JP5125020B2 - Quasi-crosslinked cyclic polymer - Google Patents

Description

  The present invention relates to a novel pseudo-crosslinked resin and a molded article made of the pseudo-crosslinked resin.

  In recent years, research and development on synthetic resins have progressed, and synthetic resins having various performances have been obtained. Among such research and development, many attempts have been made to add new performance to an existing synthetic resin without impairing the inherent performance of the resin.

  Typical synthetic polymer materials include acrylic resin or styrene resin, aromatic polyamide resin, thermosetting resin, ionomer resin, polyimide resin, and the like.

  In the case of acrylic resin or styrenic resin, it is relatively inexpensive, has excellent transparency, can produce polymers having various characteristics from rubbery materials to glassy polymers, and can be easily modified. Although it has excellent characteristics such as the above, on the other hand, since there remains a big problem in improving both strength, heat resistance and toughness, attempts have been made to improve this. For example, lack of toughness is a problem common to all acrylic resins, but several methods for solving this problem have been reported, such as adding rubber particles in the resin (Japanese Patent Laid-Open No. 3-52910). Are known. However, these methods cannot solve the whitening phenomenon (bending processability) that occurs when the resin is bent. For this reason, the present condition is that the acrylic resin which is compatible with the glass transition point more than room temperature and the formation capability (bending workability) of the thin film which requires toughness is not found. As a method for improving the heat resistance, it is known to introduce a reactive atomic group into the main chain and to thermally cure it by heating or light. In this method, it is common to introduce the atomic group in a solution state, but although heat resistance is improved, problems such as gelation are likely to occur when the solvent is removed, and curing after the solvent is removed. There are problems such as the reaction requiring a lot of time.

  In the aromatic polyamide resin, polyparaphenylene terephthalamide can be mentioned as the most typical example. The aromatic polyamide resin has particularly excellent crystallinity, a high melting point, and excellent flame retardancy, and has a high mechanical strength, a low linear expansion coefficient, etc. because of its rigid molecular structure. However, the problem of this resin is that it is hardly soluble in an organic solvent and an inorganic strong acid such as concentrated sulfuric acid must be used as a solvent. Fibers spun from concentrated solutions such as concentrated sulfuric acid are known to exhibit high strength and elastic modulus, and have been industrially implemented. However, there are few application examples to a film, and it is only known that it can be achieved by stretching in a swollen state. However, this method has a problem that the manufacturing process is extremely complicated, the productivity is lowered, and the product price is increased. As a method for improving the solubility in an organic solvent, a method is known in which a unit in which a halogen group is introduced into an aromatic nucleus or a unit having high flexibility is copolymerized (Japanese Patent Publication No. 56-45421). However, in this method, there is a concern that the heat resistance and the high flame retardance are impaired, and the metal corrosivity of halogen atoms becomes a problem.

  Since thermosetting resins are generally insoluble and infusible cured products, they have characteristics that are very excellent in durability such as solvent resistance or strength retention at high temperatures. However, since the cross-linking reaction is formed by a covalent bond, there is a problem that a long time is required for the formation of the cross-linking reaction, and there is a problem that reworking cannot be performed. This defect is a fatal defect with respect to securing recyclability in recent years.

  An ionomer resin can be mentioned as the closest one to the recyclable thermosetting resin. This is obtained by adding a metal oxide or metal hydroxide such as magnesium oxide or calcium hydroxide to a polymer having a carboxyl group in the side chain. A pseudo cross-linking point is formed by forming an ionic bond between the metal and the carboxyl group. In this method, although some improvement in heat resistance and toughness is observed, the binding force between the metal compound and the carboxyl group is weak, and because the solubility of the metal compound in the resin is low, only a small amount can be added. There is no significant improvement in properties.

Among engineering plastics, polyimide resins are extremely useful materials industrially because they have extremely high heat resistance and tough film performance. As a method for processing polyimide into a film, it is common to form an imide ring by applying a polyimide solution and then heating at a high temperature. At this time, once an imide ring is formed, the solubility in a solvent is significantly reduced. This feature is a very serious drawback when recycling polyimide. Therefore, there is a demand for a material that can achieve both solubility in a solvent and high heat resistance, and a method for improving solubility in an organic solvent by copolymerizing a unit in which a substituent such as alkyl is introduced into an aromatic nucleus is known. It has been. However, a material having a glass transition temperature of 320 ° C. or higher has not been obtained by this method. Another disadvantage of this method is that the price of the product is high because the monomer is expensive.
Japanese Patent Laid-Open No. 3-52910 Japanese Examined Patent Publication No. 56-45421

  The present invention has been made from the above viewpoint, and by forming sufficient hydrogen bonds between molecules of a cyclic synthetic resin in which molecular ends are bonded within the same molecule, it has a pseudo-crosslinked structure. , A pseudo-crosslinked resin composition having high heat resistance and new performance by simple processing and having particularly conflicting properties (for example, strength, heat resistance and toughness), and molded from this pseudo-crosslinked resin The purpose is to provide a molded product.

  As a result of intensive research to solve the above problems, the present inventors have introduced functional combinations by introducing a specific functional group into a cyclic synthetic polymer in which various molecular ends are bonded within the same molecule. It is possible to form a hydrogen bond between the synthetic cyclic polymers by the interaction of the groups and to have a structure similar to the crosslinked structure, and to easily achieve a new performance for the synthetic resin, especially The inventors have found that it is possible to produce a synthetic resin having both contradictory characteristics, and have completed the present invention.

That is, the present invention is as follows.
(1) A pseudo-crosslinked resin comprising a cyclic polymer in which one or more synthetic polymers are bonded intramolecularly at or near the molecular end,
The synthetic polymer has a first atomic group containing a group selected from the group consisting of a carbonyl group, a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group, an optionally substituted amino group, and at least one A second atomic group containing a group selected from the group consisting of a heterocyclic group containing a nitrogen atom,
A pseudo-crosslinked resin composition comprising a cyclic polymer, wherein a pseudo-crosslink is formed by a hydrogen bond between a first atomic group and a second atomic group.
Here, the hydrogen bond between the first atomic group and the second atomic group is at least an intermolecular hydrogen bond.

(2) The pseudo-crosslinked resin composition comprising the cyclic polymer according to (1), wherein the synthetic polymer has both a first atomic group and a second atomic group in the same molecule.
(3) The first atomic group is an atomic group having a basic skeleton selected from the structural formula group represented by [Chemical Formula 1] to [Chemical Formula 3] (hereinafter referred to as “Structural Formula Group A”); The atomic group is an atomic group having a basic skeleton selected from the structural formula group represented by [Chemical Formula 4] to [Chemical Formula 6] (hereinafter referred to as “Structural Formula Group B”). A pseudo-crosslinked resin composition comprising the described cyclic polymer.

[In the above formula, R ₁ , R ₂ and R ₃ each represents an aliphatic or aromatic hydrocarbon group, n represents an integer of 1 to 5, and m represents an integer of 2 to 6, respectively. ]

[In the above formula, R ₁ , R ₂ and R ₃ each represent an aliphatic hydrocarbon group. In the formula, hydrogen bonded to carbon may be substituted with an amino group that can be substituted with an acyl group or an aliphatic hydrocarbon group. ]

(4) The first atomic group is an atomic group having a basic skeleton selected from the structural formula group represented by [Chemical Formula 7] (hereinafter referred to as “Structural Formula Group C”), and the second atomic group is 8] The pseudo-crosslinked resin composition according to (3), which is an atomic group having a basic skeleton selected from the structural formula group represented by 8) (hereinafter referred to as “structural formula group D”).

[Wherein, R ₁ and R ₂ each represents an aliphatic or aromatic hydrocarbon group, n represents an integer of 1 to 3, and m represents an integer of 2 to 6, respectively. ]

[In the above formula, R ₁ , R ₂ and R ₃ each represent an aliphatic hydrocarbon group. ]

(5) The pseudo-crosslinked resin according to (1), wherein the synthetic polymer has a molecular weight of 5000 or more.

(6) the cyclic polymer is selected from cyclic synthetic polymers having at least one bond selected from the group consisting of an amide bond, an imide bond, a urethane bond, an ester bond, an ether bond, and a carbon-carbon bond; A basic skeleton in which one atomic group has a basic skeleton selected from the structural formula group represented by [Chemical Formula 9] and the second atomic group is selected from the structural formula group represented in [Chemical Formula 10] The pseudo-crosslinked resin composition comprising the cyclic polymer as described in (1), wherein

[Wherein, R ₁ and R ₂ each represents an aliphatic or aromatic hydrocarbon group, n represents an integer of 1 to 3, and m represents an integer of 2 to 6, respectively. ]

[In the above formula, R ₁ , R ₂ and R ₃ each represent an aliphatic hydrocarbon group. ]

(7) The cyclic synthetic polymer is an aromatic polyamide, the first atomic group is an atomic group having a basic skeleton selected from the structural formula group represented by [Chemical Formula 11], and the second atomic group is The pseudo-crosslinked resin composition comprising the cyclic polymer as described in (1), which is an atomic group having a basic skeleton selected from the structural formula group represented by [Chemical Formula 12].

(8) A molded product molded from the pseudo-crosslinked resin composition according to any one of (1) to (7).

(9) The molded product according to (8), wherein the molded product is a film.

  With the pseudo-crosslinked cyclic polymer resin composition of the present invention, characteristics not found in linear polymers can be obtained. That is, the pseudo-crosslinked resin composition of the present invention is obtained as having high heat resistance, low thermal expansion, solvent resistance, etc. equivalent to a thermosetting resin without removing the solvent and providing a heat curing step. Therefore, the productivity can be improved by eliminating the heat curing step.

  Hereinafter, the present invention will be specifically described with reference to embodiments.

  The pseudo-crosslinked resin composition of the present invention includes a cyclic polymer in which one or more synthetic polymers are bonded in the same molecule at or near the molecular end, and the synthetic polymer is at least hydrogenated between molecules. A pseudo-crosslinked resin composition having a pseudo-crosslinked structure by forming a bond, wherein the synthetic polymer is selected from the group consisting of a carbonyl group, a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group A heterocyclic group containing an optionally substituted amino group and at least one nitrogen atom, which can interact with the first atomic group to form a hydrogen bond. And a second atomic group containing a group selected from the group consisting of: a hydrogen bond formed through both atomic groups.

1. Cyclic Polymer First, the cyclic polymer bonded in the same molecule at or near the molecular end of the present invention will be described.

  The cyclic polymer can be produced by reacting a linear polymer having functional groups at both ends with a polyfunctional compound capable of reacting with the functional groups at both ends in a dilute solution in which intermolecular reaction is unlikely to occur. it can. Details will be described below by taking the case of polyamide resin and polyester resin as an example.

(1) Synthesis of linear polymer composed of amide bond There is no particular limitation on the synthesis of a linear polymer whose bond constituting the main chain is mainly composed of an amide bond, and a known method can be used. For example, it can be synthesized by reacting a diamine compound and diacid chloride in an inert solvent. Examples of diamine compounds that can be used include diaminobenzene, diaminonaphthalene, diaminoanthracene, alkyl diamine compounds having 1 to 15 carbon atoms, diamino compounds having a heterocycle such as diaminopyridine, diaminopiperazine, and diaminopyrimidine, and carboxyl groups. Aromatic diamino compounds, bisaminophenoxyphenylpropane, bisaminophenoxybiphenyl, bisaminophenylsulfone and the like can be mentioned, but the compounds shown here are examples and are not limited thereto.

  Examples of the diacid chloride that can be used include phthalic acid chloride, isophthalic acid chloride, terephthalic acid chloride, naphthalenediic acid chloride, anthracenedioic acid chloride, and diacid chlorides having 1 to 15 carbon atoms. The examples are merely examples, and the present invention is not limited to these examples.

