JP6632053B2 - A method for producing a molded article containing syndiotactic polystyrene and a method for producing a composite molded article. - Google Patents

Description

  The present invention relates to a method for producing a molded article containing syndiotactic polystyrene forming an ε-type crystal, and a method for producing a composite molded article containing a polymer incorporated in an ε-type crystal.

Syndiotactic polystyrene (hereinafter, sometimes referred to as “SPS”) obtained by stereoregular polymerization of styrene is a polymer having high crystallinity, and has a trans-zigzag structure and a 2 ₁ -helix structure. It can take the form of a variety of main chain structures. As the crystal form of the SPS, alpha, beta, gamma, [delta], 5 species are known in epsilon, the [delta] form and epsilon-type crystal, a main chain of the SPS to form a predominantly ₂ 1 _-helix structure. 1 and 2 show the forms of syndiotactic polystyrene forming δ-type crystals and ε-type crystals, respectively. The ε-type crystal in FIG. 2 forms an elongated tubular free space 5, and a plurality of guest compounds 20 can be arranged in the free space 5.

  Regarding a method for obtaining an SPS film containing an ε-type crystal, Non-Patent Document 1 first describes a step of preparing an SPS film containing a δ-type crystal, and annealing the SPS film containing a δ-type crystal at 120 ° C. or higher to obtain a γ-type crystal. , A step of exposing the SPS film containing the γ-type crystal to chloroform, and a step of subsequently washing the SPS film with acetonitrile.

O. Tarallo et al., Macromolecules, 43 (3), 2010, 1455-1466

  According to the conventional method disclosed in Non-Patent Document 1, a compact containing a mixed crystal including not only ε-type crystals but also γ-type crystals is easily formed. In order to obtain molded articles having various functions using ε-type crystals, SPS molded articles containing ε-type crystals with higher purity are desired.

  Therefore, a main object of the present invention is to provide a method for easily producing an SPS molded body containing ε-type crystals with high purity.

  One aspect of the present invention relates to a method for producing a molded article containing syndiotactic polystyrene forming an ε-type crystal. The method comprises contacting a molded article containing syndiotactic polystyrene with a liquid containing a compound for forming a γ-type crystal for forming a γ-type crystal, or exposing the formed body to a vapor of the compound for forming a γ-type crystal, Forming a γ-type crystal of syndiotactic polystyrene, and contacting the molded body containing the γ-type crystal and the compound for forming a γ-type crystal with a liquid containing a compound for forming an ε-type crystal for forming an ε-type crystal. Or forming the ε-type crystal of the syndiotactic polystyrene by contacting the molded body with a solvent in which the compound for forming the ε-type crystal is dissolved. And

  According to this method, an SPS film containing an ε-type crystal with high purity can be easily manufactured.

  Another aspect of the present invention relates to a composite molded article including a syndiotactic polystyrene forming an ε-type crystal and a polymer incorporated in the ε-type crystal, and a method for producing the same. The method for producing the composite molded body includes a step of incorporating a polymerizable monomer into a molded body containing syndiotactic polystyrene forming an ε-type crystal, and a step of generating a polymer of the polymerizable monomer in the molded body. Can be provided.

  By arranging the polymer in a tubular free space formed by the ε-type crystal, a composite molded body having various functions such as conductivity can be obtained.

  According to one aspect of the present invention, it is possible to easily manufacture an SPS compact including a ε-type crystal with high purity. According to another aspect of the present invention, a composite molded body having various functions such as conductivity can be easily obtained.

FIG. 2 is a schematic diagram showing one embodiment of a molded body containing syndiotactic polystyrene forming a δ-type crystal. FIG. 2 is a schematic view showing one embodiment of a molded body containing syndiotactic polystyrene forming an ε-type crystal. 3 is a flowchart showing one embodiment of a method for producing a molded article containing syndiotactic polystyrene forming an ε-type crystal. 1 is a flowchart showing a conventional method for producing a molded body containing syndiotactic polystyrene forming an ε-type crystal. 3 is a flowchart illustrating an embodiment of a method for manufacturing a composite molded body. It is a measurement result of the wide-angle X-ray diffraction of a syndiotactic polystyrene film. It is a measurement result of the wide-angle X-ray diffraction of a syndiotactic polystyrene film. It is a measurement result of the wide-angle X-ray diffraction of a syndiotactic polystyrene film. It is an FT-IR spectrum of a syndiotactic polystyrene film. It is an FT-IR spectrum of a syndiotactic polystyrene film. It is a measurement result of the wide-angle X-ray diffraction of a syndiotactic polystyrene film. It is an FT-IR spectrum of a syndiotactic polystyrene film. It is an FT-IR spectrum of a syndiotactic polystyrene film.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

<SPS molded body>
FIG. 2 is a schematic diagram showing one embodiment of a molded article containing syndiotactic polystyrene (SPS) forming an ε-type crystal. Moldings (SPS moldings) syndiotactic polystyrene (SPS) 10 in 1 shown in Figure _2, forms a 2 1 -Helix structure, free space 5 tubular between the main chain of the SPS formed ing. In the free space 5, a plurality of guest compounds 20 (for example, a compound for forming an ε-type crystal described later) are included.

