JP2748451B2 - Method for producing block copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial application field> The present invention relates to a polyphenylene sulfide (hereinafter referred to as PPS) portion and a polyphenylene sulfide ketone (hereinafter referred to as PPSK).
And a method for producing a block copolymer comprising the same.

<Prior art> PPS resins have excellent properties as engineering plastics, such as excellent chemical resistance, heat resistance, and electrical insulation, and are used in various applications, mainly for injection molding.

Generally, electronic components such as ICs, transistors, resistors or capacitors can be covered or sealed with a synthetic resin such as epoxy resin for the purpose of maintaining electrical insulation, mechanical protection, and preventing changes in characteristics due to an external atmosphere. Widely used.

Because PPS resin has excellent properties as described above,
In recent years, application to the field of sealants for electronic components is expected. On the other hand, recently, the integration of ICs and the surface mounting of circuits are rapidly progressing, and further improvement in heat resistance such as solder resistance is required for a sealing agent.

In response to this demand, attempts have been made to obtain a high heat-resistant PPS resin composition by blending a polymer having higher heat resistance than the PPS resin.
JP-A-73228 discloses a method of compounding a polyimide resin, JP-A-56-45506 discloses a method of compounding a polyamide-imide resin, and JP-A-63-35653 discloses a method of compounding polyparabanic acid. ing.

On the other hand, as a block copolymer of PPS, JP-A-61-1
No. 4228 discloses a block copolymer with polym-phenylene sulfide, JP-A-61-225218 discloses a block copolymer with polysulfone, and JP-A-62-205157 discloses a block copolymer with polyphenylene sulfide. A polymer is disclosed.

<Problems to be Solved by the Invention> However, Japanese Patent Application Laid-Open Nos.
In the methods described in 6-45506 and JP-A-63-35653, the compatibility between the resins is poor, the compatibility is insufficient,
There was almost no improvement in heat resistance, and it was far from practical use.

On the other hand, the methods disclosed in JP-A-61-14228, JP-A-61-225218 and JP-A-62-205157 all introduce amorphous polymers into PPS in blocks. This is intended to improve the brittleness of the PPS resin, and has no effect on increasing the heat resistance of the PPS resin.

Therefore, an object of the present invention is to obtain a block copolymer having more heat resistance than ordinary PPS resin, and to efficiently produce the block copolymer.

<Means for Solving the Problems> That is, the present invention provides (1) an aprotic solution containing dihalobenzene and an alkali metal sulfide after dehydrating an alkali metal sulfide (including water of crystallization) in an aprotic polar organic solvent. The first step of heating the polar organic solvent to generate a reaction solution containing polyphenylene sulfide, and after dehydrating alkali metal sulfide (including water of crystallization) in an aprotic polar organic solvent,
Add dihalo aromatic ketone, alkali metal sulfide and aprotic polar organic solvent to the reaction solution and heat,
A method for producing a block copolymer comprising a polyphenylene sulfide portion and a polyphenylene sulfide ketone portion, which comprises a second step of forming a block copolymer; (2) dihalogenated aromatic ketone and alkali metal sulfide Aprotic polar organic solvent containing a polyphenylene sulfide ketone is heated to form a first step, and dihalobenzene is added to the reaction solution to form an alkali metal sulfide and an aprotic polar organic solvent. A method for producing a block copolymer comprising a polyphenylene sulfide portion and a polyphenylene sulfide ketone portion, comprising a second step of heating in the presence to form a block copolymer; (3) alkali metal sulfide (Including water of crystallization) in an aprotic polar organic solvent After that, the first step of heating the aprotic polar organic solvent containing dihalobenzene and alkali metal sulfide to generate a reaction solution containing polyphenylene sulfide, and converting the alkali metal sulfide (including water of crystallization) to non-proton After dehydration in a polar organic solvent,
A second step in which an aprotic polar organic solvent containing a dihalo aromatic ketone and an alkali metal sulfide is heated to generate a reaction liquid containing polyphenylene sulfide ketone, and the reaction liquid obtained in each step is mixed. A method of producing a block copolymer comprising a polyphenylene sulfide portion and a polyphenylene sulfide ketone portion, which comprises a third step of heating to form a block copolymer; and (4) the process wherein the block copolymer is polyphenylene Production of the block copolymer according to any one of the above (1) to (3), which is a block copolymer comprising a sulfide portion and a polyphenylene sulfide ketone portion and having a melt flow rate at 372 ° C. of 1 to 1,000. Is the way.

