JP2000169527A - Thermoplastic elastomer, thermoplastic resin, and their production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic elastomer which can repeatedly undergo thermotropical crosslinking and de-crosslinking and can develop very easily sufficient rubber properties at a practically durable high temperature, which elastomer has carbonyl-containing groups and heterocyclic amine containing groups as the side chains and has the eapability of hydrogen bonding. SOLUTION: It is desirable that the carbonyl-containing group is at least one selected from among an amido, an ester group, an imido, and a carboxyl, and it is also desirable that it has at least one of groups of formulae I, II, III, IV and V. In the formulae, R is a heterocyclic amine. This elastomer is obtained by reacting an elastomeric polymer having cyclic acid anhydride groups as the side chains with a heterocyclic amine-containing compound at a temperature at which the heterocyclic amine containing compound can chemically combine with the cyclic acid anhydride groups. The carbonyl-containing groups and the heterocyclic amine containing groups constitute pendants as the side chains of the elastomeric polymer and are chemically stably bonded to the main chain.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel thermoplastic elastomer and a thermoplastic resin capable of repeatedly reproducing curing and fluidization by a change in temperature.

[0002]

2. Description of the Related Art Thermoplastic elastomers utilize physical crosslinking with respect to conventional vulcanized rubber having a stable three-dimensional network structure in which a polymer substance and a vulcanizing agent are covalently bonded. As in the case of the thermoplastic resin, it can be easily molded by heating and melting, without the need for complicated vulcanization and molding steps including molding.

[0003] A typical example of such a thermoplastic elastomer includes a resin component and a rubber component, and at normal temperature, the microcrystalline resin component becomes a constrained phase (hard segment) that serves as a cross-linking point of a three-dimensional network structure. It is known that the plastic deformation of a rubber component (soft segment) is prevented, and the plastic component is plastically deformed by softening or melting of a resin component due to a rise in temperature. Specific examples of the thermoplastic elastomer containing a resin component and a rubber component as described above include a styrene-butadiene block copolymer, a block copolymer such as an isoprene multi-block copolymer, and polypropylene and ethylene-propylene. Diene copolymer (EPD
A resin / rubber blend with M) is known. Further, a rubber component (EPDM) in the resin / rubber blend as described above is also crosslinked with a peroxide or the like.

[0004] The above-mentioned known thermoplastic elastomers contain a resin component in order to form a constrained phase, and it cannot be denied that the rubber elasticity is reduced as compared with a conventional vulcanized rubber. For this reason, if a thermoplastic elastomer that exhibits thermoplasticity without containing a resin component for forming a constrained phase appears, in other words, imparting thermoplasticity (fluidity) to the vulcanized rubber. If it is possible, a rubber elastic body can be obtained by simple heat molding without performing complicated steps such as kneading, preforming, and vulcanization, which were conventionally required, and its industrial utility value is Extremely high.

[0005] By the way, it is known to use hydrogen bonding as a method for modifying a thermoplastic resin. For example, Japanese Patent Application Laid-Open No. 63-69864 discloses that even if a resin is deformed by lowering the amount of hydrogen bonding (crosslinking) at a temperature higher than the glass transition point, it is restored to its original shape by cooling to a temperature lower than the glass transition point again. Such a shape memory resin has been proposed. As a preferred specific example, it is disclosed that molding is performed by including a large amount of hydrogen bonds during a curing reaction between an epoxy compound and an amine curing agent. In addition, when a compound having a low molecular weight or a thermoplastic resin having a high fluidity is added as a fluidity improver of a resin, a method of utilizing a hydrogen bond to suppress a decrease in heat resistance or rigidity has been proposed. I have. For example, a method for improving the fluidity and heat resistance of a thermoplastic resin by adding a compound having a hydroxyl group and a compound having a group capable of hydrogen bonding to the group to the thermoplastic resin (Japanese Patent Application Laid-Open No. 5-339420). Publication) or a method of improving the rigidity and fluidity of a styrene resin by adding a thermoplastic resin and a compound having a functional group capable of hydrogen bonding to the carboxyl group to a styrene resin having a carboxyl group. (Kaihei 7-33002)
Are disclosed.

