2,6-diallylphenol and 2-allyl-6-methylphenol, 2-allyl-5chlorophenol, 2-allyl-3-methoxyphenol, 2-
Allyl-3-isobutyl-6-methylphenol, 2-
Allyl-6-ethylphenol and the like, and preferably,
2-allyl-6-methylphenol.

Further, if necessary, a halogen atom, a primary or secondary alkyl, aryl, haloalkyl, or a phenol or a phenol derivative is used as a substituent.
Aminoalkyl, hydrocarbon oxy, or a halohydrocarbonoxy in which a halogen atom and an oxygen atom are bound via at least two carbon atoms (a halogen atom and an oxygen atom are separated by at least two carbon atoms) )
The monomer compound having the formula (I) may be oxidatively copolymerized with the monomer compound represented by the general formula II, and typical examples of the latter derivative include o-, m- or p-
-Cresol, 2,6-, 2,5-, 2,4- or 3,
5-dimethylphenol, 2,6-diphenylphenol, 2,6-diethylphenol, 2,3,5-, 2,
3,6-Trimethylphenol, 2-methyl-6-t-
Butylphenol and the like. Among these, 2,6-dimethylphenol and the like are preferable.

Main components are the above-mentioned monomer compounds, and bisphenol A, tetrabromobisphenol A, resorcin, hydroquinone, 2.2-bis (3 ', 5'-dimethyl-4'-hydroxy-phenyl) propane, bis (3 , 5-Dimethyl-4-hydroxy-phenyl) methane, or 3,3 ', 5,5'-tetramethyl-4.
It is also possible to use a polymer having a polyvalent hydroxyaromatic compound such as 4'-dihydroxy 4,4'-dihydroxybiphenyl as a copolymerization component.

Further, the production of the polymer can be carried out in the same manner as the usual oxidative polymerization of polyphenylene ether,
For example, US Pat. No. 3,422,062, US Pat.
No. 306,874, No. 3,306,875, No. 3,257,257, and No. 3,257,358. The catalyst used for the oxidative polymerization is not particularly limited, and any catalyst capable of obtaining a desired degree of polymerization may be used. Many catalyst systems are known in the art consisting of cuprous salt-amine, cupric salt-amine-alkali metal hydroxide, manganese salt-primary amine, and the like.

The number average degree of polymerization of the polyphenylene ether having an alkenyl group shown above is preferably 10 to 400. When it exceeds 400, handling is not easy such as deterioration of molding processability due to increase of melt viscosity. Further, in the case of a copolymer, it may be a random copolymer or a block copolymer. Specific examples of the silane compound represented by the general formula II include trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxysilane, tripentoxysilane, silylhexanoxysilane, triheptoxysilane, trioctoxysilane. , Triphenoxysilane, tris (methylphenoxy) silane, tribenzyloxysilane, tris (phenylethoxy) silane, tris (phenylpropoxy) silane, tris (phenylbutoxy) silane, methoxydibutoxysilane, methoxydiphenoxysilane, dimethoxybutoxy Silane, dimethoxyphenoxysilane, trichlorosilane, tribromosilane, trifluorosilane, methyldichlorosilane,
Examples thereof include dimethylchlorosilane, methyldimethoxysilane, dimethylmethoxysilane, ethyldichlorosilane, diethylchlorosilane, ethyldimethoxysilane, diethylmethoxysilane, phenyldichlorosilane, diphenylchlorosilane, phenyldimethoxysilane and diphenylmethoxysilane. Among these, trimethoxysilane and triethoxysilane are preferable.

In the production of the functionalized polyphenylene ether of the present invention, the amount of the silane compound used is usually 1 to 25 times mol, preferably 1 to 15 times mol, of the alkenyl group in the polyphenylene ether having an alkenyl group. When the amount used is less than 1-fold mole, the reaction rate of the alkenyl group decreases, while when it exceeds 25-fold mole, unreacted silane compound increases, which causes a problem in economic efficiency.

