JP6187479B2 - Method for producing polyarylate - Google Patents

Description

  The present invention relates to a method for producing a polyarylate, and in particular, is a production method that exhibits an effect in producing a polyarylate having a polystyrene-equivalent weight average molecular weight of 20,000 or more and less than 150,000.

  Polyarylate is excellent in mechanical properties, electrical properties and the like, and is widely used as an engineering plastic in various fields such as the electrical / electronic equipment field, the automobile field, and the OA equipment field. In particular, polyarylate having a polystyrene-equivalent weight average molecular weight of 20,000 or more and less than 150,000 has high strength when used as a coating material, and its industrial utility value is extremely high.

  Polyarylate is produced by using a known polyester polymerization method using dihydric phenol and aromatic dicarboxylic acid or a derivative thereof as raw materials. Examples of the polymerization method include interfacial polymerization, solution polymerization, and melt polymerization, and interfacial polymerization is preferable.

Interfacial polymerization is performed by mixing an aqueous phase in which a dihydric phenol is dissolved in an alkaline aqueous solution and an organic phase in which a divalent carboxylic acid halide is dissolved in an organic solvent not dissolved in water in the presence of a catalyst. . (Non-patent document 1, Patent document 1)
Interfacial polymerization is faster in reaction than solution polymerization, and hydrolysis of acid halide can be minimized. As a result, high molecular weight polyarylate can be obtained.

In particular, when producing a high molecular weight polyarylate, it is necessary to minimize hydrolysis of the acid halide. As the method, for example, as shown in Patent Document 2, in the interfacial polymerization reaction step, using a Max Blend type blade (registered trademark of Sumitomo Heavy Industries, Ltd.), a polymerization catalyst (tri-n-butyl) having a high polymerization rate is used. In the presence of benzylammonium chloride, there is a method for producing a high molecular weight polyarylate by interfacial polymerization while adjusting the rotational speed of the stirrer so that the stirring power is 0.4 to 1.2 kW / m ^3. . However, there is room for improvement in the polymerization time in the above method.

  Patent Document 3 describes a method of using a reciprocating rotary stirrer as a stirrer in a method for producing an aromatic carbonate. However, Patent Document 3 is not related to a method for producing a resin, nor is it related to a method for producing polyarylate.

  In Patent Document 4, various stirrers including a reciprocating rotary stirrer are listed as the stirrer to be used, but there is no description of a preferable stirrer. And patent document 4 is related with the manufacturing method of aliphatic polyester, and there is no description regarding the manufacturing method of polyarylate.

Japanese Patent Publication No.40-1959 JP 2007-217502 A JP 7-224008 A JP 2009-256643 A

W. M.M. EARECKSON, J.A. Poly. Sci. XL399 (1959)

  An object of the present invention is to provide a method for producing polyarylate industrially stably and more efficiently in a shorter polymerization time than a conventional production method.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by performing an interfacial polymerization reaction using a reciprocating rotary stirrer in the interfacial polymerization reaction step. The present invention has been reached. That is, the present invention includes the following aspects.
<1> A method for producing a polyarylate comprising a dihydric phenol component and an aromatic dicarboxylic acid component, wherein an interfacial polymerization reaction is performed using a reciprocating rotary stirrer in the interfacial polymerization reaction step. A method for producing polyarylate.
<2> The method for producing a polyarylate according to the above <1>, wherein an interfacial polymerization reaction is performed in the presence of a polymerization catalyst represented by the following formula (1).
(In the formula, n represents any of 2, 3, and 4, Y represents an ethyl group, a propyl group, a butyl group, or a benzyl group, and X represents Cl, Br, OH, or HSO ₄ ).
<3> In the interfacial polymerization reaction step, the polyarylate production method according to the above <1> or <2>, wherein the stirring power of the reciprocating rotary stirrer is controlled to 1 to 10 kW / m ³ .
<4> The method for producing polyarylate according to any one of <1> to <3>, wherein the blade shape of the reciprocating rotary stirrer used is a triangular blade in the interfacial polymerization reaction step.
<5> The polyarylate according to any one of <1> to <4> above, wherein a polyarylate having a polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography of 20,000 or more and less than 150,000 is obtained. It is a manufacturing method.