Although it is theoretically known that a thermoplastic elastomer can be obtained by utilizing the above-mentioned hydrogen bond for crosslinking, there is no known practical use. That is, the hydrogen bond has a smaller binding energy than the chemical bond, and is susceptible to cross-linking under the influence of heat or the like.

[0007] On the other hand, from the standpoint of environmental protection and resource saving, it is required to reuse used resins. In order to improve heat resistance and mechanical strength at high temperatures, thermoplastic resins such as olefin resins are often subjected to a crosslinking treatment by utilizing a silanol condensation reaction. However, the resin crosslinked to form a crosslinked body no longer has thermoplasticity and cannot be reused by melt molding. Therefore, compatibility between the crosslinked body and thermoplasticity is strongly demanded. JP-A-11-140578 discloses that a carboxylic acid anhydride-modified olefin-based resin does not have a hydroxyl group bonded to a primary carbon atom but has at least two hydroxyl groups bonded to a secondary carbon atom. Is disclosed. By mixing a specific hydroxyl group-containing compound with an unsaturated carboxylic anhydride-modified olefin resin, this thermoplastic resin can repeatedly form crosslinks at low temperatures and dissociate the crosslinks at high temperatures. A crosslinkable olefin-based resin composition which aims to improve crosslinkability and crosslink dissociation, heat resistance and melt fluidity. However, this thermoplastic resin composition has a high cross-linking reaction rate, but has a considerably high cross-linking dissociation temperature as compared with an unmodified olefin resin, and does not show good melt fluidity unless the temperature is high. Therefore, while exhibiting sufficient melt flowability at the molding temperature of unmodified thermoplastic resins such as olefinic resins, it has excellent mechanical strength such as breaking strength due to cross-linking at low temperatures, and is cured by temperature changes. If a thermoplastic resin capable of repeatedly reproducing fluidization appears, its industrial use value and environmental protection value are extremely high.

[0008]

DISCLOSURE OF THE INVENTION The present invention has a structure capable of self-crosslinking by providing both a group that can serve as a donor and a group that can serve as an acceptor during hydrogen bonding in a molecule.・ While being able to repeatedly reproduce de-crosslinking, extremely easily, and forming stable hydrogen bonds up to a high temperature that can withstand use, it exhibits sufficient rubber properties that can be used as a rubber, while excellent at the time of high temperature heating An object of the present invention is to provide a novel hydrogen-bonding thermoplastic elastomer exhibiting fluidity.

[0009] Further, the compound has a structure capable of self-crosslinking by having both a group that can serve as a donor and a group that can serve as an acceptor during hydrogen bonding in the molecule, and repeatedly reproduces thermotropic crosslinking / decrosslinking. Can be formed, very easily, and form a stable hydrogen bond up to a high temperature that can withstand use, showing excellent fracture physical properties and heat resistance,
On the other hand, an object of the present invention is to provide a novel hydrogen bonding thermoplastic resin exhibiting excellent fluidity when heated at a high temperature.

[0010]

Means for Solving the Problems The present inventors have studied thermoplastic elastomers utilizing hydrogen bonds. As a result, elastomers having both a carbonyl group-containing group and a heterocyclic amine-containing group in the side chain are: Not only can it form a thermotropic hydrogen-bonded cross-linked structure and can repeatedly reproduce cross-linking at room temperature (use) and de-cross-linking and fluidization during heating, but the elastomer having the above-mentioned side chain can be very easily prepared. In addition, it has been found that a stable hydrogen bond is formed up to a high temperature that can withstand use, thereby exhibiting sufficient rubber properties that can be practically used as a rubber, while exhibiting excellent fluidity when heated at a high temperature. Such a thermoplastic elastomer does not need to include a thermoplastic resin for forming a constrained phase, and can sufficiently exhibit the inherent properties of the elastomer as compared with conventionally used thermoplastic elastomers. The inventors have found that the present invention has been completed.