  FIG. 3 is a flowchart illustrating an embodiment of a method for manufacturing a molded body including SPS forming an ε-type crystal (ε-type crystal SPS molded body). The method shown in FIG. 3 involves contacting a molded article containing amorphous syndiotactic polystyrene (amorphous SPS molded article) with a liquid containing a compound for forming a γ-type crystal, or Step S1 of forming a γ-type crystal of SPS by exposing to a vapor, and contacting a molded body containing a γ-type crystal and a compound for forming a γ-type crystal with a liquid containing a compound for forming an ε-type crystal, or The method mainly comprises a step S2 of exposing to the vapor of the compound for forming a type crystal, and a step S3 of thereafter forming a ε-type crystal of SPS by bringing the molded body into contact with a solvent in which the compound for forming an ε-type crystal is dissolved. You. It is considered that the ε-type crystal is formed by a combination of Step S2 and Step S3. However, at the stage of the step S2, the formation of the ε-type crystal may have progressed to some extent.

  FIG. 4 is a flowchart showing a conventional method for producing an ε-type crystal SPS compact. The method shown in FIG. 4 includes, using a chloroform solution of SPS, a step S11 of forming an SPS film containing a δ-type crystal in which chloroform is included as a guest compound, and forming the SPS film containing the δ-type crystal at 120 ° C. or more. The method includes a step S12 of forming a γ-type crystal by annealing, a step S13 of exposing the SPS film containing the γ-type crystal to chloroform, and a step D14 of washing the SPS film with acetonitrile.

  The method of FIG. 3 does not require an annealing step and can more easily produce an ε-type crystal molded body than the method of FIG. According to the findings of the present inventors, a mixed crystal containing a γ-type crystal is easily formed in a molded body containing an ε-type crystal finally obtained through an annealing step. From such a viewpoint, it is preferable that the temperature of the molded body is maintained at 60 ° C. or less in the process S1, the process S2, the process S3, and a period between these processes (that is, from the start of the process S1 to the completion of the process S4). Good. Although the lower limit of the temperature of the molded body is not particularly limited, the temperature of the molded body may be maintained at, for example, 10 ° C. or higher.

  Hereinafter, each step constituting the method of FIG. 3 will be described.

  The amorphous SPS molded body used for step S1 is obtained by, for example, melt-molding SPS. The amorphous SPS molded body may include minute crystallized portions, but may be amorphous as a whole. Alternatively, instead of the amorphous SPS compact, an SPS compact including a crystal part formed by a method such as stretching or introduction of a guest compound may be used.

  The amorphous SPS molded body after the melt molding contains SPS as a main component. The proportion of SPS in the amorphous SPS molded body is, for example, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more based on the total mass of the molded object. Is also good.

  The shape of the molded body is not particularly limited, but may be, for example, a film. The method of melt molding can be selected from ordinary methods such as hot pressing. The heating temperature for melt molding may be equal to or higher than the melting point of SPS (270 ° C.), for example, about 300 ° C.

  Step S1 includes contacting the amorphous SPS molded body with a liquid containing a compound for forming a γ-type crystal, or exposing the amorphous SPS molded body to vapor of the compound for forming a γ-type crystal. The liquid to be brought into contact with the amorphous SPS molded body may be the liquid γ-type crystal forming compound itself or a solution containing the γ-type crystal forming compound. Specifically, the γ-type crystal can be formed by immersing the molded body in a liquid γ-type crystal forming compound or a solution containing the γ-type crystal forming compound. When the amorphous SPS molded body is exposed to the vapor of the compound for forming a γ-type crystal, for example, the amorphous SPS film can be placed in an atmosphere containing the vapor of the compound for forming a γ-type crystal. The temperature at the time of immersion or exposure is not particularly limited, but may be, for example, room temperature (about 25 ° C) to 60 ° C. The time of immersion or exposure is not particularly limited, but may be 10 minutes to 2 weeks.

