JP3409035B2 - Method for producing functionalized polyphenylene ether - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a functionalized polyphenylene ether which can be used as a plastic material for electric and electronic products, automobiles, various other industrial materials, foods and packaging fields.

[0002]

2. Description of the Related Art Polyphenylene ether is excellent in processing and productivity and can efficiently produce products and parts having a desired shape by a molding method such as a melt injection molding method and a melt extrusion molding method. Various industrial material fields,
It is widely used as a material for products and parts in the food and packaging fields. In recent years, particularly in the electric / electronic fields, automobile fields, and other various industrial fields, products and parts are diversified, and requirements for resin materials are becoming wider.

In order to meet this demand, a resin material having material properties which are not present in existing materials has been developed by a polymer alloy technology by compounding different kinds of materials or combining various existing polymer materials. Ordinary polyphenylene ether has high heat resistance and excellent mechanical properties, but since it has a poor affinity with other materials, the material of the other party that can be composited is limited. In particular, the affinity with highly polar materials such as polyamide is very poor, and functionalized polyphenylene ether is required to form a composite with such a resin.

As a means for functionalizing polyphenylene ether, a method of reacting a polyphenylene ether or a resin composition containing polyphenylene ether with a compound having a functional group has been investigated. For example, as related techniques, Japanese Patent Publication No. 52-19864 and Japanese Patent Publication No. 52-
No. 30991 discloses that a functionalized polyphenylene ether is obtained by mixing polyphenylene ether in a solution state with styrene and maleic anhydride or a polymerizable modifying compound in the presence of a radical generator, and reacting the mixture for a long time. How to get it is proposed.

However, since these methods use a solvent, a dissolving step, a polymerization step, and a solvent removing step are required,
Manufacturing costs are high in terms of equipment and energy. Further, Japanese Examined Patent Publication No. 3-52486 and Japanese Patent Laid-Open No. 62-132.
No. 924, Japanese Patent Publication No. 63-500803 and Japanese Patent Laid-Open No. 63-54425, maleic anhydride or polyphenylene ether in the presence of a radical generator, or in the absence of a radical generator, or A method has been proposed in which a functionalized polyphenylene ether is obtained by mixing with another reactive functionalized compound and reacting the resin in a molten state.

However, in this method, since the temperature for melting the resin is very high, discoloration due to thermal deterioration of the resin,
Various problems such as color tone or appearance such as generation of black gel have occurred. Further, JP-A-2000-191769 discloses a method of reacting a solid polyphenylene ether with a functionalized compound. However,
There are problems that the reaction rate is slow and the production efficiency is extremely low. Further, in Japanese Examined Patent Publication No. 63-7204, a compound capable of radical polymerization in the presence of an organic or inorganic radical polymerization initiator is supplied to polyphenylene ether in a gas phase state, but in this method, the functionalized compound itself is polymerized by itself. However, the functionalized compound was not efficiently added to the polyphenylene ether.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to efficiently obtain a functionalized polyphenylene ether excellent in color tone and appearance in a short time.

[0008]

Means for Solving the Problems As a result of earnest studies on a method for producing a functionalized polyphenylene ether, the present inventor has found that the functionalized polyphenylene ether can be shortened by supplying the functionalized compound used in the reaction in a gaseous state. They have found that they can be obtained in time, and have reached the present invention. That is, the present invention is at least one selected from the group consisting of polyphenylene ether and at least one carbon-carbon double bond or triple bond in the molecule, and a carboxyl group, an acyl oxide group, an imino group, an imide group, a hydroxyl group and a glycidyl group. 1
In a method of reacting at least one functionalized compound having a number of functional groups, the functionalized compound is supplied in a gaseous state, and is reacted with polyphenylene ether at a temperature not higher than the melting temperature of polyphenylene ether. A method for producing a functionalized polyphenylene ether is provided.

The present invention will be described in detail below. The polyphenylene ether used in the present invention has a structure of the following (formula 1), and a reduced viscosity of a chloroform solution of 0.5 g / dl at 30 ° C. is in the range of 0.15 to 1.0 dl / g, more preferably 0. It is a polymer or copolymer in the range of 20 to 0.70 dl / g.

[0010]

[Chemical 1]

[R1, R2, R3 and R4 each independently represent a hydrogen atom, an alkyl group or a halogen atom. ] Specifically, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2-methyl-6)
-Phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like.