The reaction solvent that can be used is not particularly limited as long as it can dissolve the polyphenylene ether having an alkenyl group and the silane compound represented by the general formula II. For example, benzene, toluene, xylene, mesitylene, chlorobenzene, Dichlorobenzene, chloroform, tetrahydrofuran and the like can be mentioned. The amount of these reaction solvents used is 0.01 to 60% by weight, preferably 1 to 30% by weight, of the polyphenylene ether having an alkenyl group. If it exceeds, stirring may be difficult.

In the production of the silyl-modified polyphenylene ether of the present invention, as a catalyst optionally used, tin, nickel, palladium, platinum, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, technetium, chromium, molybdenum, Mention may be made of metals such as tungsten such as IVB, VIA, VIIA or VIIIA in the periodic table, metal salts, and organometallic compounds and metal complexes of these metals.

Examples of the organic metal compound and the metal complex include dibutyltin laurate, dimethylbis (trimethylphosphine) nickel (II), diethyl (2,2 ').
-Bipyridyl) nickel (II), dimethylbis (triphenylphosphine) palladium (II), iodotrimethylplatinum (IV), tricarbonyl (7-allyl) cobalt (I) and other alkyl metal compounds, nickel tetracarbonyl, dodecacarbonyl Tetra rhodium, pentacarbonyl iron, decacarbonyl dimanganese (0), hexacarbonyl chromium (0), hexacarbonyl molybdenum (0),
Metal carbonyl compounds such as hexacarbonyltungsten (0), nickel chloride, chloroplatinic acid, cobalt chloride,
Metal complex salts such as rhodium chloride, dichlorobis (triphenylphosphine) nickel (II), terrorakis (triphenylphosphine) nickel (0), dichlorobis (benzonitrile) palladium (II), tetrakis (triphenylphosphine) palladium (0), Basic ligands such as dichlorobis (tributylphosphine) platinum (II), tetrakis (triphenylphosphine) platinum (0), chlorotris (triphenylphosphine) cobalt (I), and chlorotris (triphenylphosphine) rhodium (I) are used. The metal complex which it has can be mentioned.

Of these catalysts, preferred are palladium or platinum dispersed on carbon powder as a carrier, dibutyltin laurate, pentacarbonyliron, chloroplatinic acid, dichlorobis (benzonitrile) palladium (I
I), chlorotris (triphenylphosphine) rhodium (I), tetrakis (triphenylphosphine) palladium (0) and the like, and among them, chloroplatinic acid is preferable.

The amount of the catalyst used is usually 1 × 10 5 of the alkenyl group of the polyphenylene ether having an alkenyl group.
^-4 to 0.1 mol times, and if it is less than 1 x 10 ^-4 mol times, the reaction rate of the alkenyl group is low, while if it exceeds 0.1 mol times, a rapid reaction may occur, which is dangerous. Also,
In addition to the above metal catalysts, dibenzoyl peroxide,
Representative of organic peroxides exemplified by di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, etc., and azo compounds exemplified by azobisisobutyronitrile, azobisisovaleronitrile etc. It is also effective to use such a radical initiator or to irradiate with ultraviolet rays.

In the production of the functionalized polyphenylene ether of the present invention, the reaction temperature is usually 0 to 300 ° C., preferably 50 to 150 ° C. When the temperature is lower than 0 ° C., the reaction rate is slow, while when it exceeds 300 ° C. Rapid decomposition and side reactions of the catalyst may occur. The reaction atmosphere is preferably carried out in a reducing or inert gas in order to prevent deactivation of the catalyst, and as such a gas, hydrogen, helium, argon, nitrogen or the like is used. It is preferable to use these gases in a dry state in order to prevent side reactions. For the same reason, it is preferable to use a dried reaction solvent, but water contained in a commercially available solvent, for example, several ppm to several% of water does not change the essence of the reaction.