There is no restriction | limiting in particular about the polymerization method, A well-known method can be used. For example, it can be synthesized by reacting the diamino compound and the diacid chloride in an inert solvent. Examples of the solvent that can be used include dimethylacetamide, N-methylpyrrolidone, and γ-butyrolactone, but the examples shown here are only examples, and the present invention is not limited thereto.
A known interfacial polycondensation reaction can also be used. For example, it can be synthesized by dissolving a diamino compound in distilled water and dissolving diacid chloride in methylene chloride, chloroform, toluene, xylene or the like, which is a solvent incompatible with water, and polycondensing at the interface.

  When solution polymerization is performed, it is desirable that the produced polymer has high solubility in a solvent. This is because the molecular weight of the polymer cannot be increased any more when it is precipitated from the solvent because the produced polymer has low solubility in the solvent. As a method for increasing the solubility, salts such as lithium chloride, calcium chloride, lithium bromide, calcium bromide can be added. The salts listed here are examples and are not limited thereto.

  There is no restriction | limiting in particular in the temperature at the time of performing solution polymerization, Any temperature can be suitably selected. If the polymerization temperature is too high, side reactions with water and the like may be relatively increased, and if the polymerization temperature is too low, the reactivity may be lowered. Therefore, the polymerization temperature is preferably about 0 ° C to 100 ° C, more preferably about 10 ° C to 60 ° C, and most preferably about 10 ° C to 30 ° C. For the purpose of reducing unreacted monomers, the polymerization temperature can be raised to 100 ° C. or higher after the reaction is almost completed.

  There is no restriction | limiting in particular in the density | concentration of a monomer, It can select suitably. When the concentration is too low, the reaction rate is lowered, and the time for obtaining a high molecular weight is remarkably increased. On the other hand, if the concentration is too high, the viscosity of the polymerization system increases with the progress of the polymerization reaction, making handling difficult. The monomer concentration is preferably 5% to 50% by weight, more preferably 10% to 40% by weight, and most preferably 15% to 30% by weight.

  In the present specification, the linear polymer preferably has functional groups introduced at both ends. There is no restriction | limiting in particular in the kind of functional group introduce | transduced into both terminal, An amino group, a carboxyl group, a hydroxyl group, an isocyanate group, a phenolic hydroxyl group, a glycidyl group, a halogenated alkyl group etc. can be used.

  There is no restriction | limiting in particular in the method of introduce | transducing a functional group in the terminal, A well-known method can be used. For example, when an amide polymer is obtained by reacting a diamino compound and a diacid chloride compound, the diamino compound and diacid chloride are mixed and reacted at a predetermined concentration and temperature, and then used. An amino group can be introduced into both ends by further adding a compound and reacting an acid chloride that may be present at the end with an amino group. When it is desired to introduce an acid chloride group at both ends, it can be realized by adding an acid chloride compound instead of the diamino compound added after the reaction. However, in order to increase the purity of the target polymer, it is necessary to isolate and purify. There is no restriction | limiting in particular in an isolation method, A well-known method can be used.

  Even when a functional group other than an amino group or an acid chloride group is introduced, the method is not particularly limited, and a known method can be used. For example, it can be introduced by adding a large excess of a compound having a plurality of functional groups to be introduced into the same molecule to a polymer once having amino groups or carboxyl groups introduced at both ends. In order to increase the purity of the target polymer, it is necessary to isolate and purify it. There is no restriction | limiting in particular in an isolation method, A well-known method can be used.

(2) Synthesis of a cyclic polymer composed of a polyamide resin A cyclic polymer is produced by covalently bonding both ends of a linear polymer composed mainly of an amide bond obtained as described above within the same molecule. Can do. A method for bonding both ends in the same molecule will be described below with a specific example.

  In order to react both ends of a linear polymer composed mainly of polyamide bonds in the same molecule, it is preferably carried out in a solution. The solvent is not particularly limited as long as the linear polymer can be dissolved, and a known solvent can be used. For example, dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, dimethylformamide, and the like can be used. However, the solvent shown here is an example and is not limited thereto. In order to improve the solubility, lithium chloride, calcium chloride, lithium bromide, calcium bromide, and the like can be added. However, the compounds shown here are examples and are not limited thereto.

  There are no particular restrictions on the conditions for dissolving the linear polymer in the solvent. For example, the dissolution time can be shortened by increasing the dissolution rate by heating. The concentration of the linear polymer is not particularly limited as long as the isolated chains of the linear polymer do not overlap. It is preferably 0.1% to less than 5% by weight, more preferably 0.2% to 4% by weight, and most preferably 0.3% to 3% by weight. When the concentration of the linear polymer is less than 0.1% by weight, the productivity is greatly deteriorated. When the concentration of the linear polymer exceeds 5% by weight, the reaction between both ends in the same molecule is reduced. Since end-to-end reactions between different molecules occur preferentially, it becomes difficult to obtain a cyclic polymer.

  In order to bind both ends in the same molecule, it is effective to have functional groups at both ends of the linear polymer as described above. The functional groups at both ends may be the same or different. In the case where both terminals have the same functional group, it is necessary to use a bifunctional compound capable of reacting with the functional group. When the functional groups at both ends are different, it is necessary that each can react to form a covalent bond.

  The reaction temperature for bonding both ends of the linear polymer within the same molecule is not particularly limited except that it is necessary to select a temperature at which the distance between the molecule ends is closest. For example, the reaction temperature is preferably 0 ° C to 200 ° C, more preferably 10 ° C to 180 ° C, and most preferably 20 ° C to 150 ° C. The reaction time is not particularly limited, but it is necessary to continue until the reaction is completed.

  As a method of bonding both ends of a linear polymer having the same functional group at both ends in the same molecule, the linear polymer is used by using a polyfunctional compound having two or more functions reactive with the functional group. The method of achieving by connecting the both terminal of this is mentioned. Examples of the same functional group at both ends of the linear polymer include an amino group, an acid chloride group, a hydroxyl group, an acid anhydride group, an isocyanate group, a glycidyl group, a halogen, and the like. is not.

For example, when the functional groups at both ends of the linear polymer are both amino groups, this can be achieved by connecting both ends of the linear polymer with a covalent bond using an acid chloride having two or more functions. it can. Examples of acid chlorides that can be used include aliphatic diacid chlorides having 2 to 15 carbon atoms, phthalic acid chlorides, terephthalic acid chlorides, isophthalic acid chlorides, and the examples shown here are only examples. It is not limited.
An acid anhydride can also be used in place of the bifunctional or higher acid chloride. Examples of the acid anhydride that can be used include pyromellitic anhydride and the like, but the examples shown here are merely examples, and the present invention is not limited thereto.
Furthermore, a compound having an acid anhydride group and an acid chloride group in the same molecule can also be used. For example, trimellitic anhydride chloride and the like can be mentioned. However, the example shown here is an example, and the present invention is not limited thereto.
Moreover, the compound which changed the acid chloride group of the above-mentioned acid chloride compound into the carboxyl group can also be used.
As the polyfunctional compound having two or more functions, an aliphatic compound having two or more halogen atoms in the same molecule can be used. Examples thereof include dihalogenated alkyl having 2 to 15 carbon atoms. As the halogen, a chlorine atom or a bromine atom can be used, and a bromine atom is most preferable.
Furthermore, a compound having two or more glycidyl groups can be used. For example, an epichlorohydrin adduct of bisphenol A can be used. However, the example shown here is an example and is not limited thereto.
In addition, a compound having two or more isocyanate groups can be used. Examples thereof include phenyl diisocyanate, biphenyl diisocyanate, diphenylmethane diisocyanate, diphenylpropane diisocyanate, and aliphatic hydrocarbon compounds having 2 to 15 carbon atoms having two or more isocyanate groups. The example shown here is an example and is not limited thereto.

  As a method of bonding both ends of a linear polymer having an acid chloride group at both ends in the same molecule, a compound having two or more amino groups is used to connect both ends of the polymer with a covalent bond. The method to achieve is mentioned. Examples of the amino compound that can be used include an aliphatic hydrocarbon compound having 2 to 15 carbon atoms and having two or more amino groups. In addition, a compound having two or more hydroxyl groups can be used in place of the compound having two or more amino groups. Examples thereof include hydroquinone, resorcinol, and an aliphatic hydrocarbon compound having 2 to 15 carbon atoms having two or more hydroxyl groups. However, the example shown here is an example and is not limited thereto.

  As a method of bonding both ends of a linear polymer having a hydroxyl group at both ends within the same molecule, a compound having two or more acid chloride groups is used to connect both ends of the linear polymer with a covalent bond. A method is mentioned. For example, aliphatic diacid chloride, phthalic acid chloride, terephthalic acid chloride, isophthalic acid chloride, etc. having 2 to 15 carbon atoms can be used. Moreover, an acid anhydride (for example, pyromellitic anhydride etc.) can be used instead of the compound having two or more acid chloride groups. Furthermore, a compound having an acid anhydride group and an acid chloride group in the same molecule can also be used. However, the example shown here is an example and is not limited thereto.

  As a method of bonding both ends of a linear polymer having acid anhydride groups at both ends within the same molecule, both ends of the linear polymer are covalently bonded using a compound having two or more amino groups. A method that can be achieved by connecting together. Examples of the amino compound that can be used include an aliphatic hydrocarbon compound having 2 to 15 carbon atoms and having two or more amino groups. In addition, a compound having two or more hydroxyl groups can be used in place of the compound having two or more amino groups. Examples thereof include hydroquinone, resorcinol, and an aliphatic hydrocarbon compound having 2 to 15 carbon atoms having two or more hydroxyl groups. However, the example shown here is an example and is not limited thereto.

  As a method for bonding both ends of a linear polymer having an isocyanate group at both ends in the same molecule, a compound having two or more amino groups is used to connect both ends of the linear polymer with a covalent bond. The method achieved by this is mentioned. Examples of the amino compound that can be used include an aliphatic hydrocarbon compound having 2 to 15 carbon atoms and having two or more amino groups. In addition, a compound having two or more hydroxyl groups can be used in place of the compound having two or more amino groups. Examples thereof include hydroquinone, resorcinol, and an aliphatic hydrocarbon compound having 2 to 15 carbon atoms having two or more hydroxyl groups. Furthermore, a compound obtained by changing the acid chloride group of the acid chloride compound to a carboxyl group can also be used. However, the example shown here is an example and is not limited thereto.

  As a method for bonding both ends of a linear polymer having glycidyl groups at both ends within the same molecule, a compound having two or more amino groups is used to connect both ends of the linear polymer with a covalent bond. The method achieved by this is mentioned. Examples of the amino compound that can be used include an aliphatic hydrocarbon compound having 2 to 15 carbon atoms and having two or more amino groups. In addition, a compound having two or more hydroxyl groups can be used in place of the compound having two or more amino groups. Examples thereof include hydroquinone, resorcinol, and an aliphatic hydrocarbon compound having 2 to 15 carbon atoms having two or more hydroxyl groups. Furthermore, a compound obtained by changing the acid chloride group of the acid chloride compound to a carboxyl group can also be used. However, the example shown here is an example and is not limited thereto.

  As a method of bonding both ends of a linear polymer having a halogen such as a chlorine atom or a bromine atom at both ends in the same molecule, both compounds of the linear polymer are used by using a compound having two or more amino groups. The method of achieving by connecting a terminal with a covalent bond is mentioned. Examples of the amino compound that can be used include an aliphatic hydrocarbon compound having 2 to 15 carbon atoms and having two or more amino groups. Further, instead of the compound having two or more amino groups, a metal alcoholate of the compound having two or more hydroxyl groups described above can also be used. Examples of metals that can be used include sodium and potassium. However, the example shown here is an example and is not limited thereto.

  The amount of the polyfunctional compound to be added is preferably 0.5 to 500-fold mol with respect to the amount of both ends of the linear polymer. More preferably, it is 0.5 to 400 times mol, and most preferably 0.5 to 300 times mol. For example, when the addition amount of diacid chloride is less than 0.5-fold mol, the amount of cyclic structure polymer produced decreases, and when it exceeds 500-fold mol, intermolecular reactions occur relatively frequently. The production amount decreases.