Specific examples of the copolymer include 2,6-dimethylphenol and other phenols (for example, 2,3,6).
Examples include polyphenylene ether copolymers such as copolymers with -trimethylphenol and 2-methyl-6-methylbutylphenol). Above all, poly (2,6
-Dimethyl-1,4-phenylene ether), 2,6-
A copolymer of dimethylphenol and 2,3,6-trimethylphenol can be preferably used, most preferably poly (2,6-dimethyl-1,4-phenylene ether).
Is.

The polyphenylene ether used in the present invention can be used in the form of powder or pellets, but powder is preferred. The powdery polyphenylene ether can be obtained, for example, by adding a poor solvent such as methanol or acetone to a solution of polyphenylene ether dissolved in a good solvent such as toluene or xylene. Further, the polyphenylene ether of the present invention may be added with an appropriate additive depending on the purpose. Additives include heat stabilizers, antioxidants, UV
Absorbent, surfactant, lubricant, filler, polymer additive,
Dialkyl peroxide, peroxy, peroxy carbonate, hydroperoxide, peroxyketal and the like can be mentioned.

The functionalized compound used in the present invention has at least one carbon-carbon double bond or triple bond in the molecule and a group consisting of a carboxyl group, an acyl oxide group, an imino group, an imide group, a hydroxyl group and a glycidyl group. It is at least one organic compound having at least one functional group selected from Among these functionalized compounds, compounds having a double bond in the molecule and at least one carboxyl group, acyl oxide group or imide group in the molecule are preferable.

Specific examples thereof include maleic anhydride, maleic acid, fumaric acid, phenylmaleimide, itaconic acid, glycidyl methacrylate and glycidyl acrylate, with maleic anhydride being preferred. In the present invention, the functionalized compound is fed to the polyphenylene ether in the gaseous state. Examples of the supply method include a method of directly supplying a gasified functionalized compound, a method of diluting with an inert gas and supplying. Examples of the inert gas include helium, argon and nitrogen, with nitrogen being particularly preferable.

When diluting the gaseous functionalized compound with an inert gas, it is preferred that the functionalized compound has a volume concentration of 1% or more. The volume concentration of the functionalized compound can be obtained from the saturated vapor pressure at the temperature at which the functionalized compound vaporizes. For example, add maleic anhydride at 190 ° C in an open container.
The volume concentration of maleic anhydride is 79% when the mixture is heated to a vapor-liquid equilibrium. The higher the volume concentration of the functionalized compound, the higher the reaction rate, which is preferable. When the volume concentration is less than 1%, the reaction rate is slow and the production efficiency of the functionalized polyphenylene ether is extremely reduced.

The preferred temperature for reacting the functionalized compound with the polyphenylene ether in the present invention is 100-23.
It is 0 ° C. The higher the reaction temperature, the higher the reaction rate, but if the temperature exceeds 230 ° C., the polyphenylene ether will melt and the color tone will deteriorate. In the present invention, a radical initiator may be added to accelerate the reaction. An organic peroxide is preferably used as the radical initiator. In the present invention, when the gaseous functionalized compound and the polyphenylene ether are brought into contact with each other and reacted, the polyphenylene ether may be allowed to stand in the reaction vessel or may be stirred. The reaction apparatus for stirring and reacting is not particularly limited, but examples thereof include a Henschel mixer, a paddle mixer, and a paddle dryer, and a Henschel mixer is particularly preferable.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to Examples, but the present invention should not be limited to these Examples. <Evaluation method> 1. Amount of maleic anhydride added to the functionalized polyphenylene ether First, the reaction product was heated using a Soxhlet extractor to remove unreacted maleic anhydride remaining in the functionalized polyphenylene ether powder after the reaction. It was washed with acetone for 3 hours or more. When the functionalized polyphenylene ether after the reaction was pellets, this washing operation was performed after sufficiently pulverizing in a mortar to make powder. The washed polymer was dried under reduced pressure for 1 hour under the conditions of 150 ° C. and 0.1 mmHg. Unreacted maleic anhydride does not remain in the functionalized polyphenylene ether after drying,
After drying the powder of polyphenylene ether was dissolved in chloroform, the solution was analyzed by gas chromatography,
This was confirmed by the complete disappearance of the peak corresponding to maleic anhydride.