The order of adding the alkenyl group-containing polyphenylene ether, the silane compound and the catalyst is not particularly limited, but it is usually preferable to add the catalyst to a solution of the alkenyl group-containing polyphenylene ether and the silane compound. The method of recovering the silyl group-modified polyphenylene ether from the reaction solution is a method of removing the solvent or unreacted silane compound under heating or heating under reduced pressure, or a method of precipitating with a poor solvent such as methanol, ethanol, propanol, butanol, or acetonitrile. There is.

The production of the functionalized polyphenylene ether of the present invention is carried out by using the above-mentioned polyphenylene ether having an alkenyl group and a silane compound in an extruder, a Banbury mixer,
It can also be carried out by melt-kneading using a kneader, Labo Plastomill or the like. Also in this case, the amount of the silane compound used and the amount of the catalyst used if necessary are substantially the same as those shown above. The reaction temperature is 200 ° C to 3
It can be carried out in the range of 20 ° C. If the temperature is lower than 200 ° C, the polyphenylene ether having an alkenyl group is difficult to melt, and if the temperature is higher than 320 ° C, deterioration of the polyphenylene ether having an alkenyl group becomes a problem.

The rate of modification of the resulting functionalized polyphenylene ether with a silyl group can be arbitrarily controlled by the content of the alkenyl group in the polyphenylene ether, but when considered as a compatibilizer, the content of the silyl group is considered. Is 3 per molecule of polyphenylene ether
0 or less, preferably 1 to 25. If the number exceeds 30, gelation is likely to occur and molding becomes difficult. The number average degree of polymerization is 10 to 400. When it exceeds 400, handling is not easy such as deterioration of molding processability due to increase of melt viscosity.

[Application of functionalized polyphenylene ether]
By using the silyl-modified polyphenylene ether obtained in the present invention, the compatibility between the polyphenylene ether and the different polymer is improved, and the island polymer can be uniformly finely dispersed in the sea polymer. This improves the drawbacks of polyphenylene ether, such as moldability and solvent resistance. Specifically, the silyl-modified polyphenylene ether obtained in the present invention and the different polymer are melt-kneaded at a weight ratio of 9: 1 to 1: 9 to obtain a finely dispersed resin composition.

The heterogeneous polymer may be any polymer having a site capable of reacting with a silyl group which is a functional group in the functionalized polyphenylene ether obtained in the present invention, and specifically, polyamide, polyethylene terephthalate, polybutylene terephthalate. Etc. It is also possible to use various modified polymers having functionalized reactive sites, such as maleic anhydride modified polyolefin, hydroxyl group modified polyolefin, and unsaturated carboxylic acid modified polyphenylene sulfide.

Examples of the melt-kneading device for preparing the composition include a Labo Plastomill, a Banbury mixer, an extruder and the like. Also, other devices may be so-called high-viscosity stirrer or high-viscosity mixer, for example, multi-screw kneader,
A horizontal biaxial stirrer such as a horizontal biaxial multi-disk device or a horizontal biaxial surface renewer, or a vertical stirrer such as a double helical ribbon stirrer can be used.

The kneading temperature may be in the range of 150 ° C to 380 ° C, but is preferably in the range of 200 ° C to 320 ° C. The kneading time is preferably 0.5 minutes to 20 minutes, more preferably 1 minute to 10 minutes. The composition of the composition is composed of the silyl-modified polyphenylene ether (A) obtained in the present invention and a different polymer (B),
The composition ratio of the components (A) and (B) is a weight ratio (A):
(B) is in the range of 10:90 to 90:10, preferably 20:80 to 80:20. Further, the component (A) can be replaced with an unmodified polyphenylene ether (C), and the amount thereof is as shown below. The sum of the components A, B and C is 100% by weight.

