JP2001302797A - Method for manufacturing novel block polymer of siloxane and polyphenylene ether and its composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a block polymer of a siloxane and a polyphenylene ether having a good balance of color and appearance, and heat resistance and mechanical property, and fully meeting the requirement of industries. SOLUTION: In this method for manufacturing a block polymer of a siloxane and a polyphenylene ether, a mixture added with 0.01-50.0 pts.wt. siloxane (B) having at least a reactive organic group containing at least a carbon-carbon double bond or a triple bond in its molecular structure is subjected to the reaction with 100 pts.wt. polyphenylene ether (A) comprising a structure unit represented by formula 1 under a reaction temperature of not lower than 50 deg.C but not higher than the melting point of (A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic material in the fields of electric / electronics, automobile, various other industrial materials, food / packaging, and a block of siloxane and polyphenylene ether which can be used as a modifier for the material. The present invention relates to a method for producing a polymer.

[0002]

2. Description of the Related Art Polyphenylene ether is excellent in processability and productivity, and can efficiently produce products and parts having a desired shape by a molding method such as a melt injection molding method or a melt extrusion molding method. It is widely used as a material for products and parts in the field, various other industrial materials, and food and packaging fields. In such applications, the flame retardancy of the resin is an important property. To increase the flame retardancy of polyphenylene ether, compounds containing halogen, phosphorus and the like have been used as flame retardants. However, halogen and phosphorus compounds are highly toxic to the human body, and polluting the environment when a resin containing these compounds is discarded.

[0003] Recently, siloxanes with low toxicity and low environmental pollution have attracted attention as flame retardants. Since siloxane and polyphenylene ether have low affinity, it is necessary to increase the affinity between siloxane and polyphenylene ether for use as a flame retardant composite material. In order to increase the affinity of these resins, it is effective to chemically bond the two resins to form a block polymer. As a method for producing a block polymer of siloxane and polyphenylene ether, a method of chemically bonding a siloxane having an organic group reactive with polyphenylene ether in a solution state or a molten state has been studied. There are several problems with the method.

[0004] The solution method of dissolving polyphenylene ether in a solvent requires a dissolution, reaction, and solvent removal steps, resulting in high cost in terms of equipment and energy. In addition, in the method of reacting in the molten state of polyphenylene ether such as melt-kneading, since the temperature at which polyphenylene ether can be melt-kneaded is very high, and the melt viscosity of polyphenylene ether is very high,
Various problems have occurred due to the extremely high reaction temperature.

That is, in the conventional melt-kneading method, since the processing temperature is close to the decomposition temperature of polyphenylene ether, discoloration occurs due to thermal deterioration, and this block polymer of siloxane and polyphenylene ether causes problems in color tone and appearance. To solve the problem of color tone and appearance, heat stabilizer,
A method has been proposed in which an additive such as an antioxidant is added to polyphenylene ether for melt extrusion, but the color tone and appearance are not sufficiently improved due to a high melt kneading temperature.

[0006] Therefore, the block polymer of siloxane and polyphenylene ether obtained by the prior art is not suitable for equipment.
It does not meet the demands of the industrial world due to problems in energy or insufficient balance between color and appearance and heat resistance and mechanical properties.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a method for producing a block polymer of siloxane and polyphenylene ether, in which a block polymer of siloxane and polyphenylene ether is efficiently produced, and in terms of equipment, energy and environment. An object of the present invention is to provide a method for producing a siloxane and polyphenylene ether block polymer which has no problem, has a good balance of color tone / appearance, heat resistance / mechanical properties, and sufficiently satisfies the demands of the industry.

[0008]

Means for Solving the Problems The present inventor has conducted various studies to achieve the above object, and as a result, has found that equipment, energy and
A method for producing a block polymer of siloxane and polyphenylene ether having excellent environmental properties, excellent color tone and appearance, and excellent heat resistance and mechanical properties has been completed. That is, the present invention relates to (B) at least one carbon-carbon double bond or triple bond in the molecular structure per 100 parts by weight of (A) polyphenylene ether comprising the structural unit of the following (formula 1). Siloxane having one reactive organic group
It is intended to provide a process for producing a block polymer of siloxane and polyphenylene ether, characterized in that a mixture to which 01 to 50.0 parts by weight is added is reacted at a reaction temperature of 50 ° C. or more and a melting point of (A) or less.