The PPS portion constituting the block copolymer in the present invention has a general formula At least 70 mol%, more preferably
A polymer containing at least 90 mol%, wherein the repeating unit is 70
If it is less than mol%, it is difficult to obtain a block copolymer having excellent properties.

In the PPS portion, less than 30 mol% of the repeating unit can be constituted by a repeating unit having the following structural formula.

On the other hand, PP constituting the block copolymer in the present invention
SK part is general formula A polymer containing at least 70 mol%, more preferably at least 90 mol%, of a repeating unit represented by the formula:
If it is less than mol%, it is difficult to obtain a block copolymer having excellent properties.

In the PPSK portion, less than 30 mol% of the repeating unit can be constituted by a repeating unit having the following structural formula.

In the present invention, the molar ratio of the repeating units of the PPS portion and the PPSK portion of the block copolymer is arbitrary. This block copolymer has a melt flow rate at 372 ° C. of 1
It is in the range of ~ 1,000. Usually, the block copolymer of the present invention has a glass transition temperature (Tg) of 70 to 150 ° C and a crystal melting point (Tm) of 260 to 370 ° C.

Tg and Tm are measured at a heating rate of 20 ° C / min in a nitrogen atmosphere using a Perkin Elmer Differential Scanning Calorimeter (DSCI) of approximately 10 mg of a sample that is rapidly cooled from a molten state and is in an amorphous state. In each case, the temperature is indicated by a knick and a melting peak.

The block copolymer in the present invention has the following (1) to
It is manufactured by the method of (3).

Production method (1): alkali metal sulfide (including water of crystallization)
Is dehydrated in an aprotic polar organic solvent, and then the aprotic polar organic solvent containing dihalobenzene and alkali metal sulfide is heated to generate a reaction solution containing polyphenylene sulfide; and After dehydrating the product (including water of crystallization) in an aprotic polar organic solvent, a dihalo aromatic ketone, an alkali metal sulfide and an aprotic polar organic solvent are added to the reaction solution,
A method for producing a block copolymer comprising a polyphenylene sulfide portion and a polyphenylene sulfide ketone portion, comprising a second step of heating to form a block copolymer.

Production method (2): heating an aprotic polar organic solvent containing a dihalo aromatic ketone and an alkali metal sulfide,
A first step of producing a reaction solution containing polyphenylene sulfide ketone; adding dihalobenzene to the reaction solution; and heating in the presence of an alkali metal sulfide and an aprotic polar organic solvent to form a block copolymer. A method for producing a block copolymer comprising a polyphenylene sulfide portion and a polyphenylene sulfide ketone portion, comprising a second step of forming.

Production method (3): alkali metal sulfide (including water of crystallization)
Is dehydrated in an aprotic polar organic solvent, and then the aprotic polar organic solvent containing dihalobenzene and alkali metal sulfide is heated to generate a reaction solution containing polyphenylene sulfide; and (Including water of crystallization) in an aprotic polar organic solvent, and then heating the aprotic polar organic solvent containing a dihalo aromatic ketone and an alkali metal sulfide to form a reaction solution containing polyphenylene sulfide ketone. The second step to produce, and a polyphenylene sulfide portion and a polyphenylene sulfide ketone portion, characterized by comprising a third step of mixing and heating the reaction solution obtained in each step to produce a block copolymer A method for producing a block copolymer comprising:

Except for taking into account the formation and bonding of blocks and the type of repeating unit as described above, and a manufacturing method satisfying the above requirements, the method for manufacturing a block copolymer of the present invention uses conventional PPS and It is not essentially different from the method for producing PPSK (JP-B-45-3368, JP-B-52-12240, JP-A-63-113020, etc.).

As the alkali metal sulfide used for producing the block copolymer of the present invention, lithium, sodium, potassium,
Sulfides such as rubidium are preferred, and sulfides of sodium and lithium are particularly preferred in view of reactivity. Further, the alkali metal sulfide may be obtained by a reaction between an alkali metal hydrosulfide and an alkali metal hydroxide.

Next, the aprotic polar organic solvent is preferably a substantially liquid at the reaction temperature and pressure.