The amount of maleic anhydride added to the functionalized polyphenylene ether after washing and drying was quantified by titration using phenolphthalein as an indicator. Specifically, 1 g of the functionalized polyphenylene ether was weighed in a 500 ml Erlenmeyer flask, and 200 ml of toluene was added and completely dissolved. After adding a few drops of ethanol solution of phenolphthalein to this solution, add 0.0
A 1 mol / l solution of sodium methylate in methanol was added dropwise from a buret until the entire solution turned pink, and the amount of maleic anhydride added was determined from the volume of the dropped solution of sodium methylate in methanol.

2. Color tone of functionalized polyphenylene ether 0.5 g of functionalized polyphenylene ether was dissolved in 10 ml of chloroform, and the solution was placed in a quartz cell having an optical path length of 1 cm. The absorbance at 480 nm was measured using a spectrophotometer, and the measured value was multiplied by 20. The larger this measured value is, the more the polyphenylene ether is thermally deteriorated during the reaction, and the more the color tone is deteriorated. The color tone of the raw material polyphenylene ether powder was 0.23.

3. Number of black foreign matters contained in functionalized polyphenylene ether 5 g of functionalized polyphenylene ether was added to chloroform 50
After being dissolved in ml, the solution was filtered with a filter paper having a diameter of 10 cm. After the completion of filtration, the number of black foreign matters on the filter paper was counted with the naked eye. The raw material polyphenylene ether powder also contained three black foreign matters. The black foreign matter is a gel product of polyphenylene ether or dust mixed from the outside.

4. Reduced viscosity of polyphenylene ether Polyphenylene ether was used as a chloroform solution of 0.5 g / 100 ml, and it was 0.43 dl / g as a result of measurement using an Ubbelohde viscometer at 30 ° C.

[0023]

EXAMPLE 1 FIG. 1 shows an apparatus used for carrying out the present invention.
It comprises a tank for evaporating maleic anhydride (A tank) and a tank for reacting polyphenylene ether with maleic anhydride (B tank). Add 100 parts of powdered maleic anhydride to tank A.
g, 10 g of powdered polyphenylene ether was placed in the B tank. Both the tanks A and B were heated with a mantle heater while the pressure was reduced to 0.1 mmHg or less by a vacuum pump. At this time, the temperature of maleic anhydride was set to 190 ° C. in the tank A. Next, the valve D was gradually opened, and the gaseous maleic anhydride in the tank A was immediately introduced into the tank B. After that, the valve D was closed, the tank B was allowed to stand for 60 minutes while keeping the temperature at 190 ° C., then cooled in a water tank, and when cooled to room temperature, the tank was opened, and the functionalized polyphenylene ether powder was added. I took it out. The amount of maleic anhydride added to the functionalized polyphenylene ether was 0.51 parts by weight. The measured color tone is 0.3
0, the number of black foreign matter was 3.

[0024]

Comparative Example 1 10 g of polyphenylene ether powder and 1 g of solid maleic anhydride were mixed well and added to the tank B used in Example 1. Vacuum B in tank B is 0.1 mmH
After reducing the pressure to g, the container is sealed while keeping the pressure reduced, and the container is placed in a heated oil bath as it is. The temperature of the polyphenylene ether and maleic anhydride mixture in the B tank was adjusted to 190 ° C., and the reaction was allowed to stand for 60 minutes in this state. After standing for 60 minutes to react, B
The bath was cooled with a water bath, and when the bath was cooled to room temperature, the bath was opened, and the polyphenylene ether powder after the reaction was taken out. The amount of maleic anhydride added to the functionalized polyphenylene ether obtained in the reaction was 0.02 part by weight.

[0025]

[Example 2] The same procedure as in Example 1 was repeated except that the reaction time of standing was 180 minutes. The amount of maleic anhydride added to the functionalized polyphenylene ether was 0.73 parts by weight, the measured color tone was 0.42, and the number of black foreign matters was 3.

[0026]

[Example 3] The same operation as in Example 1 was performed except that the temperatures of the polyphenylene ether in the tank B and the maleic anhydride in the tank A were set to 110 ° C. The amount of maleic anhydride added to the functionalized polyphenylene ether was 0.32 part by weight, the measured color tone was 0.27, and the number of black foreign matters was 4.

[0027]

[Example 4] The same procedure as in Example 1 was carried out except that the temperatures of the polyphenylene ether in the tank B and the maleic anhydride in the tank A were set to 120 ° C. The amount of maleic anhydride added to the functionalized polyphenylene ether was 0.43 parts by weight, and the measured value of color tone was 0.3.
2. The number of black foreign matter was 4.