[0009]

Embedded image (R ₁ and R ₄ are each independently hydrogen, primary or secondary lower alkyl, phenyl, aminoalkyl,
Represents hydrocarbonoxy. R ₂ and R ₃ each independently represent hydrogen, primary or secondary lower alkyl, or phenyl. )

In the present invention, a crystalline polyphenylene ether having a melting point is used as a raw material, a reaction temperature of 50 ° C. or more and a melting point of (A) or less and a system substantially free of a solvent, that is, (A) ) By reacting the polyphenylene ether in the solid state with (B) a siloxane having a reactive organic group, a block polymer of siloxane and polyphenylene ether having better polymer physical properties and flame retardancy than the prior art was obtained. is there.

According to the production method of the present invention, a block polymer of siloxane and polyphenylene ether can be produced efficiently. The production method of the present invention, unlike the conventional melt-kneading method, reacts in a solid state, and does not generate shear heat at the time of melt-kneading, thermal degradation, crosslinking reaction,
It has excellent physical properties, color tone and appearance without discoloration. In addition, since the production method of the present invention reacts polyphenylene ether in a solid state, it does not require operations such as separation of a solvent and cooling of a melt-kneaded product, and is excellent in operation and energy.

Accordingly, the block polymer of siloxane and polyphenylene ether produced by the production method of the present invention has sufficient flame retardancy, has excellent color and appearance, is excellent in operation surface and energy, and It is excellent in heat resistance and mechanical properties, and the molded body obtained from this siloxane and polyphenylene ether block polymer can be widely used for applications requiring flame retardancy, and has a high operational and energy performance. There is no problem, color tone, appearance and heat resistance
Since the mechanical properties are good, it is possible to provide products and parts in various industrial fields that sufficiently satisfy the demands of the industry.

The polyphenylene ether (A) of the present invention has a repeating unit structure represented by the formula (1), and has a reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) of 0.15 to 1.0 dl / g. , More preferably 0.1.
It is a polymer or copolymer in the range of 20 to 0.70 dl / g.

[0014]

Embedded image (R ₁ and R ₄ are each independently hydrogen, primary or secondary lower alkyl, phenyl, aminoalkyl,
Represents hydrocarbonoxy. R ₂ and R ₃ each independently represent hydrogen, primary or secondary lower alkyl, or phenyl. )

Specific examples of the polyphenylene ether include poly (2,6-dimethyl-1,4-phenylene ether) and poly (2-methyl-6-ethyl-1,4
-Phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-
Dichloro-1,4-phenylene ether); and 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol and 2
-Methyl-6-butylphenol) and polyphenylene ether copolymers. Among them, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethylphenol) is most preferable. Dimethyl-1,4-phenylene ether).

US Pat. No. 3,306,687 is an example of a method for producing the polyphenylene ether (A) used in the present invention.
There is a method in which 2,6-xylenol is oxidatively polymerized using a complex of a cuprous salt and an amine described in the specification of Patent No. 4 as a catalyst. U.S. Pat. Nos. 3,306,875 and 325
Nos. 7357 and 3257358, JP-B-52-17880, JP-A-50-51197 and JP-A-63-152628 also describe (A) a method for producing polyphenylene ether. preferable.

The terminal structure of the polyphenylene ether (A) of the present invention is preferably a structure of the following (formula 3).

Embedded image [Wherein, R ₁ , R ₂ , R ₃ , and R ₄ are each the same as in the above formula (1)
Is defined similarly to R ₁ , R ₂ , R ₃ , and R ₄ . ]

The terminal structure of the polyphenylene ether (A) of the present invention more preferably has the following formula (formula 3 ').

Embedded image Wherein R ₅ and R ₅ ′ represent hydrogen or an alkyl group. ]

In the polyphenylene ether (A) of the present invention, an organic solvent derived from the polymerization solvent may remain in an amount of 5% by weight or less. It is difficult to completely remove the organic solvent caused by the polymerization solvent in the drying step after the polymerization, and usually the organic solvent remains in the range of several hundred ppm to several%. The polyphenylene ether (A) of the present invention may contain a desired additive depending on the purpose. Examples of additives used include heat stabilizers, antioxidants, UV absorbers, surfactants, lubricants, fillers, polymer additives and the like.

The siloxane having a reactive organic group (B) used in the present invention has at least one carbon-containing compound in its molecular structure.
It is at least one organic compound having a carbon double bond or a triple bond. Among them, a compound having a double bond in the molecular structure is preferable, and the reactive organic group is more preferably a structure of the following (formula 2).

[0021]

Embedded image (R ₁ represents hydrogen or a methyl group.)