The present inventor has further studied a thermoplastic resin utilizing a hydrogen bond, and a resin having both a carbonyl group-containing group and a heterocyclic amine-containing group in a side chain is a thermotrophic resin. Not only can it form a hydrogen-bonded cross-linking structure and can repeatedly reproduce cross-linking at room temperature (use) and de-cross-linking and fluidization during heating, but the resin having the above-mentioned side chain is extremely easy and easy to use. The present inventors have found that they form stable hydrogen bonds up to a high temperature that can withstand and exhibit excellent mechanical strength such as excellent breaking strength, and that they easily show excellent fluidity when heated at a high temperature, thereby completing the present invention.

That is, the thermoplastic elastomer of the present invention comprises an elastomeric polymer having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in a side chain, and is characterized by being hydrogen-bonding. And (I) above
The carbonyl group-containing group is preferably a group derived from a cyclic acid anhydride. Also, (ii) the heterocyclic amine-containing group is
(i) It is preferably bonded to the elastomeric polymer via a carbonyl group-containing group. Specifically, (i) the carbonyl group-containing group is preferably at least one of amide, ester, imide and carboxyl.
The thermoplastic elastomer of the present invention preferably has at least one group represented by the following formulas (1), (2), (3), (4), and (5) as a side chain.

[0013]

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The above-mentioned thermoplastic elastomers include, for example, an elastomeric polymer having a cyclic acid anhydride group in the side chain and a heterocyclic amine-containing compound, wherein the heterocyclic amine-containing compound is chemically bonded to the cyclic acid anhydride group. It can be produced by reacting at a temperature capable of binding.

Further, the thermoplastic resin of the present invention has
It is made of a plastic polymer having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group, and is characterized by being hydrogen-bonding. The (i) carbonyl group-containing group is preferably a group derived from a cyclic acid anhydride. Further, (ii) the heterocyclic amine-containing group is preferably bonded to the plastic polymer via (i) a carbonyl group-containing group. Specifically, (i) the carbonyl group-containing group is preferably at least one of amide, ester, imide and carboxyl. In the thermoplastic resin of the present invention, as the side chain, specifically the above formula (1),
It preferably has at least one group of (2), (3), (4) and (5).

The thermoplastic resin as described above includes, for example, a plastic polymer having a cyclic acid anhydride group in a side chain and a heterocyclic amine-containing compound, wherein the heterocyclic amine-containing compound is chemically bonded to the cyclic acid anhydride group. It can be produced by reacting at a temperature capable of binding.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The present invention includes the following two embodiments. A first aspect of the present invention: a thermoplastic elastomer comprising an elastomeric polymer having a hydrogen-bonding (i) carbonyl group-containing group and (ii) heterocyclic amine-containing group in a side chain (including a molecular terminal). (Hereinafter referred to as the thermoplastic elastomer of the present invention). Second embodiment of the present invention: a thermoplastic resin comprising a plastic polymer having a hydrogen-bonding (i) carbonyl group-containing group and (ii) heterocyclic amine-containing group in a side chain (including a molecular terminal). (Hereinafter referred to as the thermoplastic resin of the present invention).

Here, "having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group" in the side chain means that the atom (usually carbon) forming the main chain of the elastomeric polymer or the plastic polymer is , The (i) carbonyl group-containing group and (ii) the heterocyclic amine-containing group have a chemically stable bond (covalent bond). On the other hand, a “hydrogen bond” is one in which atoms having high electronegativity are physically bonded via hydrogen, for example, and the bond energy is usually about 1 to 8 kcal / mol, and Lower than that.

<First Embodiment of the Present Invention> In the first embodiment of the present invention, the elastomeric polymer serving as the main chain is a natural polymer or a polymer generally known as a rubber elastic material for vulcanization (crosslinking, curing). It is a synthetic polymer. Specific examples of such an elastomeric polymer include natural rubber, isoprene rubber, butadiene rubber, 1,2-butadiene rubber, styrene-butadiene rubber, nitrile rubber,
Diene rubbers such as chloroprene rubber, butyl rubber, ethylene-propylene rubber (EPDM, EPM), chlorosulfonated polyethylene, acryl rubber, olefin rubber such as fluorine rubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, urethane Rubber and the like can be mentioned.