  The compound for forming a γ-type crystal used in step S1 can be selected, for example, from the viewpoints of molecular volume, association property and solubility parameter. A relatively large molecular volume and having a solubility parameter close to SPS can be considered as a requirement for a compound that can function as a compound for forming a γ-type crystal. Compounds with solubility parameters close to SPS can be compatible with SPS and cause a change in the conformation of the SPS molecular chains such that crystals form. Compounds and aggregates having a relatively large molecular volume while having a solubility parameter close to that of SPS are unlikely to enter between SPS molecular chains, so that a γ-type crystal having a relatively densely packed molecular chain is formed. It is believed that they can be formed.

From the viewpoint of, gamma-type crystals forming compound, compounds having a molecular volume of 160 Å ³ or more, or a compound that forms an aggregate with a 160 Å ³ or more molecular volumes comprise two or more molecules of gamma-type crystals forming compound It may be. To easily form a γ-type crystal, the molecular volume of the γ-type crystal forming compound or the aggregates is, 300 Å ³ or less, or 250 Å ³ may be less.

  Here, in this specification, the molecular volume means a value calculated by MOPAC in a molecular modeling method. As a calculation program for MOPAC, WINNOSTAR or http://www.chemicalize.org/ can be used.

The solubility parameter (SP value) of the compound for forming a γ-type crystal formed by the Fedose equation is in the range close to the SP value of SPS of 10.4, specifically 8.0 to 14.5 (cal · cm ^3). ) It may be ^1/2 . In order to easily form a γ-type crystal, the SP value of the compound for forming a γ-type crystal is 8.3 (cal · cm ³ ) ^1/2 or more, 8.5 (cal · cm ³ ) ^1/2 or more, Or 9.0 (cal · cm ³ ) ^1/2 or more, 14.1 (cal · cm ³ ) ^1/2 or less, 12.4 (cal · cm ³ ) ^1/2 or less, and 12.1 (cal · cm ³ ) ^1/2 or less. It may be 0 (cal · cm ³ ) ^1/2 or less, or 11.5 (cal · cm ³ ) ^1/2 or less.

Examples of γ-type crystal form for a compound having a 160 Å ³ or more molecular volume, alkyl-substituted aromatic hydrocarbon compounds such as n- alkylbenzenes and the like. The n-alkylbenzene may have 5 to 10 carbon atoms. Specific examples of n-alkylbenzene include 1-phenylpentane (molecular volume (simple): 168.1Å ³ , SP value: 10.5 (cal · cm ³ ) ^1/2 ), 1-phenylnonane (molecular volume ( stand-alone): 235.5Å ^3, SP ^{value: 8.8 (cal · cm 3)} 1/2), anthracene (molecular volume (single): 170.8Å ^3, SP value: 11.1 (cal · ^cm 3) ^1/2), and Shisujasumon (molecular volume (simple substance): 177.5Å ^3, SP ^{value: 9.4 (cal · cm 3)} 1/2)) and the like.

Examples of aggregate γ-type crystal forming compounds forming with 160 Å ³ or more molecular volume include nitrogen-containing heterocyclic compound. Specific examples of the nitrogen-containing heterocyclic compound include 1-methylimidazole (molecular volume (dimer): 161.6Å ³ , SP value: 10.5 (cal · cm ³ ) ^1/2 ), triazine (molecular volume) (Trimer): 216.0Å ³ , SP value: 14.1 (cal · cm ³ ) ^1/2 , and pyrazole (molecular volume (trimer): 192.9Å ³ , SP value: 12.0) (Cal · cm ³ ) ^1/2 ).

  These compounds may be used alone or in combination of two or more as compounds for forming a γ-type crystal.

  In step S2, a liquid containing the ε-type crystal forming compound is brought into contact with the molded body containing the γ-type crystal and the compound for forming a γ-type crystal, or the molded body is exposed to vapor of the compound for forming an ε-type crystal. Including. Specifically, the molded article may be immersed in a liquid ε-type crystal forming compound or a solution containing the ε-type crystal forming compound, or may be formed under an atmosphere containing vapor of the ε-type crystal forming compound. The body may be placed. The temperature at the time of immersion or exposure is not particularly limited, but may be, for example, room temperature (about 25 ° C) to 60 ° C. The time of immersion or exposure is not particularly limited, but may be 10 minutes to 2 weeks.

  The compound for forming an ε-type crystal used in step S2 can be selected, for example, from the viewpoint of molecular volume, association property and solubility parameter. Relatively small molecular volume and having a solubility parameter close to SPS can be considered as a requirement for a compound that can function as a compound for forming an ε-type crystal. Compounds with solubility parameters close to SPS can be compatible with SPS and cause a change in the conformation of the SPS molecular chains such that crystals form. Compounds and aggregates having a relatively small molecular volume while having a solubility parameter close to that of SPS are liable to penetrate between SPS molecular chains, so that ε-type crystals having large free space between molecular chains are formed. It is thought that it can contribute.