In the method of the present invention for producing a block polymer of siloxane and polyphenylene ether, the siloxane having a reactive organic group (B) is used in an amount of 0.01 to 5 parts by weight per 100 parts by weight of (A) polyphenylene ether.
0.0 parts by weight, preferably 0.1 to 10.0 parts by weight are mixed and reacted. (B) When the siloxane having a reactive organic group is less than 0.01 part by weight, the amount of the functional group is insufficient, and when it is 50 parts by weight or more, unreacted (B) increases,
Affects the physical properties and appearance of the polymer.

In the method for producing a block polymer of siloxane and polyphenylene ether of the present invention, the reaction is carried out at a reaction temperature of 50 ° C. or more and a melting point of (A) or less. In the present invention, crystalline polyphenylene ether having a melting point is used as the raw material polyphenylene ether. References showing the relationship between crystalline polyphenylene ether and its melting point include, for example, Journal of
Polymer Science, Part A-2
(6) 1141-1148 (1968), Euro
pean Polymer Journal (9) 29
3-300 (1973), Polymer (19)
81-84 (1978).

In the present invention, the melting point of the polyphenylene ether (A) is determined based on the differential scanning calorimeter (DS)
In the measurement of C), it is defined as the peak top temperature of the peak observed in the temperature-heat flow graph obtained when the temperature is increased at 20 ° C./min. Defined by temperature. In the method for producing a block polymer of siloxane and polyphenylene ether of the present invention, (A) the polyphenylene ether is a powdery substance obtained by precipitation from a solution and has a melting point of 240.
It is preferably a polyphenylene ether having a temperature of from about 200C to about 260C. Further, this powder preferably has a heat of fusion (ΔH) obtained from a peak in DSC measurement of 2 J / g or more.

In the present invention, the reaction is carried out in a temperature range from 50 ° C. to the melting point of the polyphenylene ether (A). When the reaction temperature exceeds the melting point of (A), (A) melts and the viscosity increases, so that mixing with (B) siloxane having a reactive organic group is inhibited, and the reaction is not promoted. At this time,
If (A) and (B) are strongly kneaded to accelerate the reaction, the color tone and appearance of (A) deteriorate due to heat generation during kneading.

In the present invention, it is preferable to add a radical initiator to accelerate the reaction. Examples of the radical initiator include dialkyl peroxide, diacyl peroxide, peroxy, peroxycarbonate, hydroperoxide, and peroxyketal. The added amount of the radical initiator is preferably 0.01 to 10.0 parts by weight. When the amount is less than 0.01 part by weight, the effect of promoting the reaction is not seen, and when the amount is more than 10 parts by weight, the physical properties and color tone of the polymer are deteriorated.

In the method for producing the siloxane and polyphenylene ether block polymer of the present invention, the production is preferably carried out using a paddle dryer as a reactor.
By using a paddle dryer in which the jacket temperature is set to a desired temperature, efficient production can be achieved. Further, it is more preferable to use a Henschel mixer as the reactor. When a Henschel mixer is used as a reactor, (A) polyphenylene ether and (B) a siloxane having a reactive organic group can be efficiently mixed, and can be heated by shearing heat, so that a block polymer of the siloxane and polyphenylene ether of the present invention can be obtained. Can be manufactured efficiently.

The siloxane and polyphenylene ether block polymer of the present invention can be efficiently produced by using a hopper having a jacket temperature set to a desired temperature.

However, the method for producing the siloxane and polyphenylene ether block polymer of the present invention is not particularly limited. The siloxane and polyphenylene ether block polymer of the present invention have excellent mechanical properties,
Can be used as is. Alternatively, it can be mixed with other compositions and used as a melt-kneaded polymer alloy or polymer composite. Furthermore, it is also possible to mix it with other compositions and solvents and use it as a dissolved polymer alloy or polymer composite. Among them, it can be used very preferably for a polymer alloy kneaded with siloxane or glass fiber.

The use of the siloxane and polyphenylene ether block polymers of the present invention is not particularly limited, and is widely used in the fields of electricity and electronics, the field of automobiles, various other industrial materials, and the fields of food and packaging. Applicable. The polymer alloy containing the siloxane and polyphenylene ether block polymer of the present invention, or the polymer composite is used in the electric and electronic fields,
It can be preferably applied to applications in the automotive field, other various industrial material fields, and food / packaging fields.

The block polymer of siloxane and polyphenylene ether of the present invention is excellent in color tone / appearance, mechanical properties, and productivity. Therefore, it can be used in electric / electronic fields, automobile fields, various other industrial materials fields, food / packaging fields. It can be used very preferably for applications requiring flame retardancy.