A thermoplastic elastomer (TPE) containing a resin component may be used. For example, a polystyrene-based TPE (SBS, SIS, SEB) which may be hydrogenated may be used.
S), polyolefin-based TPE, polyvinyl chloride-based TP
E, polyurethane-based TPE, polyester-based TPE, polyamide-based TPE, and the like may be used.

The elastomeric polymer as described above is
It may be liquid or solid. The molecular weight is not particularly limited and can be appropriately selected depending on the purpose of use, crosslink density, etc., but it is convenient for producing a thermoplastic elastomer and fluidity during heating (decrosslinking) of the thermoplastic elastomer. It is preferably a liquid rubber.
The molecular weight is desirably such that it shows a liquid state. For example, in the case of diene rubbers such as isoprene rubber and butadiene rubber, the weight average molecular weight is desirably 1,000 to 500,000, preferably about 1,000 to 100,000.

In the first embodiment of the present invention, the (i) carbonyl group-containing group bonded to the side chain of the elastomeric polymer as described above is hydrogen-bonding, and specifically, a carbonyl group, a carboxyl group (OH ), An amide group, an ester group, an imide group and the like. Examples of the compound into which such a group can be introduced include a carboxylic acid and a derivative thereof without particular limitation. Examples of the carboxylic acid compound include organic acids having a saturated or unsaturated hydrocarbon group, and the hydrocarbon group may be any of aliphatic, alicyclic, and aromatic carboxylic acids. Examples of the carboxylic acid derivatives include carboxylic acid anhydrides, esters, ketones, amino acids, amides, imides, and thiocarboxylic acids (carboxylic acids containing a mercapto group).

Specifically, malonic acid, maleic acid, succinic acid, glutaric acid, phthalic acid, isophthalic acid, terephthalic acid, p-phenylenediacetic acid, p-hydroxybenzoic acid, p-aminobenzoic acid, mercaptoacetic acid, etc. Acid anhydrides such as carboxylic acids and substituent-containing carboxylic acids, succinic anhydride, maleic anhydride, glutaric anhydride, phthalic anhydride, propionic anhydride, benzoic anhydride, maleic esters, malonic esters, succinic esters , Glutarate, aliphatic esters such as ethyl acetate, phthalates, isophthalates, terephthalates, aromatic esters such as ethyl-m-aminobenzoate, methyl-p-hydroxybenzoate, quinones, anthraquinones, naphthoquinones, etc. Ketone, glycine, Shin, bicine, alanine, valine,
Amino acids such as leucine, serine, threonine, lysine, aspartic acid, glutamic acid, cysteine, methionine, proline, N- (p-aminobenzoyl) -β-alanine, maleamide, maleamic acid (maleic monoamide), succinic acid monoamide; 5-hydroxyvaleramide, N-acetylethanolamine, N,
N'-hexamethylenebisacetamide, malonamide, cycloserine, 4-acetamidophenol, p-
Examples include amides such as acetamidobenzoic acid and imides such as maleimide and succinimide.

(Ii) The heterocyclic amine-containing group is introduced from a nitrogen-containing heterocyclic ring or a compound containing the heterocyclic ring. The nitrogen-containing heterocyclic ring may be any structure that contains or generates a hydrogen-bonding amino group in the heterocyclic ring. Examples of such a nitrogen-containing heterocycle include pyrrole, histidine, imidazole, triazolidine, triazole, triazine,
Examples include pyridine, pyrimidine, pyrazine, indole, quinoline, purine, phenazine, pteridine, melamine and the like. The nitrogen-containing heterocyclic ring may include another hetero atom in the ring.