(3) Synthesis of linear polymer composed of ester bond There is no particular limitation on the synthesis of a linear polymer in which the bond constituting the main chain is mainly composed of an ester bond, and a known method can be used. For example, it can be synthesized by reacting a diol compound and a diacid chloride compound in an inactive solvent.
Examples of diol compounds that can be used include dihydroxybenzene, dihydroxynaphthalene, dihydroxyanthracene, alkyl diol compounds having 1 to 15 carbon atoms, diol compounds having a heterocycle such as dihydroxypyridine, dihydroxypiperazine, and dihydroxypyrimidine, and carboxyl groups. Aromatic diol compounds, bishydroxyphenoxyphenylpropane, bishydroxyphenoxybiphenyl, bishydroxyphenylsulfone, biphenol, and the like can be mentioned, but the compounds shown here are examples and are not limited thereto.

  Examples of the diacid chloride compound that can be used include phthalic acid chloride, isophthalic acid chloride, terephthalic acid chloride, naphthalenediic acid chloride, anthracenedioic acid chloride, diacid chloride having 1 to 15 carbon atoms, and the like. The example shown here is an example and is not limited thereto.

There is no restriction | limiting in particular in the polymerization method, A well-known method can be used. For example, it can be synthesized by reacting the diamino compound and the diacid chloride compound in an inert solvent. Examples of the solvent that can be used include dimethyl acetoester, N-methylpyrrolidone, and γ-butyrolactone, but the examples shown here are merely examples, and the present invention is not limited thereto.
A known interfacial polycondensation reaction can also be used. For example, it can be synthesized by dissolving a diol compound in distilled water and dissolving the diacid chloride compound in methylene chloride, chloroform, toluene, xylene, etc., which are incompatible with water, and polycondensing at the interface. . However, the method shown here is an example and is not limited to these methods.

  There is no restriction | limiting in particular in the solvent used when performing solution polymerization, What kind of thing can be used if the produced | generated polymer melt | dissolves. Furthermore, it is desirable that the produced polymer has high solubility in a solvent. This is because the molecular weight cannot be increased any more when the produced polymer is low in solubility in the solvent and is precipitated from the solvent. Examples of the solvent include N-methylpyrrolidone, dimethylacetamide, γ-butyrolactone, toluene, xylene, alkylbenzene, pyridine, cyclohexanone, dioxane, tetrahydrofuran, methyl ethyl ketone, acetone and the like. The compounds shown here are examples. Yes, it is not limited to these.

  There is no restriction | limiting in particular in the temperature at the time of performing solution polymerization, Any temperature can be selected suitably. If the polymerization temperature is too high, side reactions with water and the like may be relatively increased, and if the polymerization temperature is too low, the reactivity may be lowered. Therefore, the polymerization temperature is preferably about 0 ° C to 300 ° C, more preferably about 10 ° C to 200 ° C, and most preferably about 20 ° C to 180 ° C. In order to reduce unreacted monomers, it is possible to raise the polymerization temperature to 250 ° C. or higher after the reaction is almost completed.

  There is no restriction | limiting in particular in the density | concentration of a monomer, It can select suitably. When the concentration is too low, the reaction rate is lowered, and the time for obtaining a high molecular weight is remarkably increased. On the other hand, if the concentration is too high, the viscosity of the polymerization system increases with the progress of the polymerization reaction, making handling difficult. The monomer concentration is preferably 5% to 50% by weight, more preferably 10% to 40% by weight, and most preferably 15% to 30% by weight.

  In the present specification, the linear polymer preferably has functional groups introduced at both ends. There is no restriction | limiting in particular in the kind of functional group introduce | transduced into both terminals, An amino group, a carboxyl group, a hydroxyl group, an isocyanate group, a phenolic hydroxyl group, a glycidyl group, a halogenated alkyl group etc. can be used.

  There is no restriction | limiting in particular in the method of introduce | transducing a functional group in the terminal, A well-known method can be used. For example, in the case of obtaining an ester polymer by reacting a diol compound and a diacid chloride compound, an equimolar amount of the diol compound and the diacid chloride compound were mixed and reacted at a predetermined concentration and temperature, and then used. A hydroxyl group can be introduced into both ends by further adding a diol compound and reacting an acid chloride which may be present at the terminal with a hydroxyl group. When it is desired to introduce an acid chloride group at both ends, it can be realized by adding an acid chloride compound instead of the diol compound added after the reaction. However, in order to increase the purity of the target polymer, it is necessary to isolate and purify. There is no restriction | limiting in particular in an isolation method, A well-known method can be used.

  Even when a functional group other than a hydroxyl group or an acid chloride group is introduced, the method is not particularly limited, and a known method can be used. For example, it can be introduced by adding a large excess of a compound having a plurality of functional groups to be introduced in the same molecule to a polymer once having hydroxyl groups or carboxyl groups introduced at both ends. In order to increase the purity of the target polymer, it is necessary to isolate and purify it. There is no restriction | limiting in particular in an isolation method, A well-known method can be used.

(4) Synthesis of a cyclic polymer composed of a polyester resin A cyclic polymer is produced by covalently bonding both ends of a linear polymer composed mainly of an ester bond obtained as described above in the same molecule. can do. A method for bonding both ends in the same molecule will be described below with a specific example.

  In order to react both ends of a linear polymer mainly composed of a polyester bond within the same molecule, it is preferably carried out in a solution. The solvent is not particularly limited as long as the linear polymer can be dissolved, and a known solvent can be used. For example, N-methylpyrrolidone, dimethylacetamide, γ-butyrolactone, toluene, xylene, alkylbenzene, pyridine, cyclohexanone, dioxane, tetrahydrofuran, methyl ethyl ketone, acetone and the like can be used, but the solvents shown here are examples, and these It is not limited to.

  There are no particular restrictions on the conditions for dissolving the linear polymer in the solvent. For example, the dissolution time can be shortened by increasing the dissolution rate by heating. The concentration of the linear polymer is not particularly limited as long as the isolated chains of the linear polymer do not overlap. The concentration of the linear polymer is preferably 0.1% to less than 5% by weight, more preferably 0.2% to 4% by weight, and most preferably 0.3% to 3% by weight. . When the concentration of the linear polymer is less than 0.1% by weight, the productivity is greatly deteriorated. When the concentration of the linear polymer exceeds 5% by weight, the reaction between both ends in the same molecule is reduced. Since end-to-end reactions between different molecules occur preferentially, it becomes difficult to obtain a cyclic polymer.

  In order to bond both ends in the same molecule, it is effective to have functional groups at both ends of the linear polymer. The functional groups at both ends may be the same or different. When having the same functional group, it is necessary to use a bifunctional compound capable of reacting with the functional group. When the functional groups at both ends are different, it is necessary that each can react to form a covalent bond.

  The reaction temperature for bonding both ends of the linear polymer within the same molecule is not particularly limited except that it is necessary to select a temperature at which the distance between the molecule ends is closest. For example, the reaction temperature is preferably 0 ° C to 200 ° C, more preferably 10 ° C to 180 ° C, and most preferably 20 ° C to 150 ° C. The reaction time is not particularly limited, but it is necessary to continue until the reaction is completed.

  As a method of bonding both ends of a linear polymer having the same functional group at both ends in the same molecule, the linear polymer is used by using a polyfunctional compound having two or more functions reactive with the functional group. The method of achieving by connecting the both terminal of this is mentioned. Examples of the same functional group at both ends of the linear polymer include, but are not limited to, a hydroxyl group, an acid chloride group, an amino group, an acid anhydride group, an isocyanate group, a glycidyl group, and a halogen. is not.

For example, when the functional groups at both ends of the linear polymer are hydroxyl groups, this can be achieved by covalently connecting both ends of the polymer using a bifunctional or higher acid chloride compound. Examples of the acid chloride compound that can be used include aliphatic diacid chlorides having 2 to 15 carbon atoms, phthalic acid chlorides, terephthalic acid chlorides, isophthalic acid chlorides, and the examples shown here are merely examples. It is not limited to.
Further, instead of the acid chloride compound, an acid anhydride of tetracarboxylic acid (for example, pyromellitic anhydride, etc.) can be used. However, the example shown here is an example and is not limited thereto.
Furthermore, a compound having an acid anhydride group and an acid chloride group in the same molecule can also be used. For example, trimellitic anhydride chloride and the like can be mentioned. However, the example shown here is an example, and the present invention is not limited thereto.
Moreover, the compound which changed the acid chloride group of the above-mentioned acid chloride compound into the carboxyl group can also be used.
Furthermore, a compound having two or more glycidyl groups can be used. For example, an epichlorohydrin adduct of bisphenol A can be mentioned, but the example shown here is only an example and is not limited thereto.
In addition, a compound having two or more isocyanate groups can be used. Examples thereof include phenyl diisocyanate, biphenyl diisocyanate, diphenylmethane diisocyanate, diphenylpropane diisocyanate, and aliphatic hydrocarbon compounds having 2 to 15 carbon atoms having two or more isocyanate groups, but the examples shown here are only examples. However, it is not limited to these.

  As a method for bonding both ends of a linear polymer having an acid chloride group at both ends within the same molecule, a compound having two or more amino groups is used to covalently bond both ends of the linear polymer. The method to achieve by connecting is mentioned. Examples of the amino compound that can be used include an aliphatic hydrocarbon compound having 2 to 15 carbon atoms and having two or more amino groups. In addition, a compound having two or more hydroxyl groups can be used in place of the compound having two or more amino groups. Examples thereof include hydroquinone, resorcinol, and an aliphatic hydrocarbon compound having 2 to 15 carbon atoms having two or more hydroxyl groups. However, the example shown here is an example and is not limited thereto.

As a method of bonding both ends of a linear polymer having amino groups at both ends within the same molecule, by using a bifunctional or higher acid chloride compound and connecting both ends of the linear polymer with a covalent bond. The method to achieve is mentioned. Examples of the acid chloride compound that can be used include aliphatic diacid chlorides having 2 to 15 carbon atoms, phthalic acid chlorides, terephthalic acid chlorides, isophthalic acid chlorides, and the examples shown here are merely examples. It is not limited to. An acid anhydride can also be used in place of the bifunctional or higher acid chloride compound. For example, pyromellitic anhydride or the like can be used, but the example shown here is an example, and the present invention is not limited thereto.
Furthermore, a compound having an acid anhydride group and an acid chloride group in the same molecule can also be used. For example, trimellitic anhydride chloride and the like can be mentioned. However, the example shown here is an example, and the present invention is not limited thereto.
Moreover, the compound which changed the acid chloride group of the above-mentioned acid chloride compound into the carboxyl group can also be used.
Furthermore, an aliphatic compound having two or more halogen atoms in the same molecule can be used. Examples thereof include dihalogenated alkyl having 2 to 15 carbon atoms. As the halogen, a chlorine atom or a bromine atom can be used, and a bromine atom is most preferable.
In addition, a compound having two or more glycidyl groups can be used. For example, an epichlorohydrin adduct of bisphenol A can be mentioned, but the example shown here is only an example and is not limited thereto.
In addition, a compound having two or more isocyanate groups can be used. Examples thereof include phenyl diisocyanate, biphenyl diisocyanate, diphenylmethane diisocyanate, diphenylpropane diisocyanate, and aliphatic hydrocarbon compounds having 2 to 15 carbon atoms having two or more isocyanate groups, but the examples shown here are only examples. However, it is not limited to these.