[0032]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples as long as the gist is not exceeded.
In the examples and comparative examples, the following (A) polyphenylene ether was used. A-1: Poly (2,6-dimethyl-1,4 having a reduced viscosity of 0.42 obtained by oxidative polymerization of 2,6-dimethylphenol.
A-2: poly (2,6-dimethyl-1,4, having a reduced viscosity of 0.54, obtained by oxidative polymerization of 2,6-dimethylphenol.
-Phenylene ether) In Examples and Comparative Examples, the following siloxane (B) having a reactive organic group was used. B-1: A linear dimethylsiloxane having a structure of the following formula (4) at both ends and having a viscosity of 15 m
m ² / s compound

[0033]

Embedded image

In Examples and Comparative Examples, the melting point was evaluated by the following method. (A) A differential thermal scanning calorimeter (DSC) was measured for polyphenylene ether, and the peak top temperature in a temperature-heat flow graph obtained when the temperature was raised at 20 ° C./min was defined as the melting point. The temperature-heat flow graph of polyphenylene ether (A-1) shows a single peak with a melting point of 250
° C. The temperature-heat flow graph of polyphenylene ether (A-2) shows a single peak with a melting point of 245.
° C.

[0035]

Example 1 Polyphenylene ether (A-1) 100
g and 5 g of a siloxane (B-1) having a reactive organic group and 5 iron balls for stirring with a diameter of 5 mm were placed in an autoclave equipped with a gas inlet, and the inside was passed through the gas inlet at room temperature to 10 mmHg. After the pressure was reduced to atmospheric pressure, nitrogen at atmospheric pressure was introduced to replace the inside with nitrogen. This operation was repeated three times, and the autoclave was sealed. When (A-1) and (B-1) which came out of the system were collected at the time of decompression and nitrogen replacement, 0.1 g of each of (A-1) and (B-1) coming out of the system was collected. And 0.02 g.

The sealed autoclave was placed in an oil bath set at 180 ° C., vigorously shaken for 60 minutes, and then the autoclave was taken out of the oil bath and left at room temperature for 1 hour. After opening the autoclave and collecting the powder-like content, the mass of the content was 10%.
4.3 g. 50g of contents is 100ml
Of acetone and filtered off using a glass filter. This operation was repeated five times to obtain a washed product before drying and a filtrate before drying. As a result of elemental analysis, the siloxane having a reactive organic group contained in the filtrate before drying was
It was 0.01 g.

20 g of the dried material before drying
The fraction was washed with 40 ml of acetone, and filtered using a glass filter. Repeat this operation 5 times,
The washed product after drying and the filtrate after drying were obtained. As a result of elemental analysis, the siloxane (B-1) having a reactive organic group was not contained in the filtrate after drying. As a result of elemental analysis of the dried product, a siloxane having a reactive organic group (B
-1) It was confirmed that silicon derived therefrom was present. From (A-1) before the reaction, no silicon was detected by elemental analysis.

Using a press molding machine in which the mold temperature was set at 280 ° C., 20 g of the dried product was press-molded, and 50 × 8
A flat molded article having a size of 0 × 3 mm was obtained. This plate-like molded product was transparent and pale yellow, and no foreign matter was observed.

[0039]

Comparative Example 1 Polyphenylene ether (A-1) 100
g and a solution of 5 g of siloxane (B-1) having a reactive organic group in 900 g of toluene, and sealed in a nitrogen-purged autoclave in the same manner as in Example 1. (B-1) which goes out of the system at the time of decompression and nitrogen replacement is as follows:
0.03 g. As in Example 1, the sealed autoclave was placed in an oil bath set at 180 ° C.
After shaking for 0 minutes, the autoclave was taken out of the oil bath and left at room temperature for 1 hour. The autoclave was opened, and the content liquid (1002 g) was collected.

While stirring the content, methanol 10
kg was gradually added, and the precipitated powder was filtered with a glass filter, and the powder was further washed with 10 kg of methanol. This powder was dried under reduced pressure at 145 ° C. and 1 mmHg for 1 hour to obtain 96 g of the dried powder. From 50 g of the powder after drying, in the same manner as in Example 1, the washed product before drying, the filtrate before drying, and the dried product (49.5).
g) and a filtrate was obtained after drying. The siloxane (B-1) having a reactive organic group contained in the filtrate before drying and the filtrate after drying were 0.01 g and 0 g, respectively. Furthermore, as a result of elemental analysis of the dried product in the same manner as in Example 1, no silicon was detected.