The compound containing a nitrogen-containing heterocyclic ring may have any of the above-mentioned heterocyclic skeletons, and is not particularly limited. For example, a group capable of chemically (covalently) bonding to the main chain carbon of the elastomeric polymer. May be provided. Examples of such a group include an amino group, a hydroxyl group, a methylene group, an ethylene group, and a carboxylic acid. Specific examples of such a compound containing a nitrogen-containing heterocyclic ring include dipyridyl, ethylenedipyridyl, trimethylenedipyridyl, dipyridylamine, 1,2-dimethylimidazole, 2-benzimidazoleurea, pyrrole-2-carboxylic acid, -Methyl-pyrazole, pyridine, 4-methylpyridine, 4 (or 2) -hydroxymethylpyridine, 2 (or 4)-(β-hydroxyethyl) -pyridine, 2 (or 4)-(2-aminoethyl)- Pyridine, 2
(or 4) -aminopyridine, 2,6-diaminopyridine, 2-amino-6-hydroxypyridine, 6-azathymine, acetoguanamine, benzoguanamine, citrazic acid, 1,2,4-triazole, 3-amino-1,
2,4-triazole, 3-aminomethyl-1,2,4
-Triazole, 3-methylamino-1,2,4-triazole, 3-methylol-1,2,4-triazole, 3-hydroxy-1,2,4-triazole, 2-
Hydroxytriazine, 2-aminotriazine, 2-hydroxy-5-methyltriazine, 2-amino-5-methyltriazine, 2-hydroxypyrimidine, 2-aminopyrimidine, 2-aminopyrazine, 2-hydroxypyrazine, 6-aminopurine , 6-hydroxypurine and the like.

The thermoplastic elastomer of the present invention comprises an elastomeric polymer having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in a side chain and in one molecule. . The (i) carbonyl group-containing group and (ii) heterocyclic amine-containing group are pendant to the side chain of the elastomeric polymer and have a chemically stable bond as described above. At this time, (i) the carbonyl group-containing group and (ii) the heterocyclic amine-containing group may be bonded to the polymer main chain as mutually independent side chains, or may be bonded to the main chain through different groups. Thereby, (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group may form one side chain. As described above, when one side chain is formed by (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group, not only the bond with the main chain but also the (i) carbonyl group-containing group (ii) it is also chemically bonded to the heterocyclic amine-containing group. This (i) carbonyl group-containing group and (ii) heterocyclic amine-containing group may be bonded via some kind of bond.

As an example of a thermoplastic elastomer in which (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group are independently bonded to the main chain of an elastomeric polymer, (i) carbonyl is added to a side chain of isoprene rubber. A carboxyl group as a group-containing group and 1,2,4 as a (ii) heterocyclic amine-containing group.
The structure of the thermoplastic elastomer (A) bonded to triazolyl is schematically shown below.

[0028]

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An example of a thermoplastic elastomer in which (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group form one side chain by bonding to the main chain via different groups from each other. The elastomeric polymer is isoprene rubber, (i) the carbonyl group-containing group is a group derived from maleic anhydride, and (ii) the heterocyclic amine is 3-
The structure of the thermoplastic elastomer (B), which is a group derived from amino-1,2,4-triazole, is schematically shown below. This thermoplastic elastomer (B) is formed by reacting 3-amino-1,2,4-triazole with maleic anhydride to form a carboxyl group with an amide bonding group formed by ring opening of maleic anhydride. It has a branch in one side chain.

[0030]

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In the first aspect of the present invention, among the above, (i) the carbonyl group-containing group includes succinic anhydride,
Cyclic acid anhydrides such as maleic anhydride, glutaric anhydride, and phthalic anhydride, particularly groups derived from maleic anhydride are preferred.

(Ii) The heterocyclic amine-containing group is preferably a heterocyclic ring having two or more nitrogen atoms in the skeleton, more preferably a heterocyclic ring having three or more nitrogen atoms, particularly preferably a group derived from a triazole ring. preferable. Specifically 3-
Amino-1,2,4-triazole, 3-hydroxy-
1,2,4-triazole, 3-aminomethyl-1,
2,4-triazole, 3-methylamino-1,2,4
Preferred are groups derived from -triazole, 3-methylol-1,2,4-triazole and the like.