  As a method of bonding both ends of a linear polymer having acid anhydride groups at both ends within the same molecule, both ends of the linear polymer are covalently bonded using a compound having two or more amino groups. A method that can be achieved by connecting together. Examples of the amino compound that can be used include an aliphatic hydrocarbon compound having 2 to 15 carbon atoms and having two or more amino groups. In addition, a compound having two or more hydroxyl groups can be used in place of the compound having two or more amino groups. Examples thereof include hydroquinone, resorcinol, and an aliphatic hydrocarbon compound having 2 to 15 carbon atoms having two or more hydroxyl groups. However, the example shown here is an example and is not limited thereto.

  As a method for bonding both ends of a linear polymer having an isocyanate group at both ends in the same molecule, a compound having two or more amino groups is used to connect both ends of the linear polymer with a covalent bond. The method achieved by this is mentioned. Examples of the amino compound that can be used include an aliphatic hydrocarbon compound having 2 to 15 carbon atoms and having two or more amino groups. In addition, a compound having two or more hydroxyl groups can be used in place of the compound having two or more amino groups. Examples thereof include hydroquinone, resorcinol, and an aliphatic hydrocarbon compound having 2 to 15 carbon atoms having two or more hydroxyl groups. Moreover, the compound which changed the acid chloride group of the above-mentioned acid chloride compound into the carboxyl group can also be used. However, the example shown here is an example and is not limited thereto.

  As a method for bonding both ends of a linear polymer having glycidyl groups at both ends within the same molecule, a compound having two or more amino groups is used to connect both ends of the linear polymer with a covalent bond. The method achieved by this is mentioned. Examples of the amino compound that can be used include an aliphatic hydrocarbon compound having 2 to 15 carbon atoms and having two or more amino groups. In addition, a compound having two or more hydroxyl groups can be used in place of the compound having two or more amino groups. Examples thereof include hydroquinone, resorcinol, and an aliphatic hydrocarbon compound having 2 to 15 carbon atoms having two or more hydroxyl groups. Moreover, the compound which changed the acid chloride group of the above-mentioned acid chloride compound into the carboxyl group can also be used. However, the example shown here is an example and is not limited thereto.

  As a method of bonding both ends of a linear polymer having a halogen such as a chlorine atom or a bromine atom at both ends in the same molecule, both compounds of the linear polymer are used by using a compound having two or more amino groups. The method of achieving by connecting a terminal with a covalent bond is mentioned. Examples of the amino compound that can be used include an aliphatic hydrocarbon compound having 2 to 15 carbon atoms and having two or more amino groups. Further, instead of the compound having two or more amino groups, a metal alcoholate of the compound having two or more hydroxyl groups described above can also be used. Examples of metals that can be used include sodium and potassium. However, the example shown here is an example and is not limited thereto.

  The amount of the polyfunctional compound to be added is preferably 0.5 to 500 times mol, more preferably 0.5 to 400 times mol with respect to the amount of both ends of the linear polymer. Preferably, it is 0.5 to 300 times mol. For example, when the addition amount of diacid chloride is less than 0.5-fold mol, the amount of cyclic structure polymer produced decreases, and when it exceeds 500-fold mol, intermolecular reactions occur relatively frequently. The production amount decreases.

(5) Other cyclic polymers The above-mentioned examples of synthesis of cyclic polymers are examples, and in addition to the above-mentioned polymers in which the amide bond and ester bond are the main bonds constituting the main chain, imide bonds and urethanes. The present invention can also be applied to a polymer in which a bond, an ether bond, and a carbon-carbon bond are main bonds constituting the main chain.

2. First atomic group and second atomic group constituting synthetic polymer Next, the first atomic group and the second atomic group possessed by the synthetic polymer constituting the pseudo-crosslinked resin of the present invention will be described. .

(1) First atomic group The first atomic group containing a group selected from the above carbonyl group, carboxyl group, phenolic hydroxyl group and sulfonic acid group may be an atomic group having at least one of these groups. Specific examples thereof include, but are not limited to, atomic groups having a basic skeleton selected from the structural formula group A. In Structural Formula Group A, R ₁ — (COOH) _m represents a carboxylic acid compound having 2 to 6 carboxyl groups in the molecule (m represents an integer of 2 to 6). The carboxyl group may be bonded to any position of the aliphatic or aromatic hydrocarbon group represented by R ₁ in the formula.

  More specifically, as an atomic group having a basic skeleton shown in Structural Formula Group A, for an atomic group having a carbonyl group in the basic skeleton, ethyl methyl ketone, diethyl ketone, cyclohexyl-2-propanone, 2,4-hexane Dione, 3-allyl-2,4-pentanedione, 4-penten-2-one, 5-propyl-5-hexane 2,4-dione, acetone, biacetyl, 1- (2-naphthyl) -6-phenyl -2,5-hexanedione, 1,5-di- (2-furyl) -1,5-pentanedione, 1- (2-pyridyl) -1-butanone, acetophenone, 1'-butylnaphthone, 4'-chloro Undecanophenone, propiophenone, deoxybenzoin, chalcone, di-2-furyl ketone, 2-furyl 2-pyridyl ketone, bis (5-methyl-2-thienyl) ketone, 2-bromo-1-naphthyl 1-chloro- 2-naphthyl ketone, di-2-naphthyl diketone, di-3-pyridyl triketone, 2-ph -2-pyrrole-diketone,

  Cyclohexanone, 2,5-cyclohexadien-1-one, inden-1-one, 1,2,3-indanetrione, fluoren-9-one, 4H-pyran-4-one, 2 (3H) -pyrazione, 1 (2H) -Naphthyrenone, 5,8-quinolidione, 9 (10H) -phenantrone, 2-pyridone, 4-pyridone, 2-quinolone, 4-quinolone, 1-isoquinolone, 9-acridone, 4-oxazolone, 4-pyrazolone , 5-pyrazolone, 4-isoxazolone, 4-thiazolone, 4-piperidone, 2-pyrrolidone, 4-thiazolidone, p-benzoquinone, anthraquinone, 1,4-naphthoquinone, 5,6-chrysenequinone, 2-acetoyl 1,4 -Naphtroquinone, phenyl ketene, dibutyl ketene, etc. are mentioned, but not limited thereto.

  In addition, the atomic group having a carboxyl group in the basic skeleton includes acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oxalic acid, malon Acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, acrylic acid, propiolic acid, methacrylic acid, crotonic acid, isocrotonic acid, oleic acid, elaidic acid, maleic acid, fumaric acid, Citraconic acid, mezaconic acid, camphoric acid,

  Benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthoic acid, toluic acid, hydroatropic acid, atropaic acid, cinnamic acid, fluic acid, tenic acid, nicotinic acid, isonicotinic acid, 4-oxo-1-cyclohexanecarboxylic acid 5-oxo-2-pyrrolidinecarboxylic acid, 7- (1,4-benzoquinonyl) -2-naphthalenecarboxylic acid, o- (2-furoyl) benzenecarboxylic acid, 4,4′-carbonyldibenzenecarboxylic acid, 5 -(o-Carboxybenzoyl) -2-furancarboxylic acid, 2-hexene-4-indioic acid, 4-pentyl-2,4-pentanedioic acid, 4-ethyl-2-propylhexanedioic acid, 3-vinyl -4-hexynoic acid, 2,5-diphenylheptanedioic acid, 3-biphenylcarboxylic acid, 1-pyrrolecarboxylic acid,

  3- (3-phenylpropyl) -1-cyclobutanecarboxylic acid, cyclohexylcarboxylic acid, 1,3,5-naphthalenetricarboxylic acid, 3- (carboxymethyl) heptanedioic acid, 6- (2-naphthyl) hexanoic acid, 1 , 3,6-naphthalenetriacetic acid, 3-methyl-5- (1-naphthyl) hexanoic acid, 6-carboxy-1- (carboxymethyl) -2-naphthalenepropionic acid, 2,3,5-hexanetricarboxylic acid, 2- (3-carboxypyropyl) -1,1,5,6-heptanetetracarboxylic acid, 1,2,3-butanetricarboxylic acid, 2- (cyclohexylcarbonyl) -1-naphthalenecarboxylic acid, β-oxocyclohexane Propionic acid, γ-oxo-6-chrysenebutyric acid,

  β-oxo-3-pyridinepropionic acid, formylsuccinic acid, p- (2-oxobutyl) benzenecarboxylic acid, benzoylbenzenecarboxylic acid, 6-chloro-formylhexanoic acid, p- (3-formylpropyl) benzenecarboxylic acid, Examples thereof include, but are not limited to, phthalaldehyde acid, isophthalaldehyde acid, glutaraldehyde acid, malonaldehyde acid, terephthalaldehyde acid, salicylic acid, salicyloyl salicylic acid, 3,5-di-t-butylsalicylic acid, and the like.

  Specific examples of the atomic group having a phenolic hydroxyl group in the basic skeleton include phenol, m-cresol, o-cresol, p-cresol, 2,6-di-t-butyl-p-cresol, 4,4 ′ -Thiobis (6-t-butyl-3-methylphenol), 2,2-methylenebis (4-methyl-6-tbutyl-3-methylphenol), triethylene glycol bis (3- (3-t-butyl- 5-methyl-4-hydroxyphenyl) propionate, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 3, 5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2- (5-methyl-2-hydroxyphenyl) ) Benzotriazole and the like, but are not limited thereto.

  Further, the atomic group having a sulfonic acid group in the basic skeleton specifically includes benzenesulfonic acid, phenolsulfonic acid, toluenesulfonic acid, 2,4-toluenedisulfonic acid, 1-piperidinesulfonic acid, naphthionic acid, sulfanyl. Examples thereof include, but are not limited to, acid, taurine, 4,6-disulfino-1-naphthoic acid, p-sulfobenzenecarboxylic acid, 1-naphthylamine-4,7-disulfonic acid and the like.

  Among these, the first atomic group applied to the present invention is more preferably an atomic group having a basic skeleton selected from the structural formula group C, and more preferably acetic acid, propion Examples include atomic groups such as acid, butyric acid, isobutyric acid, succinic acid, benzoic acid, phthalic acid, isophthalic acid, naphthoic acid, phenol, cresol, benzenesulfonic acid, phenolsulfonic acid, and toluenesulfonic acid.

  In the basic skeletons shown in the structural formula groups of A and C and the first atomic group having them in the basic skeleton, a bond for binding them to the molecular ends, side chains, in the skeleton, etc. of the synthetic polymer Is not described, but a bond can be obtained by removing a substitutable hydrogen atom in the structural formula while leaving the carbonyl group, carboxyl group, phenolic hydroxyl group and sulfonic acid group. In addition, functional groups that can react with other functional groups to form various covalent bonds on the basic skeleton, such as vinyl groups, carboxyl groups, hydroxyl groups, amino groups, acid chloride groups, glycidyl groups, ethynyl groups, thiol groups A structure in which a functional group such as carbonyl group, carboxyl group, phenolic hydroxyl group and sulfonic acid group is left is also included in the basic skeleton of the first atomic group. In this case, the introduced functional group What is necessary is just to think that it is couple | bonded with the molecule | numerator terminal, side chain, frame | skeleton, etc. of a synthetic polymer via group.

(2) Second atomic group As a second atomic group containing a group selected from the above-mentioned acyl group or an amino group substitutable with an aliphatic hydrocarbon group and a heterocyclic group containing at least one nitrogen atom Is not particularly limited as long as it is an atomic group having at least one of these groups, and specific examples thereof include an atomic group having a basic skeleton selected from the structural formula group B described above.