  According to a preferred embodiment of the present invention, it is possible to stably and highly efficiently produce a polyarylate having a polystyrene equivalent weight average molecular weight of 20,000 or more and less than 150,000. Since the polyarylate obtained in the preferred embodiment of the present invention has a remarkably high strength, when it is used as a coating material, it can be widely used in the electrical / electronic field and the like, and its industrial utility value is extremely high.

Hereinafter, the present invention will be described in detail.
The polyarylate referred to in the present invention is a polyester composed of a dihydric phenol component and an aromatic dicarboxylic acid component.

  In the present invention, examples of the dihydric phenol component include 1,1′-biphenyl-4,4′-diol, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) sulfone, and bis (4-hydroxy). Phenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A; BPA), 2,2 -Bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z; BPZ), 1,1-bis (4-hydroxyphenyl) cyclododecane, 2,2-bis (4-Hydroxyphenyl) hexafluoropropane, 4,4 ′-[1,3-phenylenebis (1-methyl) Tylidene)] bisphenol, 2,2-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4 -Hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis ( 4-hydroxy-3-methylphenyl) propane (bisphenol C; BPC), 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl)- 1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bi (4-hydroxy-3-methylphenyl) fluorene, 2,2-bis (4-hydroxy-3-polydimethylpropylphenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3-methylphenyl) ) Ether, bis (4-hydroxy-3-ethylphenyl) ether, bis (4-hydroxy-3-tert-butylphenyl) ether, bis (4-hydroxy-3-allylphenyl) ether, bis (2-hydroxyphenyl) ) Ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3-fluorophenyl) ether, bis (4-hydroxy-3-phenylphenyl) ether, α, ω-bis [ 2- (p-hydroxyphenyl) ethyl] polydimethylsiloxane, α, ω-bi [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane, α, ω-bis [3- (4-hydroxy-3-methoxyphenyl) propyl] polydimethylsiloxane, α, ω-bis [3- (p- Hydroxyphenyl) propyl] polydimethylsiloxane, α, ω-bis [2-methyl-2- (p-hydroxyphenyl) ethyl] polydimethylsiloxane, and the like can be used. Of these, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A; BPA), 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z; BPZ), 2 , 2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C; BPC).

  Examples of the aromatic dicarboxylic acid component include adipic acid, suberic acid, sebacic acid, diphenic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4′-dicarboxylic acid, 3-tert-butylisophthalic acid, and toluene-2. , 5-dicarboxylic acid, p-xylene-2,5-dicarboxylic acid, pyridine-2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6- Dicarboxylic acid, pyridine-3,4-dicarboxylic acid, pyridine-3,5-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, biphenyl- 2,2′-dicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, diphenyl ether-2,2′-dicarboxylic acid, diphenyl Ether-2,3′-dicarboxylic acid, diphenylether-2,4′-dicarboxylic acid, diphenylether-3,3′-dicarboxylic acid, diphenylether-3,4′-dicarboxylic acid, diphenylether-4,4′-dicarboxylic acid, Bis (4-carboxy-3-methylphenyl) ether, bis (4-carboxy-2-methylphenyl) ether, bis (4-carboxy-3-ethylphenyl) ether, bis (4-carboxy-2-ethylphenyl) Ether, bis (2-carboxy-3-methylphenyl) ether, bis (2-carboxy-4-methylphenyl) ether, bis (2-carboxy-5-methylphenyl) ether, bis (2-carboxy-6-methyl) Phenyl) ether, bis (2-carboxy-3-ethylphenol) ) Ether, bis (2-carboxy-4-ethylphenyl) ether, bis (2-carboxy-5-ethylphenyl) ether, bis (2-carboxy-6-ethylphenyl) ether, bis (3-carboxy-2) -Methylphenyl) ether, bis (3-carboxy-4-methylphenyl) ether, bis (3-carboxy-5-methylphenyl) ether, bis (3-carboxy-6-methylphenyl) ether, bis (3-carboxy -2-ethylphenyl) ether, bis (3-carboxy-4-ethylphenyl) ether, bis (3-carboxy-5-ethylphenyl) ether, bis (3-carboxy-6-ethylphenyl) ether and the like. . Among these, Preferably, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, biphenyl-2,2′-dicarboxylic acid, Biphenyl-4,4′-dicarboxylic acid, diphenyl ether-2,2′-dicarboxylic acid, diphenyl ether-3,3′-dicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, bis (4-carboxy-3-methylphenyl) ) Ether, bis (4-carboxy-2-methylphenyl) ether, bis (2-carboxy-3-methylphenyl) ether, bis (2-carboxy-4-methylphenyl) ether, bis (2-carboxy-5- Methylphenyl) ether, bis (2-carboxy-6-methylphenyl) Ether, bis (3-carboxy-2-methylphenyl) ether, bis (3-carboxy-4-methylphenyl) ether, bis (3-carboxy-5-methylphenyl) ether, bis (3-carboxy-6-methyl) An aromatic dicarboxylic acid which is phenyl) ether and can be particularly preferably used is an equivalent mixture of terephthalic acid and isophthalic acid.