[0028]

Example 5 The procedure of Example 1 was repeated except that the temperatures of the polyphenylene ether in the tank B and the maleic anhydride in the tank A were 230 ° C. The amount of maleic anhydride added to the functionalized polyphenylene ether was 0.71 part by weight, and the measured color tone was 0.4.
2. The number of black foreign matter was 4.

[0029]

Example 6 The procedure of Example 1 was repeated except that the temperatures of the polyphenylene ether in the tank B and the maleic anhydride in the tank A were set to 90 ° C. The amount of maleic anhydride added to the functionalized polyphenylene ether was 0.32 parts by weight.

[0030]

[Example 7] The same procedure as in Example 1 was carried out except that the temperatures of the polyphenylene ether in the tank B and the maleic anhydride in the tank A were set to 80 ° C. The amount of maleic anhydride added at this time was 0.28.
It was part by weight.

[0031]

Comparative Example 2 The procedure of Example 1 was repeated except that the temperatures of the polyphenylene ether in the tank B and the maleic anhydride in the tank A were 240 ° C. The polyphenylene ether melted and the color tone deteriorated. The amount of maleic anhydride added at this time was 0.72
The measured values of parts by weight and color tone were 2.55.

[0032]

Example 8 2 Kg of polyphenylene ether powder was placed in a container having a capacity of 10 L equipped with a stirrer, and installed in the apparatus used in Example 1 instead of the B tank. Hereinafter, the tank containing the polyphenylene ether is referred to as a reaction tank. A
Both the tank and the reaction tank were heated with a mantle heater while the pressure was reduced to 0.1 mmHg or less by a vacuum pump. At this time, the temperature of maleic anhydride in the tank A is 20
It was adjusted to 0 ° C. Next, when valve D was gradually opened, the maleic anhydride in the gaseous state in tank A was instantaneously introduced into the reaction tank. At this point, valve D was closed and the reaction vessel was closed. While maintaining the temperature and pressure of the reaction tank, the stirrer was activated to stir and mix the polyphenylene ether powder. After stirring and mixing for 60 minutes, the mixture was cooled in a water bath, and when cooled to room temperature, the bath was opened, and the functionalized polyphenylene ether powder was taken out. The amount of maleic anhydride added to the functionalized polyphenylene ether was 0.43 parts by weight, the measured color tone was 0.35, and the number of black foreign matters was 3.

[0033]

Comparative Example 3 2 kg of polyphenylene ether powder and 21 g of solid maleic anhydride were placed in the reaction vessel used in Example 8, and the pressure inside the vessel was reduced to 0.1 mmHg using a vacuum pump. The vessel was hermetically closed while the pressure inside the vessel was reduced, and heated with a mantle heater so that the internal temperature was 190 ° C., and the mixture was stirred and mixed for 1 hour while maintaining the temperature. Maleic anhydride added to the functionalized polyphenylene ether powder was 0 parts by weight.

[0034]

Example 9 The procedure of Example 8 was repeated except that the reaction time was 2 hours. The amount of maleic anhydride added to the functionalized polyphenylene ether was 0.56 parts by weight, the measured color tone was 0.45, and the number of black foreign matters was 6.

[0035]

[Example 10] Example 8 except that the temperature of the polyphenylene ether in the reaction tank and the temperature of maleic anhydride in the tank A were set to 120 ° C.
I went the same way. The amount of maleic anhydride added to the functionalized polyphenylene ether was 0.30 part by weight, the measured color tone was 0.25, and the number of black foreign matters was 3.

[0036]

Example 11 The procedure of Example 8 was repeated except that the temperatures of the polyphenylene ether in the reaction tank and the maleic anhydride in the tank A were changed to 90 ° C. The amount of maleic anhydride added to the functionalized polyphenylene ether was 0.33 part by weight, and the measured value of color tone was 0.
25, and the number of black foreign matters was 3.

[0037]

[Comparative Example 4] 5 kg of polyphenylene ether powder and 100 g of solid maleic anhydride were mixed well, and then 320 using a twin-screw extruder ZSK-25 manufactured by Werner.
The mixture was kneaded and extruded at ℃ to obtain pellets. The amount of maleic anhydride added to the functionalized polyphenylene ether is 0.40.
Weight part, color tone measured value is 3.13, black foreign matter number is 61
It was an individual.

[0038]

[Comparative Example 5] The procedure of Comparative Example 4 was repeated except that the amount of maleic anhydride was 200 g. The amount of maleic anhydride added to the functionalized polyphenylene ether was 0.56 parts by weight, the measured color tone was 2.33, and the number of black foreign matters was 49.