  As the atomic group having the basic skeleton shown in the structural formula group B, more specifically, for the atomic group having an amino group that can be substituted with an acyl group or an aliphatic hydrocarbon group in the basic skeleton, methylamine, Aliphatic amines such as ethylamine, propylamine, butylamine and cyclohexylamine, aromatic amines such as phenylamine and benzylamine, (aminophenyl) ethane, (aminophenyl) ethylene, (aminophenyl) ethyne, (aminophenoxy) ethane, Aliphatic substituted aromatic amines such as (aminophenoxy) ethylene, (aminophenoxy) ethyne, (aminobenzyl) ethane, (aminobenzyl) ethylene, (aminobenzyl) ethyne, (phenylethyl) amine, (phenoxyethyl) amine, Aromatic substituted aliphatic amines such as (benzylethyl) amine,

  Aliphatic diamines such as diaminomethane, diaminoethane, diaminopropane, diaminobutane, aromatic diamines such as diaminobenzene, (diaminophenyl) ethane, (diaminophenyl) ethylene, (diaminophenyl) ethyne, (diaminophenoxy) ethane, (Diaminophenoxy) ethylene, (diaminophenoxy) ethyne, (diaminobenzyl) ethane, (diaminobenzyl) ethylene, (diaminobenzyl) ethyne, bis (aminophenyl) ethane, bis (aminophenyl) ethylene, bis (aminophenyl) ethyne, Aliphatic substituted aromatic diamines such as bis (aminophenoxy) ethane, bis (aminophenoxy) ethylene, bis (aminophenoxy) ethyne, bis (aminobenzyl) ethane, bis (aminobenzyl) ethylene, bis (aminobenzyl) ethyne, Phenyldiaminoeta , Phenoxy Siji aminoethane, aromatic-substituted aliphatic diamines such as benzyl diamino ethane, butane triamine, polyamines such as polyethylene polyamine,

  Aliphatic secondary amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine and dicyclohexylamine, aromatic secondary amines such as diphenylamine and dibenzylamine, methylphenylamine, ethylphenylamine, propylphenylamine, butyl Secondary amines such as phenylamine, aromatic substituted aliphatic amines such as (methylphenyl) methylamine, (ethylphenyl) methylamine, (propylphenyl) methylamine, (butylphenyl) methylamine, pyrrole, indole, isoindole , Heterocyclic amines such as carbazole, phenothiazine, phenoxazine, triazine,

  Aliphatic diamines such as bis (dimethylamino) methane, bis (dimethylamino) ethane, bis (dimethylamino) propane, bis (dimethylamino) butane, bis (phenylmethylamino) methane, bis (phenylmethylamino) ethane, bis Aromatic substitution such as (phenylmethylamino) propane, bis (phenylmethylamino) butane, bis (dimethylamino) benzene, bis (methylethylamino) benzene, bis (methylpropylamino) benzene, bis (methylbutylamino) benzene Aliphatic diamines,

  Aliphatic amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, tricyclohexylamine, dimethylethylamine, triphenylamine, tri (methylphenyl) amine, tri (ethylphenyl) amine, tri (propylphenyl) amine, tri ( (Butylphenyl) amine, tri (phenoxyphenyl) amine, aromatic amines such as tri (benzylphenyl) amine, dimethylphenylamine, diethylphenylamine, dipropylphenylamine, dibutylphenylamine, diphenylmethylamine, diphenylethylamine, diphenylpropyl Amine, diphenylbutylamine, diphenylcyclohexylamine, (methylphenyl) dimethylamine, (ethylphenyl) dimethylamine, (propylphenyl) dimethylamine Aromatic substituted aliphatic amines such as (butylphenyl) dimethylamine, bis (methylphenyl) methylamine, bis (ethylphenyl) methylamine, bis (propylphenyl) methylamine, bis (butylphenyl) methylamine, etc. However, it is not limited to these.

  Further, as the atomic group having a heterocyclic group containing at least one nitrogen atom in the basic skeleton, specifically, imidazole, pyrazole, isothiazole, isoxazole, pyridine, pyrazine, pyrimidine, indolizine, 3H-indole 1H-indazole, purine, 4H-quinolidine, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, 4aH-carbazole, β-carboline, phenanthridine, acridine, perimidine, phenanthroline, phenazine, phenalsazine, furazane, benz [H] Isoquinoline, 7H-pyrazino [2,3-c] carbazole, 5H-pyrido [2,3-d] o-oxazine, 1H-pyrazolo [4,3-d] oxazole, 4H-imidazolo [4,5 -d] Imazole, Serenazolo [5,4-f Benzothiazole, pyrazino [2,3-d] pyridazine, imidazolo [2,1-b] thiazole, furo [3,4-c] cinnoline, 4H-pyrido [2,3-c] carbazole, 4H [1,3 ] Oxathiolo [5,4-b] pyrrole, imidazolo [1,2-b] [1,2,4] triazine, pyrido [1 ', 2': 1,2] imidazolo [4,5-b] quinoxaline, Examples include, but are not limited to, 4H-1,3dioxolo [4,5-d] imidazole, 2,6-bis (alkylamido) pyridine, 2,6-bis (alkylamino) pyridine, and the like.

  Among these, the second atomic group applied to the present invention more preferably includes an atomic group having a basic skeleton selected from the structural formula group D, and more preferably triethylamine, tripropyl. Examples include amine, tributylamine, dimethylethylamine, phenylamine, pyridine, pyrazine, pyrimidine, naphthyridine, quinoxaline, 2,6-bis (alkylamido) pyridine, 2,6-bis (alkylamino) pyridine, and the like. In addition, as an alkyl group in the said compound, the C1-C6 alkyl group which may be branched is mentioned preferably.

  In the basic skeletons shown in the structural formula groups of B and D and the second atomic group having them in the basic skeleton, a bond for binding them to the molecular ends, side chains, in the skeleton, etc. of the synthetic polymer. Is not described, but a bond can be obtained by removing a substitutable hydrogen atom in the structural formula without any particular limitation. In addition, functional groups that can react with other functional groups to form various covalent bonds on the basic skeleton, such as vinyl groups, carboxyl groups, hydroxyl groups, amino groups, acid chloride groups, glycidyl groups, ethynyl groups, thiol groups The structure into which the functional group such as is introduced is also included in the basic skeleton of the second atomic group, and in this case, it is bonded to the molecular end, side chain, skeleton, etc. of the synthetic polymer via the introduced functional group. You can think of it.

3. Synthetic polymer constituting the pseudo-crosslinked resin composition of the present invention and pseudo-crosslinked resin composition of the present invention The synthetic polymer constituting the pseudo-crosslinked resin composition of the present invention includes the first atomic group. And one or more synthetic polymers having the second atomic group are not particularly limited. Here, in this specification, “one or more synthetic polymers having the first atomic group and the second atomic group” means the first atomic group and the second atom in the same molecule. It is only one type of synthetic polymer having a group or a combination of two or more types of synthetic polymers. In the case of a combination of two or more kinds of synthetic polymers, each constituent synthetic polymer has a first atomic group and / or a second atomic group, and the first atom is always included in the combination of these synthetic polymers. It is used in a concept including a combination of two or more kinds of synthetic polymers including a group and a second atomic group.

  When the pseudo-crosslinked resin composition of the present invention is composed of one kind of synthetic polymer, the synthetic polymer has both the first atomic group and the second atomic group in the same molecule. become. Moreover, as an example in which the pseudo-crosslinked resin composition of the present invention is composed of two or more kinds of synthetic polymers, for example, when it is composed of two kinds of synthetic polymers, the main constituent parts constituting the synthetic polymers Are the same, but one has only the first atomic group and the other has only the second atomic group, a combination of synthetic polymers, and two types of synthesis in which the main components constituting the synthetic polymer are different Examples include a combination in which one of the polymers has the first atomic group and the other has the second atomic group. The combination of the two kinds of synthetic polymers having different main components constituting the synthetic polymer and the first and second atomic groups is arbitrary, and both the synthetic polymers have both atomic groups. May be. Furthermore, in the case where the main constituent parts of the synthetic polymer are the same, the pseudo-crosslinked resin of the present invention using the synthetic polymer having both the first atomic group and the second atomic group in the same molecule. It can be said that the composition is preferable from the viewpoint of manufacturing man-hours.

  Specific examples of the polymer constituting the main constituent part of the synthetic polymer include polyolefin, polyimide resin, polyester, phenol resin, epoxy resin, melamine resin, polyurethane resin, acrylic resin, methacrylic resin, styrene resin, AS resin. Synthetic polymers such as ABS resin, aromatic polyester, aromatic polyesteramide, aromatic polyamide, aromatic polyamideimide, aromatic polyimide, polycarbonate, polyether, polyurethane, etc. Not. The synthetic polymer constituting the pseudo-crosslinked resin composition of the present invention has a structure in which the first atomic group and / or the second atomic group are introduced into the molecular terminals, side chains, and skeleton of the various polymers. It is what has.

  As the synthetic polymer when the pseudo-crosslinked resin composition of the present invention is composed of a single synthetic polymer, specifically, the main components constituting the synthetic polymer are the same and the same molecular Polyimide resin having both the first atomic group and the second atomic group, unsaturated polyester, resol type phenol resin, epoxy resin, acrylic resin, styrene resin, aromatic polyester, aromatic polyester amide, aromatic Examples thereof include, but are not limited to, group polyamides, polyamideimides, polyurethanes, polyurethane amides, polyurethane imides and the like.

  The bonding position of the first atomic group and the second atomic group in the synthetic polymer is such that the two interact with each other to form a hydrogen bond and make the resin pseudo-crosslinked. There is no particular limitation, and any of a molecular end, a side chain, and a skeleton may be used. A suitable bonding position can be appropriately selected depending on the type of the synthetic polymer. Further, the first atomic group may have one or more unique functional groups selected from a carbonyl group, a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group, or two or more of these functional groups in combination. It may have a functional group of When the synthetic polymer has two or more first atomic groups, these may be the same or different. Furthermore, the content of the first atomic group in the synthetic polymer is 2 to 10,000 per molecule as the total number of carbonyl groups, carboxyl groups, phenolic hydroxyl groups, and sulfonic acid groups, although it depends on the molecular weight of the synthetic polymer. The degree, preferably about 2 to 3000.

  The second atomic group may have at least one functional group selected from an optionally substituted amino group and a heterocyclic group containing at least one nitrogen atom, and these functional groups May have two or more functional groups. When the synthetic polymer has two or more second atomic groups, these may be the same or different. In addition, the content of the second atomic group depends on the molecular weight of the synthetic polymer, but the total number of amino groups which may be substituted and heterocyclic groups containing at least one nitrogen atom is per molecule. The number can be about 2 to 10000, preferably about 2 to 3000.

  Further, the ratio of the first atomic group and the second atomic group in the pseudo-crosslinked resin composition of the present invention is substituted with the total amount of carbonyl group, carboxyl group, phenolic hydroxyl group and sulfonic acid group in the resin. The ratio of the total amount of the amino group that may be present and the heterocyclic group containing at least one nitrogen atom is preferably about 1.0: 0.1 to 1.0: 10.0, more preferably 1.0: It is about 0.3 to 1.0: 3.0.

  The molecular weight of the synthetic polymer constituting the pseudo-crosslinked resin composition of the present invention is preferably 5000 or more, more preferably 20000 or more, although it depends on the type of the synthetic polymer. Moreover, although the upper limit of molecular weight is not specifically limited, About 2 million can be mentioned as an upper limit. The pseudo-crosslinked resin composition of the present invention is such that such a synthetic polymer forms a hydrogen bond at least between molecules via the first atomic group and the second atomic group. It has a pseudo-crosslinked resin structure.

(4) Production method of pseudo-crosslinked resin composition of the present invention The pseudo-crosslinked resin composition of the present invention comprises one or more synthetic compounds having the first atomic group and the second atomic group. Concerning a production method in which the pseudo-crosslinked resin composition of the present invention is composed of a single synthetic polymer having a first atomic group and a second atomic group in the same molecule. First, I will explain.