From the viewpoint of, the ε-form crystal forming compound may be a compound having a molecular volume of less than 160 Å ^3. This compound may be a compound that does not substantially form an aggregate. ε type crystal forming compound may be a compound that forms an aggregate having a molecular volume of less than 160 Å ³ comprise two or more molecules of ε type crystal forming compound. To easily form ε-type crystal, the molecular volume of ε type crystal forming compound or the aggregates is, 150 Å ³ or less, or 105 Å ³ may be less, 50 Å ³ or more, 60 Å ³ or more, or, 70 Å ^It may be ³ or more or 80 ° ³ or more.

The solubility parameter (SP value) of the compound for forming an ε-type crystal formed by the Fedose equation is in the range close to the SP value of SPS of 10.4 (cal · cm ³ ) ^1/2 , specifically 8.0. １４14.5 (cal · cm ³ ) ^1/2 . In order to easily form an ε-type crystal, the SP value of the compound for forming an ε-type crystal is 8.3 (cal · cm ³ ) ^1/2 or more, 8.5 (cal · cm ³ ) ^1/2 or more, Or 9.0 (cal · cm ³ ) ^1/2 or more, 14.1 (cal · cm ³ ) ^1/2 or less, 12.4 (cal · cm ³ ) ^1/2 or less, and 12.1 (cal · cm ³ ) ^1/2 or less. It may be 0 (cal · cm ³ ) ^1/2 or less, or 11.5 (cal · cm ³ ) ^1/2 or less.

Has a molecular volume of less than 160 Å ^3, Examples of substantially formed without ε type crystal compound for forming an aggregate, a halogenated hydrocarbon compound unsubstituted, unsubstituted ether compounds, and alkyl-substituted aromatic hydrocarbons And hydrogen compounds. Specific examples of the unsubstituted halogenated hydrocarbon compound include chloroform (molecular volume (simple): 70.2 ： ³ , SP value: 8.8 (cal · cm ³ ) ^1/2 ), and boiling point: 61.0 ° C. ), Trichloroethylene (molecular volume (simple): 80.4Å ³ , SP value: 10.7 (cal · cm ³ ) ^1/2 ), boiling point: 87.2 ° C), dichloromethane (molecular volume (simple): 56. 6Å ³ , SP value: 9.4 (cal · cm ³ ) ^1/2 , boiling point: 39.6 ° C.). Specific examples of the unsubstituted ether compound include tetrahydrofuran (molecular volume (simple): 77.9Å ³ , SP value: 8.3 (cal · cm ³ ) ^1/2 ), boiling point: 66.0 ° C. Can be Examples of the alkyl-substituted aromatic hydrocarbon compound include p-diethylbenzene (molecular volume (simple): 150 ° ³ , SP value: 9.0 (cal · cm ³ ) ^1/2 ), and n-propylbenzene (molecular volume (simple) ): 134 ° ³ , SP value: 9.0 (cal · cm ³ ) ^1/2 ). Compounds similar to the polymerizable monomers described below can also be used as compounds for forming ε-type crystals. For example, a cyclic ketone compound such as 2-methyl-2-cyclopenten-1-one (molecular volume (simple): 99.3Å ³ , SP value: 10.3 (cal · cm ³ ) ^1/2 ), and benzaldehyde An aromatic aldehyde compound such as (molecular volume (simple): 103Å ³ , SP value: 11.7 (cal · cm ³ ) ^1/2 ) can be used as a compound for forming an ε-type crystal.

  Step S3 includes contacting the molded article after step S2 with a predetermined solvent in which the compound for forming ε-type crystals is dissolved. Usually, the molded body is immersed in a solvent for a predetermined time. The temperature at the time of immersion is not particularly limited, but may be, for example, room temperature (about 25 ° C.) to 60 ° C. The immersion time is not particularly limited, but may be 10 minutes to 2 weeks.

  The solvent used in step S3 may be any solvent in which the compound for forming ε-type crystals is dissolved, and may be, for example, acetonitrile or acetone.

<Composite molded body>
By forming the polymer in the SPS compact containing the ε-type crystal, a composite compact having various functions can be obtained. FIG. 5 is a flowchart illustrating one embodiment of a method of manufacturing a composite molded body. The method shown in FIG. 5 includes a step S4 of incorporating a polymerizable monomer into an ε-type crystal SPS molded article, a step S5 of polymerizing the polymerizable monomer incorporated in the molded article, and a step S6 of washing the molded article with a solvent. And The composite molded article obtained by this method may include SPS forming ε-type crystals and a polymer of a polymerizable monomer incorporated in ε-type crystals.