[0041]

Example 2 Polyphenylene ether (A-2) 100
g and a siloxane (B-1) having a reactive organic group, 5 g,
And sealed in a nitrogen-purged autoclave in the same manner as in Example 1. (A-2) and (B-1) out of the system at the time of decompression and nitrogen replacement were 0.1 g and 0.03 g, respectively. As in Example 1, the sealed autoclave was placed in an oil bath set at 180 ° C.
Shake for 60 minutes, 104.2 g of powdery contents
Obtained.

From 50 g of the contents, in the same manner as in Example 1, the washed product before drying, the filtrate before drying, and the dried product (4
9.5 g) and a filtrate was obtained after drying. The siloxane (B-1) having a reactive organic group contained in the filtrate before drying and the filtrate after drying were 0.01 g and 0 g, respectively.
Met. Further, the dried product was subjected to elemental analysis in the same manner as in Example 1, and as a result, a siloxane having a reactive organic group (B
-1) Silicon derived from it was detected. As in Example 1,
A flat molded body was obtained. As in the case of Example 1, the flat molded body was transparent and pale yellow, and no foreign matter was observed.

[0043]

Example 3 Polyphenylene ether (A-1) 100
g, and 5 g of siloxane (B-1) having a reactive organic group, further using 5 g of 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, in the same manner as in Example 1, The vessel was sealed in a nitrogen-purged autoclave. (A-1), (B-1) which come out of the system at the time of decompression and nitrogen substitution
Was 0.1 g and 0.04 g, respectively.
The sealed autoclave is placed in an oil bath set at 180 ° C., shaken for 60 minutes, and the powdery content 10
4.3 g were obtained.

From 50 g of the contents, in the same manner as in Example 1, the washed product before drying, the filtrate before drying, and the dried product (4
9.5 g) and a filtrate was obtained after drying. The siloxane (B-1) having a reactive organic group contained in the filtrate before drying and the filtrate after drying were 0.01 g and 0 g, respectively. Further, the dried product was subjected to elemental analysis by the same operation as in Example 1, and as a result, a siloxane having a reactive organic group (B-1) was obtained.
Originated silicon was detected. In the same manner as in Example 1, a transparent molded article having a pale yellow color and no foreign matter was observed.

[0045]

Example 4 Polyphenylene ether (A-1) 100
g and 5 g of a siloxane having a reactive organic group (B-1), and sealed in a nitrogen-purged autoclave in the same manner as in Example 1. (A-1) and (B-1) out of the system at the time of decompression and nitrogen replacement were 0.1 g and 0.06 g, respectively. 1 sealed autoclave
The mixture was placed in an oil bath set at 30 ° C. and shaken for 60 minutes to obtain 104.2 g of a powdery content.

From 50 g of the contents, in the same manner as in Example 1, the washed product before drying, the filtrate before drying, and the dried product (4
9.6 g) and a filtrate was obtained after drying. The siloxane (B-1) having a reactive organic group contained in the filtrate before drying and the filtrate after drying were 0.02 g and 0 g, respectively. Furthermore, a film after the reaction was obtained from the dried product in the same manner as in Example 1. Further, the dried product was subjected to elemental analysis in the same manner as in Example 1, and as a result, silicon derived from siloxane (B-1) having a reactive organic group was detected. In the same manner as in Example 1, a transparent molded article having a pale yellow color and no foreign matter was observed.

[0047]

Example 5 Polyphenylene ether (A-1) 100
g and 5 g of a siloxane having a reactive organic group (B-1), and sealed in a nitrogen-purged autoclave in the same manner as in Example 1. (A-1) and (B-1) out of the system at the time of decompression and nitrogen replacement were 0.1 g and 0.04 g, respectively. 8 sealed autoclaves
Put in an oil bath set at 0 ° C, shake for 60 minutes,
104.3 g of a powdery content was obtained.

From 50 g of the contents, in the same manner as in Example 1, the washed product before drying, the filtrate before drying, and the dried product (4
9.5 g) and a filtrate was obtained after drying. The siloxane (B-1) having a reactive organic group contained in the filtrate before drying and the filtrate after drying were 0.05 g and 0 g, respectively. Further, the dried product was subjected to elemental analysis in the same manner as in Example 1, and as a result, a siloxane having a reactive organic group (B-
1) Originated silicon was detected. In the same manner as in Example 1, a transparent molded article having a pale yellow color and no foreign matter was observed.

[0049]

Example 6 Polyphenylene ether (A-1) 100
g and 5 g of a siloxane having a reactive organic group (B-1), and sealed in a nitrogen-purged autoclave in the same manner as in Example 1. (A-1) and (B-1) out of the system at the time of decompression and nitrogen replacement were 0.1 g and 0.04 g, respectively. 2 sealed autoclaves
It was placed in an oil bath set at 00 ° C. and shaken for 60 minutes to obtain 104.3 g of a powdery content.