  In the present invention, basically, an aqueous phase in which a dihydric phenol is dissolved in an alkaline aqueous solution and an organic phase in which a divalent carboxylic acid halide is dissolved in an organic solvent not dissolved in water are mixed in the presence of a catalyst. Thus, interfacial polymerization is performed to produce polyarylate. Examples of the alkali used in the aqueous phase include sodium hydroxide and potassium hydroxide.

  As the solvent used in the organic phase, a solvent that is incompatible with water and dissolves the polyarylate produced is used. Specifically, methylene chloride, 1,2-dichloroethane, chloroform, Chlorinated solvents such as carbon chloride, chlorobenzene, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, toluene, benzene, xylene, etc. Aromatic hydrocarbons, tetrahydrofuran and the like.

The specific polymerization catalyst used in the present invention is preferably a quaternary ammonium salt having a chemical structure represented by the following formula (1). Moreover, the quaternary ammonium salt which has a chemical structure shown by following formula (1) 'is also mentioned preferably.

(In the formula, n represents any of 2, 3, and 4, Y represents an ethyl group, a propyl group, a butyl group, or a benzyl group, and X represents Cl, Br, OH, or HSO ₄ ).
(In the formula, Y represents a butyl group or a benzyl group, and X represents Cl, Br, OH, or HSO _4. )
Specifically, triethylbenzylammonium chloride, triethylbenzylammonium bromide, triethylbenzylammonium hydroxide, triethylbenzylammonium hydrogensulfate, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium hydroxide, tetraethylammonium hydrogensulfate, tripropyl Benzylammonium chloride, tripropylbenzylammonium bromide, tripropylbenzylammonium hydride, tripropylbenzylammonium hydrogen sulfate, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium hydroxide Id, tetrapropylammonium hydrogen sulfate, tri-n-butylbenzylammonium chloride, tri-n-butylbenzylammonium bromide, tri-n-butylbenzylammonium hydride, tri-n-butylbenzylammonium hydrogen sulfate, tetra-n-butylammonium Examples include chloride, tetra n-butylammonium bromide, tetra n-butylammonium hydroxide, and tetra n-butylammonium hydrogen sulfate.

  In order to adjust the molecular weight of the polyarylate, an end-stopper can be used during the polymerization. Examples of end terminators include phenol, p-cresol, o-cresol, 2,4-xylenol, p-t-butylphenol, o-allylphenol, p-allylphenol, p-hydroxystyrene, p-hydroxy-α-. Monovalent phenols such as methylstyrene, p-propylphenol, p-cumylphenol, p-phenylphenol, o-phenylphenol, p-trifluoromethylphenol, p-nonylphenol, p-dodecylphenol, eugenol, benzoic acid And monovalent acid chlorides such as acid chloride, methanesulfonyl chloride, and phenyl chloroformate.