Further, as shown above as the thermoplastic elastomer (B), a structure in which (i) a heterocyclic amine-containing group is bonded to a main chain via a (i) carbonyl group-containing group to form a side chain. Are preferred. In a structure in which (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group form one side chain, (ii) a heterocyclic amine-containing group and a carbonyl group in the (i) carbonyl group-containing group It is preferable that at least one kind of bond of amide, amide, ester and imide, or at least one kind of bond and a carboxyl group are formed. In particular, the side chain formed by the bond between the cyclic acid anhydride and (ii) the heterocyclic amine-containing group has a carboxyl group together with an amide, ester or imide. Such bonds, amides,
Specific examples of the side chain having an ester or an imide are shown below (amide: the following formulas (1) and (2), ester: the following formulas (3) and (4), and imide: the following formula (5)).

[0034]

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The heterocyclic amine represented by R is not particularly limited.

Embedded image And the like.

When (i) the carbonyl group-containing group is a group derived from a cyclic acid anhydride, and / or (ii) the heterocyclic amine-containing group is a group derived from a triazole compound, these groups are Those independently bonded to the main chain are also preferred.

The thermoplastic elastomer of the present invention as described above can be produced by a method having a structure having the above-mentioned (i) carbonyl group-containing group and (ii) heterocyclic amine-containing group in the side chain of the elastomeric polymer. Is not particularly limited. For example, during the production of an elastomeric polymer, a monomer capable of forming the main chain of the polymer and a copolymerizable monomer capable of introducing the above group are copolymerized to form (i) a carbonyl group-containing group and (ii) a heterocyclic group on the side chain. A thermoplastic elastomer having a structure having a cyclic amine-containing group may be directly produced, or a main chain (elastomeric polymer) is formed in advance by polymerization or the like, and then (i) a carbonyl group-containing group and (ii) a heterocyclic amine The compound may be graft-modified with a compound capable of introducing a group.

Among the thermoplastic elastomers of the present invention, those having both (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in one side chain include, for example,
(i) an elastomer modified with a carbonyl group-containing group,
It can be obtained by reacting (ii) a compound into which a heterocyclic amine-containing group can be introduced, and bonding (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group. (i) the modified elastomer having a carbonyl group-containing group,
For example, a toluene solution containing a diene rubber such as butadiene rubber and mercaptoacetic acid can be stirred at room temperature under a nitrogen atmosphere for 1 hour, and the reaction mixture can be precipitated in methanol and dried under reduced pressure.

As such a modified elastomer, a commercially available product can be used. For example, as an elastomer having a carbonyl group-containing group in a side chain, LIR-410M
Maleic anhydride-modified isoprene rubber such as (Kuraray), carboxyl-modified isoprene rubber such as LIR-410 (Kuraray), Clinac 110, -221,-
Carboxyl-modified nitrile rubber such as 231 (manufactured by Policer); carboxyl-modified polybutene such as CPIB (manufactured by Nisseki Chemical Co., Ltd.); HRPIB (produced by Nisseki Chemical Lab.);
And Yucaron (manufactured by Mitsubishi Chemical Corporation).

Further, (i) a carbonyl group-containing group and (i)
i) The compounds capable of introducing a heterocyclic amine-containing group may be bonded to each other, and then bonded to a side chain of the elastomeric polymer. In each of the above-described production methods, whether each group of the side chain of the elastomeric polymer is independently bonded or bonded to each other can be confirmed by conventional analysis means such as an NMR spectrum. it can.

In the first embodiment of the present invention, among the above, the groups of (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group are added to the side chain of the preformed elastomeric polymer (main chain). Preferably, the modified elastomer having a cyclic acid anhydride group in the side chain and the heterocyclic amine-containing compound are combined at a temperature at which the heterocyclic amine-containing compound can chemically bind to the cyclic acid anhydride group. Is preferably reacted. By this reaction, the acid anhydride may be opened.