From 50 g of the contents, in the same manner as in Example 1, the washed product before drying, the filtrate before drying, and the dried product (4
9.5 g) and a filtrate was obtained after drying. The siloxane (B-1) having a reactive organic group contained in the filtrate before drying and the filtrate after drying were 0.01 g and 0 g, respectively. Further, the dried product was subjected to elemental analysis in the same manner as in Example 1, and as a result, a siloxane having a reactive organic group (B-
1) Originated silicon was detected. In the same manner as in Example 1, a transparent molded article having a pale yellow color and no foreign matter was observed.

[0051]

Comparative Example 2 Polyphenylene ether (A-1) 100
g and 5 g of a siloxane having a reactive organic group (B-1), and sealed in a nitrogen-purged autoclave in the same manner as in Example 1. (A-1) and (B-1) out of the system at the time of decompression and nitrogen replacement were 0.1 g and 0.05 g, respectively. 2 sealed autoclaves
It was placed in an oil bath set at 60 ° C. and shaken for 60 minutes to obtain the contents. The contents solidified in the autoclave and were difficult to remove. Furthermore, as a result of elemental analysis of the dried product in the same manner as in Example 1, no silicon was detected.

[0052]

Comparative Example 3 5 kg of polyphenylene ether (A-1)
And siloxane having reactive organic group (B-1) 100 g
Is mixed with a Henschel mixer, and the barrel temperature is set to 340 ° C.
Extrusion kneading was performed using a ZSK-25 extruder manufactured by Werner Co., Ltd. Further, in the same operation as in Example 1,
As a result of elemental analysis of the dried product, no silicon was detected.

[0053]

Example 7 Polyphenylene ether (A-1) 100
g and a siloxane having a reactive organic group (B-1) 0.3
g and sealed in a nitrogen-purged autoclave in the same manner as in Example 1. (A-1) and (B-1) which come out of the system at the time of decompression and nitrogen replacement are 0.1 g, respectively.
And 0.01 g. The sealed autoclave was placed in an oil bath set at 180 ° C. and shaken for 60 minutes to obtain 100 g of a powdery content.

From 50 g of the contents, in the same manner as in Example 1, the washed product before drying, the filtrate before drying, and the dried product (4
9.5 g) and a filtrate was obtained after drying. The siloxane (B-1) having a reactive organic group contained in the filtrate before drying and the filtrate after drying were 0.01 g and 0 g, respectively. Further, the dried product was subjected to elemental analysis in the same manner as in Example 1, and as a result, a siloxane having a reactive organic group (B-
1) Originated silicon was detected. In the same manner as in Example 1, a transparent molded article having a pale yellow color and no foreign matter was observed.

[0055]

Comparative Example 4 Polyphenylene ether (A-1) 100
g and a siloxane (B-1) having a reactive organic group 0.0
The same operation as in Example 1 was carried out using 05 g, and sealed in a nitrogen-purged autoclave. (A-1) and (B-1) which come out of the system at the time of decompression and nitrogen replacement are 0.2% each.
g and 0.01 g. The sealed autoclave was placed in an oil bath set at 180 ° C. and shaken for 60 minutes to obtain 100 g of a powdery content.

From 50 g of the contents, in the same manner as in Example 1, the washed product before drying, the filtrate before drying, and the dried product (4
9.4 g) and a filtrate was obtained after drying. The siloxane (B-1) having a reactive organic group contained in the filtrate before drying and the filtrate after drying were 0.01 g and 0 g, respectively. Furthermore, as a result of elemental analysis of the dried product in the same manner as in Example 1, no silicon was detected.

[0057]

Example 8 Polyphenylene ether (A-1) 100
g and 30 g of a siloxane having a reactive organic group (B-1)
And sealed in a nitrogen-purged autoclave in the same manner as in Example 1. (A-1) and (B-1) out of the system at the time of decompression and nitrogen replacement were 0.1 g and 0.3 g, respectively. 18 sealed autoclaves
Put in an oil bath set at 0 ° C, shake for 60 minutes,
126.2 g of a powdery content was obtained.