Specifically, formamide, acetamide, N-methylamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ε-caprolactam, N-methyl-ε- Amides such as caprolactam, hexamethylphosphoramide, tetramethylurea, 1.3-dimethyl-2-imidazolidinone, urea and lactams, sulfones such as sulfolane and dimethylsulfolane, nitriles such as benzonitrile, methylphenylketone, etc. And the like, and mixtures thereof. Among these solvents, amides, lamtams or sulfones are particularly preferred.

Among the dihaloaromatic compounds used in the production of the block copolymer of the present invention, as the dihalobenzene to form the PPS portion, paradichlorobenzene, paradibromobenzene and the like are preferably used, and the dihaloaromatic ketone to form the PPSK portion is used. For example, 4,4'-dichlorobenzophenone is preferably used. As the dihalo aromatic compound which can be used in a small amount together with the dihalo aromatic compound necessary for forming the above-mentioned block, the following are preferable.

(In the above formula, X and Y each represent a halogen atom, and R ₁ and R ₂ each represent an alkyl group having 1 to 20 carbon atoms.) In addition, three such as 1,2,3- or 1,2,4-trihalobenzene Polyfunctional compounds having the above halogen groups can be used. Further, a polymerization catalyst such as an alkali metal carboxylate may be used for the purpose of increasing the degree of polymerization.

The above manufacturing methods (1) to (3) will be described more specifically. Note that a specific example of the manufacturing method (1) is the manufacturing method (I),
A specific example of the production method (2) is the production method (II) and a specific example of the production method (3) is the production method (III).

[Production method (I)] Production method (I) is a repeating unit of the PPS part. After forming the block, the repeating unit of the PPSK part on the spot And bonding.

An alkali metal sulfide (including water of crystallization), which is a raw material, is charged into an organic solvent, and heated to about 200 ° C. to distill water, thereby removing water from the reaction system. Thereafter, dihalobenzene is added in an amount usually corresponding to 0.95 to 1.05 / sulfide (mole / mole), and the mixture is heated to 160 to 300 ° C. to carry out a polymerization reaction to form a reaction mixture containing PPS. The required time is usually about 0.5 to 30 hours.

On the other hand, after the raw material alkali metal sulfide is dehydrated in an organic solvent in the same manner as described above, the dihalo aromatic ketone is usually 0.95
Add an amount corresponding to ~ 1.05 / sulphide (mol / mol) to form an unreacted mixture.

The unreacted mixture and the reaction mixture containing PPS are mixed at a predetermined ratio, and heated to 160 to 300 ° C. to perform a polymerization reaction, whereby the block copolymer of the present invention can be obtained. .

The polymer can be recovered as a granular or powdery form by washing, separating, and drying as necessary, as in the method for producing PPS.

[Production method (II)] Production method (II) is the reverse of production method (I).
After forming the block of the part, the PPS part is formed and combined on the spot.

In this method, an alkali metal sulfide is charged into an organic solvent, heated and dehydrated in the same manner as in the production method (I), and the dihalo-aromatic ketone is usually 0.95 to 1.05 / sulfide (mol / mol).
Is added, and the mixture is heated to 160 to 300 ° C. to carry out a polymerization reaction to prepare a reaction mixture containing PPSK.

On the other hand, in the same manner as in the production method (I), an alkali metal sulfide is charged into an organic solvent, heated and dehydrated. Make a mixture.

The unreacted mixture and the reaction mixture containing PPSK are mixed at a predetermined ratio, and heated to 160 to 300 ° C. to perform a polymerization reaction, whereby the block copolymer of the present invention can be obtained. . The recovery and purification of the block copolymer may be performed in the same manner as in the production method (I).

[Manufacturing method (III)] The manufacturing method (III) is to form each block separately and connect them together.

The reaction mixture of the production method (I) and the reaction mixture of the production method (II) are mixed at a predetermined ratio and heated to 160 to 300 ° C. to carry out a polymerization reaction, whereby the block copolymer of the present invention is obtained. Can be obtained.

The recovery and purification of the block copolymer is carried out by the production method (I)
What is necessary is just to do.