  Step S4 includes, for example, contacting a liquid containing a polymerizable monomer with the ε-type crystal SPS compact, or exposing the compact to vapor of the polymerizable monomer. Specifically, the molded article may be immersed in a liquid polymerizable monomer or a solution containing the polymerizable monomer, or the molded article may be placed in an atmosphere containing a vapor of the polymerizable monomer. The temperature at the time of immersion or exposure is not particularly limited, but may be, for example, room temperature (about 25 ° C) to 60 ° C. The time of immersion or exposure is not particularly limited, but may be 10 minutes to 2 weeks.

The polymerizable monomer is not particularly limited as long as it is a compound that can be included in the ε-type crystal and is polymerized by oxidation polymerization, radical polymerization, or the like. Polymerizable monomers, like ε type crystal forming compound, molecular volume of less than 160 Å ^3, or a compound that forms an aggregate having a molecular volume of less than 160 Å ³ comprise two or more molecules of the polymerizable monomer Is also good. The solubility parameter (SP value) calculated by the Fedose formula of the polymerizable compound may be 8.0 to 14.5.

  The polymerizable monomer is, for example, selected from a monocyclic organic compound having a hetero atom, a fused bicyclic organic compound having a hetero atom, and a bridged or spiro bicyclic organic compound having a bridged ring or a spiro ring. It may contain at least one compound.

  The monocyclic organic compound as the polymerizable monomer may be a monocyclic aromatic organic compound. The monocyclic organic compound may have an optionally substituted 5-membered ring or an optionally substituted 6-membered ring. The 5-membered ring and the 6-membered ring may contain a hetero atom, or may be an amino group, an aldehyde group, a carboxylic acid group, a ketone group, an amide group, an imide group, an acyl halide group, -OR (R is May be substituted with a substituent having at least one functional group selected from a group represented by the formula:

  The hetero atom contained in the polymerizable monomer is an atom other than a carbon atom and a hydrogen atom, for example, at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a selenium atom. Specific examples of the hetero atom and the substituent also apply to the condensed ring described below.

Examples of the substituent having an amino group include a primary amino group (—NH ₂ ) and an alkylamino group (—NHR ¹ , —N (R ¹ ) R ² (R ¹ and R ² represent an alkyl group). ). Examples of the group having an aldehyde group include a group represented by —R ³ CHO (R ³ represents a direct bond, an alkylene group, an alkenylene group, or an arylene group). Examples of the substituent having a carboxylic acid group (—COOH) include a group represented by —R ⁴ COOH (R ⁴ represents a direct bond, an alkylene group, an alkenylene group, or an arylene group). The substitution having a ketone group is represented, for example, by -R ⁵ COR ⁶ (R ⁵ represents a direct bond, an alkylene group, an alkenylene group or an arylene group, and R ⁶ represents an alkyl group, an alkenyl group or an aryl group). Groups. Examples of the substituent having an amide group include a primary amide group (—CONH ₂ ), —R ⁷ CON (R ⁸ ) R ^{9, and} —R ¹⁰ N (R ¹¹ ) COR ¹² (R ⁷ and R ¹⁰ are a direct bond) , An alkylene group, an alkenylene group or an arylene group, R ⁸ and R ¹¹ represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, and R ⁹ and R ¹² represent an alkyl group, an alkenyl group or an aryl group.) And the group represented by Examples of the group having an imide group include -R ¹³ CONR ¹⁴ COR ¹⁵ (R ¹³ represents a direct bond, an alkylene group, an alkenylene group, or an arylene group, and R ¹⁴ and R ¹⁵ represent a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. Represents a group). Examples of the substituent having a halogenated acyl group include a group represented by —R ¹⁶ COX (R ¹⁶ represents a direct bond, an alkylene group, an alkenylene group, or an arylene group, and X represents a halogen atom). Can be As a group represented by -OR (R represents an optionally substituted hydrocarbon group), for example, -R ¹⁷ OR ¹⁸ (R ¹⁷ represents a direct bond, an alkylene group, an alkenylene group or an arylene group; R ¹⁸ represents an alkyl group, an alkenyl group or an aryl group.). Examples of the substituent having a hydroxy group include a hydroxy group (—OH), —R ¹⁹ (OH) R ²⁰ (R ¹⁹ represents an alkylene group, an alkenylene group, or an arylene group, and R ²⁰ represents a hydrogen atom, an alkyl group, An alkenyl group or an aryl group.). Specific examples of the substituent also apply to the condensed ring described below.

  Examples of the 5-membered ring containing a hetero atom include pyrrole, 1,2,4-triazole, 1H-1,2,3-triazole, imidazole, pyrazole, pyrrolidine, thiazole, thiophene, selenophene, isoxazole, and tetrafudrofuran. Is mentioned. Examples of the 6-membered ring containing a hetero atom include pyridine, pyrazine, piperidine, and triazine.