[0039]

Reference Example 1 The reaction product obtained in Example 9 was added to 150
The mixture was allowed to stand and dry under vacuum at 2 ° C. for 2 hours to remove unreacted maleic anhydride. The complete removal of the released maleic anhydride was confirmed by analyzing the powdered chloroform solution after drying by gas chromatography and confirming the complete disappearance of the peak corresponding to maleic anhydride. The amount of maleic anhydride added to the dried polyphenylene ether powder was quantified, and the result was 0.56 parts by weight, the same as before drying. After thoroughly mixing 30 parts by weight of the powder of the functionalized polyphenylene ether after drying, 59 parts by weight of the hydrogenated styrene-butadiene block copolymer, 66 parts of polyamide 66 resin and 5 parts by weight of polyamide 6 resin, the product of Werner Co. 32 using the twin-screw extruder ZSK-25
Kneading and extrusion were performed at 0 ° C. to obtain pellets. This pellet is molded into an ASTM standard test piece by an injection molding machine,
Izod (notched) impact strength (ASTM D-2
56: 23 ° C.) was measured and found to be 199 J / m.

[0040]

Reference Example 2 Pellets were obtained in the same manner as in Reference Example 1 except that the functionalized polyphenylene ether powder obtained in Example 8 was used. This pellet is AS
The test piece was molded into a TM standard test piece, and the Izod (notched) impact strength (ASTM D-256: 23 ° C.) was measured. As a result, it was 170 J / m.

[0041]

Reference Example 3 Pellets were obtained in the same manner as in Reference Example 1 except that the functionalized polyphenylene ether powder obtained in Comparative Example 3 was used. This pellet is AS
It was 49 J / m as a result of molding into a TM standard test piece and measuring the Izod (notched) impact strength (ASTM D-256: 23 ° C).

[0042]

The method of the present invention makes it possible to provide a functionalized polyphenylene ether which is fully functionalized in a short time and which is excellent in color tone, appearance and mechanical properties.

[Brief description of drawings]

1 is a schematic diagram of an apparatus for functionalizing a polyphenylene ether with a gas of a functionalizing compound.

[Explanation of symbols]

A: Tank for gasifying functionalized compound (A tank) Volume is 1 L, ratio of internal diameter (D) to height (L) (L / D) is 2 B: Polyphenylene ether and functionalized compound are reacted The reaction tank capacity is 10 L, the ratio of inner diameter (D) to height (L) (L / D)
2 C, D, E: Pipe for introducing nitrogen gas into valve F: A G: Pipe for introducing mixed gas of gaseous functionalized compound and nitrogen into B: H: B for discharging gas from B Pipes I, J: Thermocouple thermometer K, L: Pressure gauge

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 2000-191769 (JP, A) JP 2001-19839 (JP, A) JP 2001-302873 (JP, A) JP 2001-302901 (JP, A) JP 2001-302739 (JP, A) JP 2001-302738 (JP, A) JP 2002-220460 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 65 / 48

Claims (7)

(57) [Claims] 1. From (A) polyphenylene ether and (B) at least one carbon-carbon double bond or triple bond in the molecule, and a carboxyl group, an acyl oxide group, an imino group, an imide group, a hydroxyl group and a glycidyl group. A method of reacting at least one functionalized compound having at least one functional group selected from the group consisting of supplying the functionalized compound to the polyphenylene ether in a gaseous state, and at a temperature not higher than the melting temperature of the polyphenylene ether. A method for producing a functionalized polyphenylene ether, which comprises reacting with a polyphenylene ether. 2. The method for producing a functionalized polyphenylene ether according to claim 1, wherein the functionalized compound is maleic anhydride. 3. The method for producing a functionalized polyphenylene ether according to claim 1, wherein the functionalized compound in a gaseous state is diluted with an inert gas. 4. The volume concentration of the functionalized compound in the gaseous state is 1%.
It is above, The manufacturing method of functionalized polyphenylene ether of Claim 3 characterized by the above-mentioned. 5. The method for producing a functionalized polyphenylene ether according to claim 1, wherein the reaction rate is 100 ° C. to 230 ° C. 6. The method for producing a functionalized polyphenylene ether according to claim 1, wherein the reaction is carried out using a Henschel mixer. 7. The method for producing a functionalized polyphenylene ether according to claim 1, wherein the reaction is carried out using a paddle dryer.