In addition, the block copolymer in the present invention, as long as the effects of the present invention are not impaired, the usual addition of antioxidants, heat stabilizers, lubricants, crystal nucleating agents, UV inhibitors, coloring agents, flame retardants, etc. Agents and small amounts of other polymers can be added, and in order to control the degree of crosslinking of the PPS portion of the block copolymer, a conventional peroxide agent and JP-A-59-131650 are used.
JP-A-58-204045, JP-A-58-204045, and JP-A-58-204045.
It is also possible to add a crosslinking inhibitor such as dialkyltin dicarboxylate and aminotriazole described in JP 204046 and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples.

<Example> Example 1 An autoclave was charged with 3.26 kg of sodium sulfide (25 mol, containing 40% of water of crystallization), 4 g of sodium hydroxide, 1.36 kg of sodium acetate trihydrate (about 10 mol) and 7.9 kg of NMP, The temperature was gradually raised to 205 ° C. while stirring, and about 1.5 of distillate water containing 1.36 kg of water was removed. 3.75 kg (25.5 mol) of 1,4-dichlorobenzene and 2 kg of NMP were added to the residual mixture,
The mixture was heated at 265 ° C. for 4 hours to prepare a PPS reaction mixture (A), which was extracted from the autoclave and stored. The same operation was repeatedly performed for the following operations.

An autoclave was charged with 3.26 kg of sodium sulfide (25 mol, containing 40% of crystallization water) and 7.9 kg of NMP, and the temperature was gradually raised to 205 ° C. with stirring, and about 1.5 g of distillate containing 1.36 kg of water was added.
Was removed. To the residue were added 6.28 kg (25 mol) of 4,4'-dichlorobenzophenone and NMP, and the mixture was cooled with stirring to prepare an unreacted mixture (H), which was extracted from the autoclave and stored. The same operation was repeated and subjected to the operation described below.

11.8 kg / 6.63 kg, 8.45 kg / 11.1 kg, 5.07 kg of the reaction mixture (A) / unreacted mixture (H) were added to the autoclave, respectively.
The mixture was charged at a rate of kg / 15.5 kg and reacted at 250 ° C. for 3 hours. After completion of the reaction, the reaction mixture was washed five times with warm water of 70 ° C, and washed at 80 ° C.
And dried under reduced pressure for 24 hours.
-1), (1-2) and (1-3) were obtained.

The melt flow rate at 372 ° C. of the obtained block copolymer was measured and found to be as shown in Table 1.

In addition, the obtained block copolymer was melted at a temperature about 30 ° C. higher than the melting point by a high-temperature press, pressed and quenched with water to prepare a film.
The measured Tm and Tm were as shown in Table 1.

Comparative Example 1 A PPS reaction solution (A) was prepared in exactly the same manner as in Example 1, washed 5 times with warm water at 70 ° C., and dried under reduced pressure at 80 ° C. for 24 hours. Melt viscosity about 2,500 poise (320 ° C, shear rate 1,
Approximately 2 kg of a powdery PPS (Comparative Example 1) of 000 sec- ¹ ) was obtained.

The Tg and Tm of the PPS were measured and found to be as shown in Table 1.

Table 1 clearly shows that the block copolymer of Example 1 of the present invention has higher Tg and Tm than PPS.

Example 2 An autoclave was charged with 3.26 kg of sodium sulfide (25 mol, containing 40% of crystallization water) and 7.9 kg of NMP, and the temperature was gradually raised to 205 ° C. while stirring, and about 1.5% of distillate containing 1.36 kg of water was added.
Was removed. 6.28 kg (25 mol) of 4,4'-dichlorobenzophenone and 6 kg of NMP were added to the residue and heated at 250 ° C. for 3 hours to prepare a PPSK reaction mixture (B), which was extracted from the autoclave and stored. The same operation was repeated and subjected to the operation described below.

An autoclave was charged with 3.26 kg of sodium sulfide (25 mol, containing 40% of crystallization water) and 7.9 kg of NMP, and the temperature was gradually raised to 205 ° C. with stirring, and about 1.5 g of distillate containing 1.36 kg of water was added.
Was removed. 3.75 kg of 1,4-dichlorobenzene in the residue
(25.5 mol) and 2 kg of NMP were added, and the mixture was cooled with stirring to prepare an unreacted mixture (I), which was extracted from the autoclave and stored. The same operation was repeated and subjected to the operation described below.

15.5 kg / 4.68 kg, 11.1 kg / 7.80 kg, 6.63 kg of the reaction mixture (B) / unreacted mixture (I) were added to the autoclave.
kg / 10.9 kg, and reacted at 250 ° C. for 8 hours.