The temperature at which the heterocyclic amine-containing compound can be chemically bonded varies depending on the type of the compound, but is usually about room temperature to about 150 ° C. More specifically, for example, in the reaction of maleic anhydride-modified isoprene rubber with 3-amino-1,2,4-triazole as a heterocyclic amine-containing compound, if the reaction temperature is about 120 ° C., maleic anhydride And 3-amino-1,2,4-triazole are chemically bonded to form a side chain having an amide bond as shown in the above formula (A), but when the carbonyl group is a carboxyl group However, even at the same reaction temperature, 3-amino-1,2,4-triazole may form a hydrogen bond with either a carboxyl group or an elastomer main chain, but is difficult to chemically bond. The reaction time is usually about 3 to 5 hours.

Next, a second embodiment of the present invention will be described. <Second Embodiment of the Present Invention> A second embodiment of the present invention relates to a hydrogen-bonding polymer comprising a plastic polymer having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in a side chain. Is a thermoplastic resin. In the second embodiment of the present invention, the plastic polymer serving as the main chain is a synthetic polymer generally known as a thermoplastic resin. Specific examples of such a plastic polymer include, for example, a homopolymer of ethylene (branched or linear) such as low density / medium density / high density polyethylene, ethylene, propylene, butene-1,3- Methylbutene-1, pentene-
1,3-methylpentene-1,4-methylpentene-
Α- such as 1, hexene-1, octene-1, and decene-1
Ethylene-based resins such as copolymers with olefins, copolymers of ethylene with other monomers such as vinyl esters such as vinyl acetate, acrylic acid, methacrylic acid, or esters thereof, and homopolymers of propylene ( Polypropylene, P
P), propylene and ethylene, butene-1,3-methylbutene-1, pentene-1,3-methylpentene-
Copolymers with α-olefins such as 1,4-methylpentene-1, hexene-1, octene-1, decene-1, propylene, isoprene, 1,3-butadiene, 1,3
Propylene-based resins such as copolymers with other monomers such as diene compounds such as pentadiene, 1,4-hexadiene, 1,5-hexadiene, and 1,9-decadiene;
Α-olefin homopolymers and copolymers such as 1,4-methylpentene-1 and hexene-1, acrylonitrile,
Graft polymer with butadiene, styrene (ABS resin), copolymer with acrylonitrile, styrene (AS
Resins), styrene resins such as general-purpose polystyrene and impact-resistant polystyrene, vinyl chloride resins, acrylic resins, polycarbonates, polyamide resins and the like. Among these, an olefin resin such as an ethylene resin or a propylene resin is particularly preferable because it is excellent in heat resistance, mechanical strength, and adhesion.

The plastic polymer as described above is
The molecular weight is not particularly limited, and can be appropriately selected depending on the purpose of use, crosslink density, and the like.From the viewpoint of convenience in producing a thermoplastic resin and fluidity during heating (decrosslinking) of the thermoplastic resin, As for the molecular weight, for example, in the case of polypropylene, the number average molecular weight is preferably 1,000 to 500,000.

In the second embodiment of the present invention, the (i) carbonyl group-containing group bonded to the side chain of the plastic polymer as described above is hydrogen-bonding, and specifically includes a carbonyl group, a carboxyl group, and an amide group. Groups, ester groups, imide groups and the like. Examples of the compound into which such a group can be introduced include a carboxylic acid and a derivative thereof without particular limitation. Examples of the carboxylic acid compound include organic acids having a saturated or unsaturated hydrocarbon group, and the hydrocarbon group may be any of aliphatic, alicyclic, and aromatic carboxylic acids. Further, as the carboxylic acid derivative, carboxylic anhydride, ester, ketone, amino acid,
Examples include amides, imides, and thiocarboxylic acids (carboxylic acids containing a mercapto group).

Specific examples of the carboxylic acid compound and the carboxylic acid derivative include the same compounds as the compounds exemplified as the specific examples of the carboxylic acid compound and the carboxylic acid derivative in the first embodiment of the present invention.