From 50 g of the contents, in the same manner as in Example 1, the washed product before drying, the filtrate before drying, and the dried product (4
5.6 g) and a filtrate was obtained after drying. The siloxane (B-1) having a reactive organic group contained in the filtrate before drying and the filtrate after drying were 0.01 g and 0 g, respectively. Furthermore, a film after the reaction was obtained in the same manner as in Example 1. Further, the dried product was subjected to elemental analysis in the same manner as in Example 1, and as a result, a siloxane having a reactive organic group (B
-1) Silicon derived from it was detected. As in Example 1,
A transparent, pale yellow, plate-like molded product without any foreign matter was obtained.

[0059]

Embodiment 9 Polyphenylene ether (A-1) 10k
g and a siloxane (B-1) 500 having a reactive organic group
g was placed in a paddle dryer manufactured by Nara Machinery Co., Ltd., and purged with nitrogen while stirring the inside. After the replacement with nitrogen, the paddle dryer was sealed, and the jacket temperature was raised from room temperature to 180 ° C. over 1 hour while stirring the inside. 18 for 5 minutes
After keeping the temperature at 0 ° C., the jacket temperature was lowered to room temperature over 1 hour to obtain 10.1 kg of a powdery content.

From 50 g of the contents, in the same manner as in Example 1, the washed product before drying, the filtrate before drying, and the dried product (4
9.5 g) and a filtrate was obtained after drying. The siloxane (B-1) having a reactive organic group contained in the filtrate before drying and the filtrate after drying were 0.01 g and 0 g, respectively. Further, the dried product was subjected to elemental analysis in the same manner as in Example 1, and as a result, a siloxane having a reactive organic group (B-
1) Originated silicon was detected. In the same manner as in Example 1, a transparent molded article having a pale yellow color and no foreign matter was observed.

Further, 2 kg of the contents, 0.2 kg of polystyrene “685” manufactured by A & M Polystyrene, Inc.
Is mixed with a Henschel mixer, and the barrel temperature is set to 340 ° C.
The mixture was extruded and kneaded using a ZSK-25 type extruder manufactured by Werner Co., Ltd. to obtain pellets. Using an injection molding machine, an ASTM standard test piece is injection molded from the pellet,
According to the ASTM standard, the tensile strength (ASTM D-63)
8: 23 ° C), tensile elongation at break (ASTM D-638:
23 ° C), Izod (with notch) impact strength (AST
(MD-256: 23 ° C). As a result of the measurement, the tensile strength was 60 MPa, the tensile elongation at break was 100% or more, and the Izod (notched) impact strength was 208 J / m. As a result of a combustion test by UL94, the average combustion time was 7.1 seconds.

[0062]

Comparative Example 5 In the same manner as in Example 9, (A-1) 2 kg and polystyrene "6" manufactured by A & M Polystyrene Co., Ltd.
85 kg of 0.2 kg and a viscosity of 20 mm ² / s, 0.1 kg of siloxane oil “KF96” manufactured by Shin-Etsu Siloxane Co., Ltd. were mixed with a Henschel mixer, and a ZSK-25 extruder manufactured by Werner Co., Ltd. was set at a barrel temperature of 340 ° C. The mixture was extruded and kneaded to obtain pellets. Using an injection molding machine,
Injection molding of ASTM standard test piece from pellet
According to the TM standard, the tensile strength, tensile elongation at break, and Izod (notched) impact strength were measured. As a result of the measurement,
The tensile strength was 59 MPa, the tensile elongation at break was 5%, and the Izod (notched) impact strength was 150 J / m. As a result of the UL94 combustion test, the average combustion time was 1
2.3 seconds.

[0063]

Comparative Example 6 In the same manner as in Example 9, (A-1) 2 kg and polystyrene "6" manufactured by A & M Polystyrene Co., Ltd.
85 ”0.2 kg by a Henschel mixer and ZSK-2 manufactured by Werner Co., Ltd. in which the barrel temperature was set to 340 ° C.
Extrusion kneading was performed using a 5-type extruder to obtain pellets.
Using an injection molding machine, an ASTM standard test piece was injection molded from the pellet, and the tensile strength, tensile elongation at break, and Izod (notched) impact strength were measured according to the ASTM standard. As a result of the measurement, the tensile strength was 57 MPa, the tensile elongation at break was 5%, and the Izod (notched) impact strength was 25 J
/ M. As a result of a combustion test by UL94, the average burning time was 12.7 seconds.

[0064]

Example 10 Polyphenylene ether (A-1) 50
kg and siloxane (B-1) having a reactive organic group 2k
g can be heated by Nara Machine Co., Ltd.
It was placed in a -16W paddle dryer and the inside was replaced with nitrogen. Heated steam was introduced into the jacket and heated to 180 ° C. for 1 hour. After the jacket temperature reached 180 ° C., the temperature was maintained for 15 minutes, and then cooled by flowing cold water through the jacket.