  The pseudo-crosslinked resin composition composed of a single synthetic polymer having the first and second atomic groups in the same molecule can be obtained, for example, by polymerization with a monomer unit constituting the main constituent part of the synthetic polymer. It is usually obtained by polymerizing the monomer units to be the first atomic group and the second atomic group under the same conditions as the monomer units constituting the main constituent part are polymerized. Furthermore, after introducing a functional group to the molecular terminal by the above-described method, a cyclic polymer can be obtained by reacting a polyfunctional compound capable of reacting with these in a dilute solution state. According to this method, the first atomic group and the second atomic group are composed of a single synthetic polymer mainly having the first atomic group and the second atomic group in the skeleton of the synthetic polymer or at the molecular end. The pseudo-crosslinked resin composition of the present invention is obtained in which the synthetic polymer is pseudo-crosslinked by forming hydrogen bonds between molecules through atomic groups.

  The monomer units that become the first atomic group and the second atomic group by polymerization differ depending on the synthetic polymer in which they are contained, but various types of synthetic polymers have bonding modes such as addition polymerization, ester bond, acid It is produced according to an amide bond, an imide bond, an ether bond or the like. As for the monomer unit serving as the first atomic group, a carbonyl group, a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group remain, and a vinyl group, a carboxyl group, a hydroxyl group, an amino group, a glycidyl group, an acid chloride group, and an ethynyl group. And those into which a group, a thiol group and the like are introduced. Similarly, with respect to the monomer unit serving as the second atomic group, the basic skeleton shown in the structural formula group B has a vinyl group, a carboxyl group, a hydroxyl group, an amino group, a glycidyl group, an acid chloride group, an ethynyl group, a thiol group, and the like. Is introduced.

  In order to obtain a pseudo-crosslinked resin composition comprising a synthetic polymer having a first atomic group and a second atomic group in the side chain, for example, the monomer unit constituting the main constituent part of the synthetic polymer is used. A synthetic polymer having a functional group in the side chain can be produced by introducing an appropriate functional group that does not participate in polymerization into at least a part of the polymer and then reacting with this functional group in the side chain. What is necessary is just to make the 1st atomic group and the 2nd atomic group into which the functional group was introduce | transduced like the above react.

  Furthermore, if the above production methods are combined appropriately, a pseudo-polymer composed of a single synthetic polymer having a first atomic group and a second atomic group at a desired site selected from a side chain and a skeleton in the same molecule. A cross-linked resin composition is obtained.

  In addition, the main constituent parts constituting the synthetic polymer are the same, but one has only the first atomic group and the other has only the second atomic group. Regarding the pseudo-crosslinked resin composition of the present invention comprising a combination in which one of two kinds of synthetic polymers having different main constituent parts has the first atomic group and the other has the second atomic group, The use of the first atomic group and the second atomic group in the production of the synthetic polymer having both atomic groups in the same molecule as the two synthetic polymers constituting the pseudo-crosslinked resin composition, respectively. It can be produced by mixing in the same manner as described above except that the first atomic group or the second atomic group is used, and mixing the resulting two synthetic polymers. At this time, the method of mixing the two kinds of synthetic polymers is that the synthetic polymers form hydrogen bonds between the molecules via the first atomic group and the second atomic group, and are simulated. The method is not particularly limited as long as the method is a resin composition having a crosslinked structure.

  Furthermore, the pseudo-crosslinked resin composition of the present invention is composed of two kinds of synthetic polymers having different main components constituting the synthetic polymer, and both of them have a first atomic group and a second atomic group. In some cases, it may be produced by a method according to the above production method even when it is composed of 3 or more synthetic polymers.

(5) Application of pseudo-crosslinked resin composition of the present invention The resin to which the present invention is particularly preferably applied will be described in detail below.

(A) Aromatic polyamide When the synthetic polymer constituting the pseudo-crosslinked resin composition of the present invention is an aromatic polyamide, the functional groups at both ends of the linear polymer are polyfunctional. There is no particular limitation as long as the compound has low reactivity with the atomic group in the side chain or main chain skeleton of the linear polymer. Any polyfunctional compound can be used in this range. In the case of an aromatic polyamide cyclic polymer, the first atomic group is selected from the group consisting of propionic acid, benzoic acid, phthalic acid, naphthoic acid, phenol, and benzene sulfonic acid; Examples include combinations in which the atomic group is selected from the group consisting of triethylamine, tripropylamine, pyridine, pyrazine, pyrimidine, naphthyridine, quinoxaline, 2,6-bis (alkylamido) pyridine, and 2,6-bis (alkylamino) pyridine. It is done.

  Further, as the aromatic polyamide constituting the pseudo-crosslinked resin composition of the present invention, more specifically, diaminobenzene, bis (aminophenyl) sulfone, aminobiphenyl, bis (aminophenyl) propane, bis (amino Aromatic diamines such as phenoxyphenyl) propane and aminophenyl ether, phthalic acid, isophthalic acid, terephthalic acid, biphenyltetracarboxylic acid, trimellitic acid, naphthalenedicarboxylic acid, naphthalenetetracarboxylic acid, and acid anhydrides thereof, Monomer units constituting aromatic polyamides usually obtained from aromatic dicarboxylic acids such as halides, monomer units that can be converted into the first atomic group by being introduced (carbonyl group, carboxyl group, phenolic hydroxyl group, and sulfone) Select from acid group And an amino group or a carboxyl group for bonding, such as diaminobenzoic acid, diaminophenol, diaminobenzenesulfonic acid, and the like, and a monomer unit that can become a second atomic group by being introduced ( A group selected from an optionally substituted amino group and a heterocyclic group containing at least one nitrogen atom, and an amino group or a carboxyl group for bonding, such as diaminopyridine, diaminopyrimidine, diaminonaphthyridine , Diaminoquinoxaline, etc.), and further, as an optional monomer unit, an aromatic system obtained by polycondensation of monomer units such as diaminohexane, diaminosilicone, diaminocyclohexane, etc., which are usually optionally added to an aromatic polyamide Examples thereof include polyamide. After introducing a reactive functional group into both ends of these linear polymers, a cyclic polymer can be obtained using a polyfunctional compound reactive with them.

  Among such aromatic polyamides, for example, the monomer unit that can be the first atomic group and the monomer unit that can be the second atomic group are derivatives of aromatic diamines and aromatic dicarboxylic acids, such as diamino When benzoic acid, diaminopyridine, diaminopyrimidine, diaminonaphthyridine, diaminoquinoxaline and the like are included, the monomer units mentioned as monomer units constituting the aromatic polyamide can be used as arbitrary monomer units.

  The molecular weight of the pseudo-crosslinked linear aromatic polyamide resin composition of the present invention is preferably about 5,000 to 300,000, more preferably 20,000 as the molecular weight of the covalently bonded polymer ignoring pseudo-crosslinking by hydrogen bonding. About 200,000. Further, the content of the first atomic group is about 2 to 1500, preferably about 2 to 1000 per molecule of the covalently bonded polymer as the total number of carbonyl group, carboxyl group, phenolic hydroxyl group and sulfonic acid group. can do. Further, the content of the second atomic group is about 2 to 1500 per covalently bonded polymer molecule as the total number of optionally substituted amino groups and heterocyclic groups containing at least one nitrogen atom, preferably Can be about 2 to 1000.

  The ratio of the first atomic group to the second atomic group in the pseudo-crosslinked aromatic polyamide resin composition of the present invention is such that the carbonyl group, carboxyl group, phenolic hydroxyl group and sulfonic acid in the resin composition The ratio of the total amount of the group and the total amount of the optionally substituted amino group and the heterocyclic group containing at least one nitrogen atom is preferably about 1.0: 0.1 to 1.0: 10.0. More preferably, it is about 1.0: 0.3 to 1.0: 3.0.

  In addition, among the linear aromatic polyamides, there are aromatic polyamides made of a polymer having an amino group or a carboxyl group at the molecular end, but the amino group or carboxyl group present at the molecular end is cyclic. Disappears when converted to polymer. Therefore, it is not included in the category of the crosslinkable resin composition of the present invention. In the pseudo-crosslinked aromatic polyamide resin composition of the present invention, the bonding positions of the first atomic group and the second atomic group interact with each other to form a hydrogen bond, thereby pseudo-crosslinking the resin. As long as the bonding position is of the type, it may be in the side chain or skeleton, but at least one of the first atomic group and the second atomic group is in the side chain or skeleton. A suitable coupling position is desirable. Specifically, a preferable bonding relationship is shown in which the aromatic polyamide resin composition is composed of two types of aromatic polyamides, one of which has a first atomic group in the side chain or skeleton, and the other also has a second atom. What has a group in a side chain or frame | skeleton is mentioned.

  In this way, the pseudo-crosslinked aromatic polyamide resin composition of the present invention in which the first atomic group and the second atomic group are introduced into the cyclic aromatic polyamide has a low linear expansion coefficient and a high glass. It is an unprecedented aromatic polyamide resin composition that has a transition temperature and the like, has improved processability, and can be easily processed into a molded product, film or the like.

(B) Suitable resin of the present invention Examples of resins that are preferably applied other than the aromatic cyclic polyamides include aromatic cyclic polyamideimides, aromatic cyclic polyurethanes, aromatic cyclic polyesters, aromatic polyethers, and the like. Can be mentioned. As the first atomic group and the second atomic group that can be used, the same ones as in the case of the aromatic cyclic polyamide can be used.

4). Molded Article Consisting of Pseudocrosslinked Resin of the Present Invention The molded article of the present invention is molded from the pseudocrosslinked resin composition of the present invention. Specific examples of the molded product include a film, a sheet, and an injection-molded product. As the molded product of the present invention, a film is particularly preferable. Further, when producing these molded products, the pseudo-crosslinked resin composition obtained above is added to a moldability improving agent, a stabilizer, a lubricant, a weathering agent, a flame retardant, a filler, a pigment, an antibacterial agent, and a plasticizer. It is possible to add various additives that are generally added when a synthetic resin is molded into a molded product.

  The method for producing the molded product of the present invention is not particularly limited, and a conventionally known method such as an extrusion molding method, an injection molding method, a blow molding method, or a stretch molding method, depending on the type of the pseudo-crosslinking resin composition. A method such as a casting method can be applied.

  Further, among the pseudo-crosslinked resin compositions of the present invention, particularly for the aromatic polyamide resin composition, the processability to a film can be simplified by improving the solubility in a solvent.

  Hereinafter, the present invention will be specifically described by way of examples. In each of the following examples and comparative examples, various physical properties of the obtained resin molded product such as a film are measured. The measurement method is as follows.

<Physical property measurement method>
(1) Molecular weight measurement The molecular weight measurement and hydrodynamic radius measurement of the polymers obtained in Examples and Comparative Examples were performed by GPC ( gel permeation chromatography) using L6000 manufactured by Hitachi, Ltd. The measurement was performed at a flow rate of 1 ml / min at 25 ° C. using dimethylform ester (lithium bromide concentration = 0.6% by weight) in which lithium bromide was dissolved in the eluent.
(2) Glass transition temperature (Tg), melting point (Tm)
Tg and Tm of the polymers obtained in Examples and Comparative Examples were measured by DSC (Differential Scanning Calorimetry) at a temperature increase rate of 10 ° C./min. As a measuring instrument, DSC7 manufactured by PERKIN-ELMER was used.
(3) Measurement of thermal decomposition temperature The thermal decomposition temperature of the polymers obtained in Examples and Comparative Examples was measured by TG / DTA (simultaneous differential thermothermogravimetry) using SEIKO INSTRUMENT TG / DTA6300. went. Heating was started from 25 ° C. at a temperature rising rate of 10 ° C./min under an air stream, and the temperature was raised to 600 ° C. The temperature at which weight reduction started with heating and the weight at 5% by weight was reduced was defined as the thermal decomposition temperature.
(4) Coefficient of thermal expansion (CTE) measurement The thermal expansion coefficient of the polymers obtained in the examples and comparative examples was measured by TMA (thermomechanical analysis) using RIMAKU's TMA8140. I went. Heating was started from 25 ° C. at a rate of temperature rise of 10 ° C./min under a nitrogen stream, and the temperature was raised to 200 ° C. The average value of the expansion coefficient from 80 ° C. to 180 ° C. was defined as the thermal expansion coefficient.