  Specific examples of the monocyclic organic compound having a 5- or 6-membered ring containing a hetero atom include 1-methylimidazole, pyrrolidine, pyrazole, thiophene, selenophene, pyridine, and thiazole.

  Specific examples of the monocyclic organic compound having a 5- or 6-membered ring substituted with a substituent containing an amino group include aniline and cyclohexylamine. Specific examples of the monocyclic organic compound having a 5- or 6-membered ring substituted with a substituent containing an aldehyde group include benzaldehyde. Specific examples of the monocyclic organic compound having a 5- or 6-membered ring substituted with a substituent containing a hydroxy group include phenol, benzyl alcohol, and phenethyl alcohol. Specific examples of the monocyclic organic compound having a 5- or 6-membered ring substituted with a substituent containing a group represented by -OR include 4-methylanisole.

  The polymerizable monomer may be a fused bicyclic organic compound having a fused ring composed of two optionally substituted 6-membered rings. The condensed ring may contain a hetero atom, or may be an amino group, an aldehyde group, a carboxylic acid group, a ketone group, an amide group, an imide group, an acyl halide group, -OR (R is a carbon atom which may be substituted. A hydrogen group) and a substituent having at least one functional group selected from a hydroxy group.

  Examples of the condensed ring composed of two 6-membered rings containing a hetero atom include quinoxaline, quinoline, and isoquinoline.

  Specific examples of the condensed bicyclic organic compound having a condensed ring substituted with a substituent containing an amino group include 7-quinolineamine. Specific examples of the condensed bicyclic organic compound having a condensed ring substituted with a substituent containing an aldehyde group include 2-naphthaldehyde. Specific examples of the condensed bicyclic organic compound having a condensed ring substituted with a substituent containing a hydroxy group include 8-hydroxyquinoline.

  The polymerizable monomer is a bridged or spiro bicyclic organic compound having a bridged or spiro ring composed of two optionally substituted rings selected from a 4-membered ring, a 5-membered ring and a 6-membered ring It may be.

  Bridged rings containing a heteroatom include, for example, quinuclidine. Spiro rings containing a heteroatom include, for example, spiropentane in which one carbon atom is replaced by a heteroatom.

  Specific examples of the bicyclic organic compound having a bridged ring or a spiro ring substituted with a substituent containing an amino group include aminonorbornadiene and luminol. Specific examples of the bicyclic organic compound having a bridged ring or a spiro ring substituted with a substituent containing an aldehyde group include formyl spiropentane and formyl spirodecane. Specific examples of the bicyclic organic compound having a bridged ring or a spiro ring substituted with a substituent containing a hydroxy group include quinuclidin-3-ol and indanol.

  Among the above examples, the polymerizable monomer is a monocyclic aromatic organic compound (monocyclic heteroaromatic) having a 5-membered ring or a 6-membered ring which may be substituted and contains a hetero atom. Compound), and an amino group, an aldehyde group, a carboxylic acid group, a ketone group, an amide group, an imide group, an acyl halide group, and -OR (R represents an optionally substituted hydrocarbon group). And at least one compound selected from monocyclic or condensed bicyclic aromatic hydrocarbon compounds substituted with a substituent having at least one functional group selected from a group selected from the group consisting of an aromatic group and a hydroxy group.

  More specifically, the polymerizable monomer may be an aromatic amine, thiophene, bromothiophene, pyrrole, or 4-vinylpyridine, or may be a derivative in which these are substituted with a substituent. Aromatic amines include aniline, aminonaphthalene, and carbazole. Aromatic amines and derivatives thereof can be oxidatively polymerized in a reaction solution containing, for example, ammonium persulfate and an inorganic acid. Thiophene and its derivatives can be oxidatively polymerized in a reaction solution containing, for example, iron (III) chloride, copper (I) chloride / pyridine complex. Pyrrole and its derivatives can be oxidatively polymerized in a reaction solution containing an oxidizing agent such as an iron salt. Vinylpyridine and its derivatives can undergo radical polymerization in a reaction solution containing a radical generator such as ammonium persulfate.

  In step S5, the polymerizable monomer is polymerized, and a polymer is formed in the molded article. In the present specification, the polymer also includes oligomers such as dimers and trimers. Step S5 includes, for example, immersing the molded body in which the polymerizable monomer has been incorporated into a reaction solution containing a polymerization catalyst. For example, when polymerizing a polymerizable monomer by oxidative polymerization of aniline, the reaction solution may be an aqueous solution containing ammonium persulfate and hydrochloric acid. The temperature and time of the polymerization reaction are appropriately adjusted so that the polymerization proceeds sufficiently.