(A) 10 to 90% by weight (B) 10 to 90% by weight (C) 0 to 80% by weight If necessary, glass fiber, pigment, inorganic filler, flame retardant,
Antioxidants, lubricants, antistatic agents, ultraviolet absorbers and the like can be added.

[0029]

Since a phenylene ether having an arbitrary number of alkenyl groups is reacted with a silane compound represented by the general formula I, a known poly (2,6-dimethylphenylene ether) is later grafted with vinylsilane to introduce a functionalized silyl group. It is easier to control the silyl group content than is the case.
Also, a large number of silyl groups can be introduced.

[0030]

EXAMPLES In order to more specifically illustrate the present invention, examples thereof will be shown below, but the present invention is not limited thereto.
The parts and percentages shown below are based on weight. For the content of alkenyl groups in the polyphenylene ether, the reaction rate was shown in mol% based on the number of main chain phenylene rings, and calculated from the integrated intensity of ¹ H-NMR. Also, the number average molecular weight (assumed to be Mn) and the molecular weight distribution value (assumed to be Q value)
Is a polystyrene conversion value measured by GPC.

Synthesis Example 1 Synthesis example of polyphenylene ether having alkenyl group 2-61 parts of allyl-6-methylphenol, 950 parts of 2,6-dimethylphenol and sodium hydroxide 9.
1 part was dissolved in a mixed solvent of 2890 parts of xylene and 766 parts of methanol. Next, diethanolamine 20.5
Parts, dibutylamine 12.6 parts, and manganese chloride tetrahydrate 0.48 parts dissolved in methanol 316 parts were added in this order. The polymerization reaction was divided into two stages, and in the former stage, the temperature was kept at 40 ° C., oxygen gas was introduced at a flow rate of 0.8 liter / min to carry out the reaction, and the reaction was continued until a solid was deposited.
In the latter stage, the temperature was kept at 30 ° C., oxygen gas was introduced at a flow rate of 0.8 liter / min, and nitrogen gas was introduced at 8 liter / min until the precipitation of the polymer stopped. The polymer was washed with hydrochloric acid-methanol to deactivate the catalyst. As a result, polyphenylene ether in which the structural units represented by the following formulas III and IV were randomly polymerized (molar ratio 5:99) was obtained.

[0032]

[Chemical 5]

[0033]

[Chemical 6]

Alkenyl group content: 4.8 mol% Polymer yield: 86% Mn: 15,800 Q value: 2.58

[Synthesis Example 2] Synthesis Example of Polyphenylene Ether Having Alkenyl Group 2- Synthesis except that the amount of allyl-6-methylphenol used was 243 parts and the amount of 2,6-dimethylphenol used was 800 parts. The reaction was carried out as in Example 1. As a result, polyphenylene ether in which the structural units represented by the above formulas III and IV were randomly polymerized (molar ratio 25:94) was obtained. Alkenyl group content; 21 mol% Polymer yield; 81% Mn; 11,800 Q value; 2.57

[Synthesis Example 3] Polyphenylene ether with vinyltrimethoxysilane
Of 50 parts vinyltrimethoxysilane and polyphenylene ether [manufactured by Nippon Polyether Co., Ltd., poly (2,6-dimethylphenylene ether), intrinsic viscosity of 0.31 dl measured in chloroform at 30 ° C. / G)] 100 parts was dissolved in chlorobenzene. At the reflux temperature, 100 parts of a 5% solution of dicumyl peroxide in chlorobenzene was added dropwise and the reaction was carried out for 3 hours. After the reaction was completed, the polymer was reprecipitated and washed with a large amount of methanol. Finally, it was dried under vacuum at 100 ° C. to obtain vinyltrimethoxysilane graft-modified polyphenylene ether. Yield: 96%