<Examples and comparative examples>
[Example 1]
(Synthesis of linear polymer A having atomic group 1)
In a three-necked flask equipped with a condenser, 150 g of dimethylacetamide dehydrated with calcium hydride was weighed, and 7.11 g of m-diaminobenzoic acid and 7.51 g of anhydrous lithium chloride were added thereto. M-Diaminobenzoic acid and lithium chloride were dissolved while stirring under a dry argon stream, then cooled to 10 ° C. or lower, and 10.95 g of sebacoyl chloride was added dropwise over about 5 minutes. The temperature was maintained at 10 ° C. or lower while suppressing temperature rise due to heat generation, and left for 5 hours. Thereafter, the mixture was stirred for 20 hours while being kept at about 25 ° C. Thereafter, 0.28 g of m-diaminobenzoic acid was added, and the mixture was kept warm at 60 ° C. with stirring for 3 hours. This time was taken as the reaction end point.
The obtained reaction mixture was dropped into 500 g of distilled water over about 1 hour to precipitate a solid content. After separating the precipitated solid content by filtration, the solid content was dispersed in 500 g of distilled water and pulverized with a cutter mixer. This was filtered off, dispersed in 200 g of distilled water, and the remaining solvent was eluted in water while stirring. Washing with distilled water after pulverization was repeated three times, and then the solid content was separated by filtration. This solid content was dispersed in 150 g of acetone, and unreacted monomers and low molecular weight substances were eluted while stirring at 50 ° C. for 1 hour, and then the solid content was separated by filtration. Washing with acetone was repeated three times. The separated solid was dried at 50 ° C. under reduced pressure for about 5 hours to obtain a linear polymer A having the target atomic group 1. The number average molecular weight of the obtained linear polymer was about 40700.

(Synthesis of linear polymer B having atomic group 2)
In a three-necked flask equipped with a condenser, 150 g of dimethylacetamide dehydrated with calcium hydride and 15 g of linear polymer A having the above atomic group 1 were weighed and dissolved at room temperature with stirring. After confirming that it was visually dissolved, 17.3 g of 2,2,6,6-tetramethyl-p-pyrimidine and 17.2 g of triphenoxy phosphorus were added. The reaction was carried out at 80 ° C. for about 12 hours with stirring. After cooling this reaction mixture to room temperature, it was dripped in distilled water 500g over 30 minutes, and polymer solid content was deposited. After separating the precipitated solid content by filtration, the solid content was dispersed in 500 g of distilled water and pulverized with a cutter mixer. This was filtered off, dispersed in 200 g of distilled water, and the remaining solvent was eluted in water while stirring. Washing with distilled water after pulverization was repeated three times, and then the solid content was separated by filtration. This solid content was dispersed in 150 g of acetone, and unreacted monomers and low molecular weight substances were eluted while stirring at 50 ° C. for 1 hour, and then the solid content was separated by filtration. Washing with acetone was repeated three times. The separated solid was dried at 50 ° C. under reduced pressure for about 5 hours to obtain a linear polymer B having the target atomic group 2. The number average molecular weight of the obtained linear polymer was about 40900.

(Synthesis of cyclic polymer C having atomic group 1)
In a three-necked flask equipped with a cooling tube, 380 g of dimethylacetamide dehydrated with calcium hydride was weighed, 1.5 g of linear polymer A having atomic group 1 was added under a dry argon stream, and dissolved by stirring. The temperature of the reaction system was maintained at 25 ° C. ± 3 ° C. After the linear polymer was dissolved, 0.176 g of sebacoyl chloride was added. Thereafter, the mixture was stirred for about 30 hours while maintaining the same temperature. At this point, the reaction was terminated.
4 g of distilled water was added to the resulting reaction mixture, and the mixture was stirred for about 30 minutes, then transferred to an eggplant-shaped flask, and when the solvent was distilled off at 90 ° C. using an evaporator, the distillation of the solvent was stopped. Thereafter, the concentrated reaction mixture was dropped into 200 g of distilled water over about 1 hour. The precipitated solid was separated by filtration, then dispersed in 150 g of distilled water, and the remaining solvent was eluted in water while stirring for 1 hour. Thereafter, the solid content was separated by filtration. After this operation was repeated three times, the solid content was dispersed in 100 g of acetone and held at 50 ° C. with stirring, and unreacted sebacic acid was eluted in acetone. Thereafter, the solid content was separated by filtration. This operation was repeated three times, and then dried at 50 ° C. under reduced pressure for 5 hours to obtain the target cyclic polymer C. The number average molecular weight of the obtained polymer was about 28500.

(Synthesis of cyclic polymer D having atomic group 2)
In a three-necked flask equipped with a condenser tube, 380 g of dimethylacetamide dehydrated with calcium hydride was weighed, and 1.5 g of linear polymer B having atomic group 2 was added and dissolved by stirring under a dry argon stream. The temperature of the reaction system was maintained at 25 ° C. ± 3 ° C. After the linear polymer was dissolved, 0.176 g of sebacoyl chloride was added. Thereafter, the mixture was stirred for about 30 hours while maintaining the same temperature. At this point, the reaction was terminated.
4 g of distilled water was added to the resulting reaction mixture, and the mixture was stirred for about 30 minutes, then transferred to an eggplant-shaped flask, and when the solvent was distilled off at 90 ° C. using an evaporator, the distillation of the solvent was stopped. Thereafter, the concentrated reaction mixture was dropped into 200 g of distilled water over about 1 hour. The precipitated solid was separated by filtration, then dispersed in 150 g of distilled water, and the remaining solvent was eluted in water while stirring for 1 hour. Thereafter, the solid content was separated by filtration. After this operation was repeated three times, the solid content was dispersed in 100 g of acetone and held at 50 ° C. with stirring, and unreacted sebacic acid was eluted in acetone. Thereafter, the solid content was separated by filtration. This operation was repeated three times, and then dried at 50 ° C. under reduced pressure for 5 hours to obtain the target cyclic polymer D. The number average molecular weight of the obtained polymer was about 28600.

(Characteristic evaluation)
The cyclic polymer C1g having the atomic group 1 and the cyclic polymer D1g having the atomic group 2 obtained by the above method were weighed, and 10 g of N-methylpyrrolidone was added and dissolved at room temperature. This solution was cast on a glass plate, dried in a drying oven at 100 ° C./30 min, and then dried under conditions of 150 ° C./60 min / 20 mmHg to remove N-methylpyrrolidone to produce a film. . This was used as a characteristic evaluation sample. As characteristic evaluation, glass transition temperature, thermal decomposition temperature, melting point, coefficient of thermal expansion, and re-solubility in a solvent were examined.

[Comparative Example 1]
(Synthesis of linear polymer A having atomic group 1)
The same operation as in Example 1 was performed.
(Synthesis of linear polymer B having atomic group 2)
The same operation as in Example 1 was performed.
(Characteristic evaluation)
The same procedure as in Example 1 was performed except that the linear polymers A and B of Comparative Example 1 were used instead of the cyclic polymers C and D of Example 1.

  Tables 1 and 2 show the synthesis examples of Example 1 and Comparative Example 1 and the results of their characteristic evaluation. From these results, it was found that the characteristics in Example 1 were improved with respect to the glass transition temperature (Tg), the coefficient of thermal expansion (CTE), and the melting point (Tm) as compared with Comparative Example 1.

[Example 2]
(Synthesis of linear polymer E having atomic group 1)
The same operation as in Example 1 was performed.
(Synthesis of linear polymer F having atomic group 2)
The procedure was the same as in Example 1 (Synthesis of linear polymer having atomic group 1), except that 5.10 g of m-diaminopyridine was used instead of m-diaminobenzoic acid. The number average molecular weight obtained was about 31200.
(Synthesis of cyclic polymer G having atomic group 1)
The same procedure as in Example 1 was performed except that the linear polymer E of Example 2 was used instead of the linear polymer A of Example 1.
(Synthesis of cyclic polymer H having atomic group 2)
Similar to Example 1 except that 0.230 g was used instead of 0.176 g of sebacoyl chloride and that the linear polymer F of Example 2 was used instead of the linear polymer A of Example 1. went. The number average molecular weight of the obtained cyclic polymer was about 23100.
(Characteristic evaluation)
The same procedure as in Example 1 was performed except that the cyclic polymers G and H of Example 2 were used instead of the cyclic polymers C and D of Example 1.

[Comparative Example 2]
(Synthesis of linear polymer I)
The same procedure as in Example 1 was performed except that 5.05 g of m-diaminobenzene was used instead of 7.11 g of m-diaminobenzoic acid. The number average molecular weight of the obtained linear polymer was about 37800.
(Synthesis of cyclic polymer J)
The same procedure as in Example 1 was performed except that the above linear polymer I was used. The number average molecular weight of the obtained cyclic polymer was about 27900.
(Characteristic evaluation)
The same procedure as in Example 1 was performed except that the cyclic polymer J of Comparative Example 2 was used instead of the cyclic polymers G and H of Example 2.

  Tables 3 and 4 show the synthesis examples of Example 2 and Comparative Example 2 and the results of their characteristic evaluation. From these results, it was found that the characteristics of Example 2 were improved with respect to glass transition temperature (Tg), coefficient of thermal expansion (CTE), and melting point (Tm) as compared with Comparative Example 2.

[Example 3]
(Synthesis of linear polymer K having atomic group 1)
In a three-necked flask equipped with a condenser, 150 g of N-methylpyrrolidone dehydrated with calcium hydride was weighed, and 3.48 g of m-diaminobenzoic acid and 9.40 g of diaminophenoxyphenylpropane were added thereto. M-Diaminobenzoic acid and diaminophenoxyphenylpropane were dissolved while stirring under a dry argon stream, then cooled to 10 ° C. or lower and 9.65 g of pyromellitic anhydride chloride was added. The temperature was maintained at 10 ° C. or lower while suppressing temperature rise due to heat generation, and left for 2 hours. Thereafter, the mixture was stirred for 5 hours while being kept at about 50 ° C. Thereafter, the temperature was raised to 150 ° C., and the same temperature was maintained for 2 hours. Furthermore, after cooling this to 80 degreeC, the acetic anhydride 10.0g and the pyridine 5.0g were added, and the same temperature was hold | maintained for 5 hours. Thereafter, 0.28 g of m-diaminobenzoic acid was added, and the mixture was kept warm at the same temperature with stirring for 3 hours. This time was taken as the end point of the reaction.
The obtained reaction mixture was cooled to room temperature and then added dropwise to 500 g of dry methanol over about 1 hour to precipitate a solid content. The precipitated solid was separated by filtration, then dispersed in 200 g of methanol and the remaining solvent was eluted in methanol with stirring. After washing with methanol three times, the solid content was separated by filtration. This solid content was dispersed in 150 g of acetone, and unreacted monomers and low molecular weight substances were eluted while stirring at 50 ° C. for 1 hour, and then the solid content was separated by filtration. Washing with acetone was repeated three times. The separated solid was dried at 50 ° C. under reduced pressure for about 5 hours to obtain a linear polymer K having the target atomic group 1. The number average molecular weight of the obtained linear polymer was about 57400.

(Synthesis of linear polymer L having atomic group 2)
In a three-necked flask equipped with a cooling tube, 150 g of dimethylacetamide dehydrated with calcium hydride and 15 g of linear polymer K having the above atomic group 1 were weighed and dissolved at room temperature with stirring. After confirming dissolution by visual observation, 2,58,6,6-tetramethyl-p-pyrimidine (10.58 g) and triphenoxy phosphorus (5.25 g) were added. The reaction was carried out at 80 ° C. for about 12 hours with stirring. After cooling this reaction mixture to room temperature, it was dripped in methanol 500g over 30 minutes, and polymer solid content was deposited. The precipitated solid was separated by filtration, then dispersed in 200 g of methanol and the remaining solvent was eluted in water while stirring. After pulverization, washing with methanol was repeated three times, and then the solid content was separated by filtration. This solid content was dispersed in 150 g of acetone, and unreacted monomers and low molecular weight substances were eluted while stirring at 50 ° C. for 1 hour, and then the solid content was separated by filtration. Washing with acetone was repeated three times. The separated solid was dried at 50 ° C. under reduced pressure for about 5 hours to obtain a linear polymer L having the target atomic group 2. The number average molecular weight of the obtained linear polymer was about 57300.