  Step S6 includes, for example, contacting the molded article after the polymerization in step S5 with a predetermined solvent in which the polymerizable monomer is dissolved. Usually, the molded body is immersed in a solvent for a predetermined time. The temperature at the time of immersion is not particularly limited, but may be, for example, room temperature (about 25 ° C.) to 60 ° C. The immersion time is not particularly limited, but may be 10 minutes to 2 weeks. By the step S6, the remaining polymerizable monomer and / or the polymer not included in the crystals in the molded body can be washed away. The solvent used in step S5 may be, for example, acetonitrile or acetone.

  The content of the polymer in the composite molded body is not particularly limited, but may be, for example, 1 to 50% by mass based on the mass of the composite molded body.

  By selecting a polymer constituting the composite molded article, various functions or properties such as conductivity, antistatic property, moisture absorption property, anticorrosion property, heat resistance, and adsorptivity can be imparted to the molded article. By enclosing the polymer in the tubular free space of the ε-type crystal, the polymer can be arranged in a state where the molecular chains of the polymer are oriented in a specific direction.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

1. Evaluation method 1-1. Wide-angle X-ray diffraction (WAXD)
<Apparatus>
Wide-angle X-ray diffractometer Imaging plate X-ray detector: R-AXIS IV ++
<Measurement conditions>
DETECTOR DISTANCE: 150mm
EXPOSURE TIME: 120 sec.
X-ray two-dimensional data processing software: FIT2D
1-2. Fourier transform infrared spectroscopy (FT-IR)
<Apparatus>
Perkin Elmer FT-IR Spectrometer SPECTRUM1000
<Condition>
Measurement range: 4000 to 400 cm ^-1
Number of scans: 32 Resolution: 1.0 cm ^-1
Interval: 0.5cm ^-1

2. ε-type crystal SPS film 2-1. Amorphous syndiotactic polystyrene (SPS) film Syndiotactic polystyrene (manufactured by Idemitsu Kosan Co., Ltd., melting point: 270 ° C., Mw: 1.94 × 10 ⁵ , Mw / Mn = 3.37 (Mw: weight average molecular weight, Mn (number average molecular weight) is placed between two aluminum foils placed in an opening of a frame-shaped mold (about 7 cm × 7 cm, thickness 0.25 mm), and gold The mold and the aluminum foil were sandwiched between the lower copper plate and the upper iron plate.In this state, the mold and the aluminum foil were set in a hot press having a hot plate facing the same.The temperature of the hot plate was set to 300.degree. The upper iron plate was adjusted to contact the upper hot plate, and the syndiotactic polystyrene was melted by heating without pressure for 4 minutes. The pressure was released to MPa and held for 4 minutes, after which the pressure was released and the film was quenched in ice water before the SPS film formed was carefully peeled off the aluminum foil. The film was dried by vacuum drying for 24 hours, had a thickness of about 300 μm, and was subjected to wide-angle X-ray diffraction measurement.

2-2. Immersion in γ-type crystal forming compound The obtained amorphous SPS film is immersed in 1-methylimidazole, 1-phenylpentane or 1-phenylnonane as a γ-type crystal forming compound at 60 ° C. for 2 hours. I let it. After immersion, the film was rinsed with distilled water.

2-3. Exposure to Compound for Forming ε-Type Crystal (Chloroform) The film after immersion in the compound for forming γ-type crystal was not annealed, and chloroform was placed inside a sample tube containing chloroform as a compound for forming ε-type crystal. Hanged so as not to touch. The sample tube was then sealed with a lid, and the film was exposed to chloroform vapor at room temperature for about 1 day. Thereafter, the film was rinsed with distilled water.

2-4. Immersion in acetonitrile The film after exposure to chloroform was immersed in acetonitrile at room temperature for 2 hours. After immersion, the film was rinsed with distilled water.

2-5. Evaluation The wide-angle X-ray diffraction (WAXD) of the film after immersion in the compound for forming a γ-type crystal, after exposure to chloroform, and after immersion in acetonitrile was measured. 6 shows the results of WAXD measurement using 1-methylimidazole, FIG. 7 shows the results of measurement using 1-phenylpentane, and FIG. 8 shows the results of measurement using 1-phenylnonane. In each case, the films after immersion in acetonitrile showed clear peaks derived from ε-type crystals at around 6.9 ° and 8.1 °. Since the peaks at 9.4 ° and 10.4 ° derived from the γ-type crystal were not observed, it was confirmed that a high-purity ε-type crystal substantially containing no γ-type crystal was formed.