  In the interfacial polymerization, the organic phase solution is mixed with the aforementioned aqueous phase solution, and the interfacial polycondensation reaction is performed with stirring at a temperature of usually 40 ° C. or lower, more preferably 25 ° C. or lower for 0.1 to 5 hours. Thus, a high molecular weight polyarylate can be obtained.

  The polyarylate of the present invention preferably has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter abbreviated as GPC) of 20,000 or more and less than 150,000, more preferably 30,000. More than 130,000. The number average molecular weight (Mn) in terms of polystyrene is preferably from 4,000 to 80,000. When the polystyrene-equivalent weight average molecular weight (Mw) is less than 20,000, the mechanical strength as a coating material is reduced. On the other hand, when the polystyrene-equivalent weight average molecular weight (Mw) is more than 150,000, the processability when forming a film is obtained. May decrease.

As the polyarylate reactor used in the present invention, a tank reactor equipped with a reciprocating rotary stirrer can be used. The present invention is characterized in that in the interfacial polymerization reaction step, an interfacial polymerization reaction is carried out using a reciprocating rotary stirrer. In the present invention, the reciprocating agitator refers to an agitator in which the agitation shaft is not rotated in one direction but is reversed every 1/4 rotation. For stirring during the reaction, it is preferable to control the stirring power in the range of 1~10kW / ^{m 3,} more preferably from 1~8kW / ^{m 3,} particularly preferably 1~5kW / ^{m 3.} When the stirring power is less than 1 kW / m ³ , sufficient mixing of the aqueous phase and the organic phase cannot be obtained, the contact area between the aqueous phase and the organic phase is reduced, and the reaction rate is reduced. Polyarylate resin may not be produced.

On the other hand, when the stirring power exceeds 10 kW / m ³ , the decomposition rate of the polymer chain or acid halide increases, and it may be difficult to control the molecular weight. Moreover, the resin solution purification efficiency after completion | finish of a polymerization process may fall because a resin solution emulsifies and becomes cloudy. For the above two reasons, it may not be possible to produce the polyarylate resin stably and highly efficiently.

  In addition, as the stirring blade for stirring with the stirring power, it is preferable to use a triangular blade from the viewpoint of homogenizing the time until mixing and heat transfer in the can. Here, the triangular blade indicates a stirring blade having a triangular cross-sectional shape.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples.

<GPC conditions>
Waters Alliance HPLC system,
2 Shodex 805L columns made by Showa Denko KK
0.25 w / v% chloroform solution sample, 1 ml / min chloroform eluent,
Measured under UV detection conditions at 254 nm.
The polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) were determined.

<Example 1>
In the tank type reaction vessel, a reciprocating rotary stirrer agitator (registered trademark of Shimazaki Seisakusho Co., Ltd.) was equipped with a triangular blade as a stirrer. Among them, 49 g (0.21 mol) of 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as BPA) as a dihydric phenol and p-tert-butylphenol (hereinafter referred to as PTBP) as a terminal terminator. Abbreviated.) 0.63 g (0.0042 mol), tri-n-butylbenzylammonium chloride (hereinafter abbreviated as TBBAC), which is a polymerization catalyst, is 1 mol% (0.67 g) with respect to the total dihydric phenol. Dissolved in 730 ml of 3 w / w% aqueous sodium hydroxide solution (aqueous phase). Separately, 44 g (0.22 mol) of a terephthalic acid chloride / isophthalic acid chloride = 1/1 mixture (hereinafter abbreviated as MPC) was dissolved in 530 ml of methylene chloride (organic phase).

The organic phase was added to the aqueous phase adjusted so that the stirring power of the stirrer was 7 kW / m ³ under strong stirring, and an interfacial polycondensation reaction was performed at 15 ° C. for 1 hour. After stopping the polymerization, the polymerization solution is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, the pH of the washing solution becomes neutral, and the conductivity of the aqueous phase is 10 μS / cm or less. After repeating the washing with water until it was, the obtained polymer solution was dropped into warm water kept at 50 ° C., and the solvent was removed by evaporation while pulverizing with a homogenizer to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 120 ° C. for 24 hours to obtain a dry powder.