From 50 g of the contents, in the same manner as in Example 1, the washed product before drying, the filtrate before drying, and the dried product (4
9.4 g) and a filtrate was obtained after drying. The siloxane having a reactive organic group (B-1) contained in the filtrate before drying and the filtrate after drying were 0.02 and 0 g, respectively. In the same manner as in Example 1, a transparent molded article having a pale yellow color and no foreign matter was observed.

[0066]

Example 11 Polyphenylene ether (A-1) 15
Siloxane (B-1) 2 having 0 kg and a reactive organic group
kg can be jacket heated by FM from Mitsui Mining Co., Ltd.
It was placed in a 500 type Henschel mixer and the inside was replaced with nitrogen. The stirring blade is rotated at high speed, and the content is reduced to 1
Heated to 80 ° C. over 50 minutes. Jacket temperature is 1
After the temperature reached 80 ° C., the high-speed rotation was continued for 5 minutes, and then cooled by flowing cold water through a jacket.

From 50 g of the contents, in the same manner as in Example 1, the washed product before drying, the filtrate before drying, and the dried product (4
9.5 g) and a filtrate was obtained after drying. The siloxane having a reactive organic group (B-1) contained in the filtrate before drying and the filtrate after drying were 0.02 and 0 g, respectively. In the same manner as in Example 1, a transparent molded article having a pale yellow color and no foreign matter was observed.

[0068]

Example 12 Polyphenylene ether (A-1) 15
Siloxane (B-1) 2 having 0 kg and a reactive organic group
kg was placed in a jacket-heatable hopper and the inside was replaced with nitrogen. Introduce heated steam into jacket 180
Heated to C over 1 hour. Jacket temperature 180
After reaching ℃, the mixture was kept warm for 15 minutes and then cooled by flowing cold water through a jacket.

From 50 g of the contents, in the same manner as in Example 1, the washed product before drying, the filtrate before drying, and the dried product (4
9.5 g) and a filtrate was obtained after drying. The siloxane (B-1) having a reactive organic group contained in the filtrate before drying and the filtrate after drying were 0.03 and 0 g, respectively. In the same manner as in Example 1, a transparent molded article having a pale yellow color and no foreign matter was observed.

[0070]

Industrial Applicability According to the method for producing a block polymer of siloxane and polyphenylene ether of the present invention, there is no problem in terms of equipment and energy, and the color tone / appearance is well balanced with heat resistance / mechanical properties. It has become possible to provide a block polymer of siloxane and polyphenylene ether which sufficiently satisfies the requirements of the above.

Claims (8)

[Claims] (A) 100 parts by weight of a polyphenylene ether comprising a structural unit of the following (formula 1), and (B) at least one carbon-carbon double bond or triple bond in a molecular structure. Wherein a mixture containing 0.01 to 50.0 parts by weight of a siloxane having one reactive organic group is reacted at a reaction temperature of 50 ° C. or higher and a melting point of (A) or lower, wherein the block polymer is a siloxane and a polyphenylene ether. Manufacturing method. Embedded image (R ₁ and R ₄ are each independently hydrogen, primary or secondary lower alkyl, phenyl, aminoalkyl,
Represents hydrocarbonoxy. R ₂ and R ₃ each independently represent hydrogen, primary or secondary lower alkyl, or phenyl. ) 2. The block polymer of siloxane and polyphenylene ether according to claim 1, wherein the reactive organic group of the siloxane having a reactive organic group (B) has a structure represented by the following formula (2). Production method. Embedded image (R ₁ represents hydrogen or a methyl group) 3. The method for producing a block polymer of siloxane and polyphenylene ether according to claim 1, wherein 0.01 to 10 parts by weight of a radical initiator is added. 4. The polyphenylene ether (A) is a powder obtained by precipitation from a solution and has a melting point of 24.
The method for producing a block polymer of siloxane and polyphenylene ether according to any one of claims 1 to 3, wherein the polyphenylene ether is 0 ° C to 260 ° C. 5. The method for producing a block polymer of siloxane and polyphenylene ether according to claim 1, wherein the block polymer is produced using a paddle dryer. 6. The method for producing a block polymer of siloxane and polyphenylene ether according to claim 1, wherein the block polymer is produced using a Henschel mixer. 7. The method for producing a block polymer of siloxane and polyphenylene ether according to claim 1, wherein the production is carried out using a hopper. 8. A block polymer of siloxane and polyphenylene ether produced by the production method according to claim 1.