9 and 10 are FT-IR spectra of a film obtained using 1-methylimidazole before and after immersion in acetonitrile. FIG. 9 is an enlarged view of the spectrum around 1200 cm ⁻¹ and FIG. 10 is an enlarged view of the spectrum near 2250 cm ⁻¹ . From FIG. 9, it can be seen that the absorption peak near 1200 cm ⁻¹ derived from cyclic C = N disappeared by acetonitrile immersion. This suggests that 1-methylimidazole was washed away by acetonitrile. As shown in FIG. 10, an absorption peak appeared around 2250 cm ⁻¹ after immersion in acetonitrile. This suggests that a small amount of acetonitrile has penetrated the film.

3. Composite molded body (polyaniline / SPSε type crystal)
The amorphous SPS film is treated in the same procedure as in “2. ε-type crystal SPS film” in the order of immersion in 1-methylimidazole, exposure to chloroform, and immersion in acetonitrile to obtain an ε-type crystal. Was obtained. The SPS film was exposed to aniline vapor at room temperature for 3 days. Thereafter, the film was immersed in a reaction solution containing ammonium persulfate and hydrochloric acid at 25 ° C. for 0.5 hour. The reaction solution was prepared by adding 0.01 g of ammonium persulfate to 10 mL of 0.1 mol / L hydrochloric acid. The initially white SPS film was partially stained green, suggesting that polyaniline was formed. The film was then immersed in acetonitrile at room temperature for 2 hours.

  FIG. 11 shows the results of WAXD measurement of the film from before aniline exposure to after immersion in acetonitrile. (C-1) is an ε-type crystal SPS film (before aniline exposure), (C-2) is after aniline exposure, (C-3) is a white portion of the SPS film after polymerization reaction, (C-4) and (C-4). C-5) is the portion of the SPS film that has been dyed green after the polymerization reaction, and (C-6) is the measurement result after immersion in acetonitrile. In (C-4) and (C-5) after the polymerization reaction, the peak of the δ-type crystal (8.0 °, 10.3 °) and the peak of the ε-type crystal (6.9 °, 8.1) °) both were observed. In (C-6) after immersion in acetonitrile, the peak of the δ-type crystal disappeared, and a sharp peak of the ε-type crystal was observed. 12 and 13 are FT-IR spectra of (C-2), (C-3), (C-4) and (C-6). Regarding (C-6) after immersion in acetonitrile, the peak derived from aniline disappeared. That is, it is considered that excess aniline was washed away by acetonitrile immersion. These results strongly suggest that polyaniline was formed in a state where a co-crystal was formed with the ε-type crystal.

  It is possible to obtain an SPS molded article having various functions or characteristics that have been difficult to impart to polystyrene, such as conductivity, antistatic property, hygroscopic property, anticorrosive property, heat resistance, and adsorptive property. Therefore, application of the polystyrene molded article to a wider field than before is expected.

  DESCRIPTION OF SYMBOLS 1 ... A molded object, 5 ... Free space, 10 ... Syndiotactic polystyrene, 20 ... Guest compound (compound for formation of (epsilon) type crystal).

Claims (4)

Forming the molded body containing the syndiotactic polystyrene, by contacting the liquid containing the compound for forming a γ-type crystal, or by exposing to the vapor of the compound for forming a γ-type crystal, to form the γ-type crystal of the syndiotactic polystyrene The process of
The molded body containing the γ-type crystal and the compound for forming a γ-type crystal is brought into contact with a liquid containing the compound for forming an ε-type crystal, or exposed to a vapor of the compound for forming an ε-type crystal, and thereafter, the molding is performed. Forming a ε-type crystal of the syndiotactic polystyrene by contacting the body with a solvent in which the ε-type crystal forming compound dissolves;
Equipped with a,
The γ-type crystal forming compound, to form an aggregate having 160 Å ³ or more molecular volumes including said two or more molecules of γ-type crystal forming compound is a compound,
A method for producing a molded article containing syndiotactic polystyrene forming an ε-type crystal. Before Symbol γ-type crystal forming compounds, the solubility parameter calculated by the equation of Fedosu a ^{8.0~14.5 (cal · cm 3) 1/2} ,
The method of claim 1. A compound wherein the compound for forming an ε-type crystal has a molecular volume of less than 160 ° ³ and / or which comprises two or more molecules of the compound for forming an ε-type crystal and forms an aggregate having a molecular volume of less than 160 ° ³ ; And
The solubility parameter of the compound for forming an ε-type crystal formed by the Fedose equation is 8.0 to 14.5 (cal · cm ³ ) ^1/2 .
The method according to claim 1.   The process according to any one of claims 1 to 3, wherein the temperature of the molded body is maintained at 60 ° C or lower during the step of forming a γ-type crystal, the step of forming an ε-type crystal, and a period between these steps. A method according to claim 1.

Images