(Synthesis of cyclic polymer M having atomic group 1)
380 g of N-methylpyrrolidone dehydrated with calcium hydride was weighed into a three-necked flask equipped with a cooling tube, and 1.5 g of linear polymer K having atomic group 1 was added and dissolved by stirring under a dry argon stream. . The temperature of the reaction system was maintained at 25 ° C. ± 3 ° C. After the linear polymer was dissolved, 0.125 g of sebacoyl chloride was added. Thereafter, the mixture was stirred for about 30 hours while maintaining the same temperature. At this point, the reaction was terminated.
The obtained reaction mixture was transferred to an eggplant-shaped flask, and when the solvent was distilled off at 110 ° C. using an evaporator, the solvent distillation work was stopped. Thereafter, this concentrated reaction mixture was dropped into 200 g of methanol over about 1 hour. The precipitated solid was separated by filtration, then dispersed in 150 g of methanol, and the remaining solvent was eluted while stirring for 1 hour. Thereafter, the solid content was separated by filtration. This operation was repeated three times, and then the solid content was dispersed in 100 g of acetone and kept at 50 ° C. with stirring to elute unreacted sebacoyl chloride in acetone. Thereafter, the solid content was separated by filtration. This operation was repeated three times, and then dried at 50 ° C. under reduced pressure for 5 hours to obtain the target cyclic polymer M. The number average molecular weight of the obtained polymer was about 37300.

(Synthesis of cyclic polymer N having atomic group 2)
In a three-necked flask equipped with a condenser tube, 380 g of dimethylacetamide dehydrated with calcium hydride was weighed, and 1.5 g of linear polymer L having atomic group 2 was added and dissolved by stirring under a dry argon stream. The temperature of the reaction system was maintained at 25 ° C. ± 3 ° C. After the linear polymer was dissolved, 0.125 g of sebacoyl chloride was added. Thereafter, the mixture was stirred for about 30 hours while maintaining the same temperature. At this point, the reaction was terminated.
The obtained reaction mixture was transferred to an eggplant-shaped flask, and when the solvent was distilled off at 110 ° C. using an evaporator, the solvent distillation work was stopped. Thereafter, this concentrated reaction mixture was dropped into 200 g of methanol over about 1 hour. The precipitated solid was separated by filtration, then dispersed in 150 g of methanol, and the remaining solvent was eluted while stirring for 1 hour. Thereafter, the solid content was separated by filtration. After this operation was repeated three times, the solid content was dispersed in 100 g of acetone and kept at 50 ° C. with stirring, and unreacted sebacoyl chloride was eluted in acetone. Thereafter, the solid content was separated by filtration. This operation was repeated three times, and then dried at 50 ° C. under reduced pressure for 5 hours to obtain the target cyclic polymer N. The number average molecular weight of the obtained polymer was about 37500.

(Characteristic evaluation)
The same procedure as in Example 1 was performed except that the cyclic polymers M and N of Example 3 were used instead of the cyclic polymers C and D of Example 1.

[Comparative Example 3]
(Synthesis of linear polymer K having atomic group 1)
The same operation as in Example 3 was performed.
(Synthesis of linear polymer L having atomic group 2)
The same operation as in Example 3 was performed.
(Characteristic evaluation)
The same procedure as in Example 1 was performed except that the linear polymers K and L of Comparative Example 3 were used instead of the cyclic polymers M and N of Example 3.

  Tables 5 and 6 show synthesis examples of Example 3 and Comparative Example 3, and the results of their characteristic evaluation. From these results, it was found that the characteristics of Example 3 were improved with respect to glass transition temperature (Tg), coefficient of thermal expansion (CTE), and melting point (Tm) as compared with Comparative Example 3.

[Example 4]
(Synthesis of linear polymer O having atomic group 1 and atomic group 2)
The same procedure as in Example 3 was performed except that 1.74 g of m-diaminobenzoic acid and 1.25 g of m-diaminopyridine were used instead of 3.48 g of m-diaminobenzoic acid of Example 3. The number average molecular weight of the obtained linear polymer was about 42800.
(Synthesis of cyclic polymer P having atomic group 1 and atomic group 2)
The same operation as in Example 3 was performed. The number average molecular weight of the obtained cyclic polymer was about 30,000.
(Characteristic evaluation)
The same procedure as in Example 1 was performed except that the cyclic polymer P of Example 4 was used instead of the cyclic polymers C and D of Example 1.

[Comparative Example 4]
(Synthesis of linear polymer Q)
The same procedure as in Example 3 was performed except that 2.48 g of m-diaminobenzene was used instead of 3.48 g of the linear polymer m-diaminobenzoic acid of Example 3. The number average molecular weight of the obtained linear polymer was about 51200.
(Synthesis of cyclic polymer R)
The same procedure as in Example 4 was performed except that the linear polymer Q of Comparative Example 4 was used instead of the linear polymer O of Example 4. The number average molecular weight of the obtained cyclic polymer was about 38000.
(Characteristic evaluation)
The same procedure as in Example 1 was performed except that the cyclic polymer R of Comparative Example 4 was used instead of the cyclic polymer P of Example 4.

  Tables 7 and 8 show the synthesis examples of Example 4 and Comparative Example 4 and the results of their characteristic evaluation. From these results, it was found that the characteristics in Example 4 were improved with respect to the glass transition temperature (Tg), the coefficient of thermal expansion (CTE), and the melting point (Tm) as compared with Comparative Example 4.

[Example 5]
(Synthesis of linear polymer S having atomic group 1)
In a three-necked flask equipped with a condenser, 150 g of dimethylacetamide dehydrated with calcium hydride was weighed, and 7.06 g of m-hydroxybenzoic acid was added thereto. After m-hydroxybenzoic acid was dissolved while stirring under a dry argon stream, 10.95 g of sebacoyl chloride was added dropwise at room temperature over about 5 minutes. While suppressing the temperature rise due to heat generation, the temperature was kept at 40 ° C. or lower and left for 5 hours. Thereafter, the mixture was stirred for 20 hours while being kept at about 120 ° C. Thereafter, 0.42 g of m-hydroxybenzoic acid was added, and the mixture was kept warm at 120 ° C. with stirring for 8 hours. This time was taken as the reaction end point.
The obtained reaction mixture was dropped into 500 g of distilled water over about 1 hour to precipitate a solid content. After separating the precipitated solid content by filtration, the solid content was dispersed in 500 g of distilled water and pulverized with a cutter mixer. This was filtered off, dispersed in 200 g of distilled water, and the remaining solvent was eluted in water while stirring. Washing with distilled water after pulverization was repeated three times, and then the solid content was separated by filtration. This solid content was dispersed in 150 g of acetonitrile, and unreacted monomers and low molecular weight substances were eluted while stirring at about 25 ° C. for 1 hour, and then the solid content was separated by filtration. Washing with acetonitrile was repeated three times. The separated solid was dried at 50 ° C. under reduced pressure for about 5 hours to obtain a linear polymer S having the target atomic group 1. The number average molecular weight of the obtained linear polymer was about 30300.

(Synthesis of linear polymer T having atomic group 2)
In a three-necked flask equipped with a cooling tube, 150 g of dimethylacetamide dehydrated with calcium hydride and 15 g of the linear polymer S having the atomic group 1 were weighed and dissolved at room temperature with stirring. After confirming that it was visually dissolved, 14.63 g of 2,2,6,6-tetramethyl-p-pyrimidine and 14.09 g of triphenoxy phosphorus were added. The reaction was carried out at 80 ° C. for about 12 hours with stirring. After cooling this reaction mixture to room temperature, it was dripped in distilled water 500g over 30 minutes, and polymer solid content was deposited. After separating the precipitated solid content by filtration, the solid content was dispersed in 500 g of distilled water and pulverized with a cutter mixer. This was filtered off, dispersed in 200 g of distilled water, and the remaining solvent was eluted in water while stirring. Washing with distilled water after pulverization was repeated three times, and then the solid content was separated by filtration. This solid content was dispersed in 150 g of acetonitrile, and unreacted monomers and low molecular weight substances were eluted while stirring at about 25 ° C. for 1 hour, and then the solid content was separated by filtration. Washing with acetonitrile was repeated three times. The separated solid was dried at 50 ° C. under reduced pressure for about 5 hours to obtain a linear polymer T having the target atomic group 2. The number average molecular weight of the obtained linear polymer was about 30600.

(Synthesis of cyclic polymer U having atomic group 1)
The same procedure as in Example 1 was performed except that the linear polymer S of Example 5 was used instead of the linear polymer A of Example 1. The number average molecular weight of the obtained cyclic polymer was about 23100.

(Synthesis of cyclic polymer V having atomic group 2)
The same procedure as in Example 1 was performed except that the linear polymer T of Example 5 was used instead of the linear polymer B of Example 1. The number average molecular weight of the obtained cyclic polymer was about 22900.

(Characteristic evaluation)
The same procedure as in Example 1 was performed except that the cyclic polymers U and V of Example 5 were used instead of the cyclic polymers C and D of Example 1.

[Comparative Example 5]
(Synthesis of linear polymer S having atomic group 1)
The same operation as in Example 5 was performed.
(Synthesis of linear polymer T having atomic group 2)
The same operation as in Example 5 was performed.
(Characteristic evaluation)
The same procedure as in Example 1 was performed except that the linear polymers S and T of Comparative Example 5 were used instead of the cyclic polymers U and V of Example 5.

  Tables 9 and 10 show synthesis examples of Example 5 and Comparative Example 5 and the results of their characteristic evaluation. From these results, it was found that the characteristics in Example 5 were improved with respect to the glass transition temperature (Tg), the coefficient of thermal expansion (CTE), and the melting point (Tm) as compared with Comparative Example 5.

As described above, in the pseudo-crosslinked resin composition of the present invention, the number of pseudo-crosslinking points between molecules due to the cyclic structure increases, so that the glass transition temperature (Tg), the coefficient of thermal expansion (CTE), and the melting point (Tm). It is estimated that the characteristics have improved.

Claims (6)

A pseudo-crosslinked resin composition comprising a cyclic polymer in which one or two or more synthetic polymers are intramolecularly bonded at their molecular ends ,
The one or more synthetic polymers are aromatic polyamides, a first atomic group containing a carboxyl group , an optionally substituted amino group, and a heterocyclic group containing at least one nitrogen atom A second atomic group containing a group selected from the group consisting of:
A pseudo-crosslinked resin composition, wherein pseudo-crosslinking is formed by hydrogen bonding between the first atomic group and the second atomic group.   The pseudo-crosslinked resin composition according to claim 1, wherein the synthetic polymer has both a first atomic group and a second atomic group in the same molecule. The first atomic group is an atomic group having a basic skeleton represented by [Chemical Formula 1] , and the second atomic group is an atomic group having a basic skeleton represented by [Chemical Formula 2] , Item 5. A pseudo-crosslinked resin composition according to Item 1.

[Wherein, R ₁ represents an aliphatic or aromatic hydrocarbon group. ]

[Wherein, R ₁ and R ₂ each represents an aliphatic hydrocarbon group. ]   The pseudo-crosslinked resin composition according to claim 1, wherein the synthetic polymer has a molecular weight of 5000 or more.   A molded product molded from the pseudo-crosslinked resin composition according to any one of claims 1 to 4.   The molded article according to claim 5, wherein the molded article is a film.