Example 1 Synthesis Example 1 under nitrogen gas atmosphere
After 1300 parts of dehydrated toluene and 78 parts of trimethoxysilane were sequentially added to 150 parts of the polyphenylene ether having an alkenyl group obtained in above, the temperature was kept at 80 ° C. to obtain a uniform solution. 24 parts of a catalyst (0.001 mol / liter of chloroplatinic acid in isopropanol) was added thereto, and the mixture was reacted at 80 ° C. for 12 hours. After the reaction was completed, the polymer was reprecipitated and washed with a large amount of methanol. Finally, it was dried under vacuum at 100 ° C. to obtain the desired polyphenylene ether functionalized with a trimethoxysilyl group. Yield: 89% Reaction rate of allyl group: About 100%

Example 2 The reaction was carried out under the same conditions as in Example 1 except that 150 parts of the polyphenylene ether having an alkenyl group obtained in Synthesis Example 2 and 64 parts of trimethoxysilane were used. Yield: 95% Reaction rate of allyl group: 84%

[Application Example] Trimethoxysilyl-modified polyphenylene ether obtained in Example 1 and polyamide-6 [B
ASF Ultramid KR4411 (trade name)] according to the composition shown in Table 1, each component was kneaded at 280 ° C. and 180 rpm for 5 minutes using a Labo Plastomill kneader manufactured by Toyo Seiki Seisakusho, and then pulverized. To obtain a granular resin composition. This resin composition was press-molded at 280 ° C. to give a thickness of 2
mm sheets were created. Test pieces were cut out from this sheet and evaluated for physical properties.

Comparative Application Example The reaction was carried out in the same manner as in the application example except that the vinyltrimethoxysilane graft-modified functionalized polyphenylene ether obtained in Synthesis Example 3 was used in place of the functionalized polyphenylene ether obtained in Example 1. It was

The characteristics of the resin compositions obtained in the application examples and comparative application examples were measured and evaluated by the following methods. The measurement results are shown in Table 1. (1) Izod impact strength: In accordance with JIS K7110, three notched Izod impact strengths at 23 ° C. were measured by stacking three 2 mm-thick test pieces. (2) Flexural modulus: A test piece having a width of 25 mm and a length of 80 mm was cut, and measured according to JIS K7203 using an Instron tester.

[0042]

[Table 1]

[0043]

The polyphenylene ether functionalized with an alkoxysilyl group, aryloxysilyl group or halogenated silyl group is useful as a compatibilizing agent for polymer alloys.

[Brief description of drawings]

FIG. 1 is a ¹ H-NMR chart of polyphenylene ether having an alkenyl group in Synthesis Example 1.

FIG. 2 is a ¹ H-NMR chart of trimethoxysilyl-modified polyphenylene ether obtained in Example 1.

Claims (2)

[Claims] 1. A method for producing a silyl-modified polyphenylene ether by reacting a polyphenylene ether having an alkenyl group with a silane compound represented by the general formula I. Embedded image H-Si (Q ¹ ) _n (Q ² ) _3-n (I) (In the formula, n is an integer of 1 to 3, Q ¹ is an alkoxy group having 1 to 20 carbon atoms, an aromatic oxy group. .Q ² showing a group or a halogen group, a hydrogen atom, an aromatic group, an aromatic alkyl group of the alkyl group or C1-20 C20 .n or (3-n) is 2 or more , Then each Q ¹ and Q ² may be different.) 2. A polyphenylene ether having an alkenyl group and a compound represented by the general formula I are represented by periodic tables IVB, VIA,
A method for producing a silyl-modified polyphenylene ether by reacting in the presence of a metal of VIIA or VIIIA and a compound containing these metals. Embedded image H-Si (Q ¹ ) _n (Q ² ) _3-n (I) (In the formula, n is an integer of 1 to 3, Q ¹ is an alkoxy group having 1 to 20 carbon atoms, an aromatic oxy group. .Q ² showing a group or a halogen group, a hydrogen atom, an aromatic group, an aromatic alkyl group of the alkyl group or C1-20 C20 .n or (3-n) is 2 or more , Then each Q ¹ and Q ² may be different.)