After completion of the reaction, the copolymer was washed and dried in the same manner as in Example 1, and the block copolymers (2-1), (2-2) and (2) were respectively obtained.
-3) was obtained. The melt flow rate, Tg and Tm of the obtained block copolymer were as shown in Table 1.

Example 3 The reaction mixtures (A) and (B) prepared in Examples 1 and 2 were combined with 11.8 kg / 6.63 kg, 8.45 kg / 11.1 kg and
It was charged at a ratio of 5.07 kg / 15.5 kg and reacted at 250 ° C. for 20 hours. After completion of the reaction, washing and drying were performed in the same manner as in Example 1 to obtain block copolymers (3-1), (3-2), and (3-3), respectively.

Melt flow rate of the obtained block copolymer, Tg
And Tm were as described in Table 1.

Comparative Example 2 The unreacted mixed liquids (H) and (I) prepared in Examples 1 and 2 were charged at a ratio of 11.1 kg / 7.80 kg and 15.5 kg / 4.68 kg, respectively, and reacted at 250 ° C. for 5 hours. After the reaction,
The reaction solution was washed and dried in the same manner as in Example 1 to obtain random copolymers (Comparative Example 2-1) and (Comparative Example 2-2), respectively. The obtained random copolymer was measured in the same manner as in Example 1, and the results shown in Table 1 were obtained.

Example 4 The block copolymers (3-1) and (3-2) obtained in Example 3 were pelletized by a screw extruder set at 300 to 380 ° C. Next, the pellets were supplied to a screw in-line injection molding machine set at 300 to 380 ° C, and a test piece was formed under the condition of a mold temperature of 150 ° C.

The heat distortion temperature (ASTM
D-648) was as described in Table 2.

Comparative Example 3 The PPS powder obtained in Comparative Example 1 was subjected to pelletizing and injection molding in the same manner as in Example 4 to evaluate the heat deformation temperature of the test piece as shown in Table 2.

<Effect of the Invention> According to the production method of the present invention, a block copolymer can be efficiently produced.

Further, the block copolymer obtained by the production method of the present invention has better heat resistance than conventional PPS resins.

Claims (4)

(57) [Claims] 1. An alkali metal sulfide (including water of crystallization) is dehydrated in an aprotic polar organic solvent, and then the aprotic polar organic solvent containing dihalobenzene and alkali metal sulfide is heated to convert polyphenylene sulfide. A first step of producing a reaction solution containing the compound, and after dehydrating the alkali metal sulfide (including water of crystallization) in an aprotic polar organic solvent, the reaction solution is added to a dihalo aromatic ketone, an alkali metal sulfide and A method for producing a block copolymer comprising a polyphenylene sulfide portion and a polyphenylene sulfide ketone portion, comprising a second step of adding a protic polar organic solvent and heating to produce a block copolymer. 2. A first step in which an aprotic polar organic solvent containing a dihalo aromatic ketone and an alkali metal sulfide is heated to form a reaction solution containing polyphenylene sulfide ketone, and dihalobenzene is added to the reaction solution. Then, heating in the presence of an alkali metal sulfide and an aprotic polar organic solvent, a polyphenylene sulfide portion and a polyphenylene sulfide ketone portion characterized by comprising a second step of forming a block copolymer A method for producing a block copolymer. 3. Dehydration of an alkali metal sulfide (including water of crystallization) in an aprotic polar organic solvent, followed by heating of the aprotic polar organic solvent containing dihalobenzene and alkali metal sulfide to convert polyphenylene sulfide. A first step of producing a reaction solution containing an alkali metal sulfide (including water of crystallization) in an aprotic polar organic solvent, followed by dehydration of the alkali metal sulfide (including water of crystallization). From the second step of heating the organic solvent to generate a reaction solution containing polyphenylene sulfide ketone, and from the third step of mixing and heating the reaction solutions obtained in each step to generate a block copolymer A method for producing a block copolymer comprising a polyphenylene sulfide portion and a polyphenylene sulfide ketone portion. 4. A block copolymer comprising a polyphenylene sulfide portion and a polyphenylene sulfide ketone portion, and having a melt flow rate at 372 ° C. of 1 to 1,000.
Claims (1) to (4) which are block copolymers in the range of
The method for producing the block copolymer according to any one of (3).