<Example 2>
In Example 1, except that 55 g (0.21 mol) of 2,2-bis (4-hydroxy-3-methylphenyl) propane (hereinafter abbreviated as BPC) was used as the dihydric phenol instead of BPA. 1 to obtain a polyarylate resin.

<Example 3>
In Example 1, 57.5 g (0.21 mol) of 1,1-bis (4-hydroxyphenyl) cyclohexane (hereinafter abbreviated as BPZ) was used as a dihydric phenol in place of BPA, and PTBP as a terminal stopper was used. A polyarylate resin was obtained in the same manner as in Example 1 except that the amount was changed to 0.51 g (0.0034 mol).

<Example 4>
A polyarylate resin was obtained in the same manner as in Example 1 except that the stirring power was changed to ³ kW / m ³ in Example 1.

<Example 5>
A polyarylate resin was obtained in the same manner as in Example 1, except that the stirring power was changed to 1 kW / m ³ in Example 1.

<Example 6>
In Example 1, except that the polymerization catalyst was changed to triethylbenzylammonium chloride (hereinafter abbreviated as TEBAC) and the amount used was changed to 10 mol% (4.9 g) with respect to the total dihydric phenol, The same operation as in Example 1 was performed to obtain a polyarylate resin.

<Example 7>
In Example 1, except that the stirring power was changed to 12 kW / m ³ , the same operation as in Example 1 was performed. As a result, a polyarylate resin could be obtained, but the resin solution was emulsified and became cloudy. The resin solution purification efficiency after completion of the polymerization process was lowered.

<Example 8>
A polyarylate resin was obtained in the same manner as in Example 1 except that the stirring power was changed to 0.8 kW / m ³ in Example 1.

<Comparative Example 1>
In Example 1, the same operation as in Example 1 was performed, except that the one-turn type stirrer was equipped with a Max Blend type blade and the interfacial polycondensation reaction was performed while controlling the stirring power to 1 kW / m ^3. A polyarylate resin was obtained.

<Comparative example 2>
In Comparative Example 1, except that the stirring power was changed to ³ kW / m ³ , the same operation as in Comparative Example 1 was performed. As a result, the solution was strongly pressed against the wall surface by the stirring flow, and was scattered from the reaction vessel and synthesized. I could not.

<Comparative Example 3>
In Comparative Example 1, except that the stirring power was changed to 7 kW / m ³ , the same operation as in Comparative Example 1 was performed. As in Comparative Example 2, the solution was excessively pressed against the wall surface by the stirring flow. It was scattered from the tank and could not be synthesized.

Table 1 summarizes the results of Examples 1-8 and Comparative Examples 1-3.

  According to the present invention, polyarylate can be produced industrially stably and more efficiently in a shorter polymerization time than conventional production methods. Since the produced polyarylate has a high molecular weight, its strength is remarkably high. Therefore, when it is used as a coating material, it can be widely used in the electric and electronic fields, and its industrial utility value is extremely high.

Claims (4)

A method for producing a polyarylate comprising a dihydric phenol component and an aromatic dicarboxylic acid component,
Include interfacial polymerization reaction step of interfacial polymerization reaction using a round trip rotary stirrer, the process for preparing polyarylate, wherein the airfoil shape of the reciprocating rotary agitator is delta wing. The method for producing polyarylate according to claim 1, wherein an interfacial polymerization reaction is carried out in the presence of a polymerization catalyst represented by the following formula (1).
(In the formula, n represents any of 2, 3, and 4, Y represents an ethyl group, a propyl group, a butyl group, or a benzyl group, and X represents Cl, Br, OH, or HSO ₄ ). The method for producing polyarylate according to claim 1 or 2, wherein in the interfacial polymerization reaction step, the stirring power of the reciprocating rotary stirrer is controlled to 1 to 10 kW / m ³ . The method for producing a polyarylate according to any one of claims 1 to 3 , wherein a polyarylate having a polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography of 20,000 or more and less than 150,000 is obtained.