Further, (ii) the heterocyclic amine-containing group is introduced from a nitrogen-containing heterocyclic ring or a compound containing the heterocyclic ring. The nitrogen-containing heterocyclic ring may be any structure that contains or generates a hydrogen-bonding amino group in the heterocyclic ring. Examples of such a nitrogen-containing heterocyclic ring include the same compounds as the compounds exemplified as the nitrogen-containing heterocyclic ring in the first embodiment of the present invention. The nitrogen-containing heterocyclic ring may include another hetero atom in the ring.

The compound containing a nitrogen-containing heterocyclic ring is not particularly limited as long as it has a heterocyclic skeleton as exemplified as the above-described nitrogen-containing heterocyclic ring. It may have a (covalent) bondable group. Examples of such a group include an amino group, a hydroxyl group, a methylene group, an ethylene group, and a carboxylic acid. Examples of such a compound containing a nitrogen-containing heterocyclic ring include the same compounds as the compounds exemplified as specific examples of the compound containing a nitrogen-containing heterocyclic ring in the first embodiment of the present invention.

The thermoplastic resin of the present invention has the above-mentioned properties.
It consists of a plastic polymer having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in a side chain and in one molecule. (I) a carbonyl group-containing group and (ii)
The heterocyclic amine-containing group is pendant to the side chain of the plastic polymer and has a chemically stable bond as described above. At this time, (i) the carbonyl group-containing group and (ii) the heterocyclic amine-containing group may be bonded to the polymer main chain as mutually independent side chains, or may be bonded to the main chain through different groups. Thereby, (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group may form one side chain. As described above, when one side chain is formed by (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group, not only the bond with the main chain but also the (i) carbonyl group-containing group (ii) it is also chemically bonded to the heterocyclic amine-containing group. This (i) carbonyl group-containing group and (ii) heterocyclic amine-containing group may be bonded via some kind of bond.

As an example of a thermoplastic resin in which (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group are independently bonded to a main chain of a plastic polymer, (i) a carbonyl group is added to a side chain of polypropylene. The structure of a thermoplastic resin (C) in which a carboxyl group as a containing group and (ii) 1,2,4-triazole as a heterocyclic amine-containing group are schematically shown below.

[0051]

Embedded image (Where x = 40-99.8, y = 0.1-30, z =
0.1 to 30. )

Further, by bonding to the main chain of the plastic polymer via different groups from each other, the heat which forms one side chain by (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group is formed. As an example of the plastic resin, the plastic polymer is polypropylene, (i) the carbonyl group-containing group is a group derived from maleic anhydride, and (ii) the heterocyclic amine is 3-amino-1,2,4-triazole. The structure of the thermoplastic resin (D), which is a group derived from the above, is schematically shown below. This thermoplastic resin (D) reacts a 3-amino-1,2,4-triazole with maleic anhydride to form a carboxyl group with an amide bonding group formed by ring opening of maleic anhydride. It has a branch in one side chain.

[0053]

Embedded image (Where x = 70 to 99.9 and y = 0.1 to 30)

Further, as another example of the thermoplastic resin in which (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group form one side chain, the plastic polymer is polypropylene, and (i) ) The structure of the thermoplastic resin (E) in which the carbonyl group-containing group is a group derived from maleic anhydride and (ii) the heterocyclic amine is a group derived from aminopyridine (γ-form) is schematically shown below. Show. This thermoplastic resin (E) has an amide bonding group formed by the ring-opening of maleic anhydride and a carboxyl group by the reaction of aminopyridine (γ-isomer) with maleic anhydride into one side chain. It has a branched shape.

[0055]

Embedded image (Where x = 70 to 99.9 and y = 0.1 to 30)

In the second embodiment of the present invention, among the above, (i) the carbonyl group-containing group includes succinic anhydride,
Cyclic acid anhydrides such as maleic anhydride, glutaric anhydride, and phthalic anhydride, particularly groups derived from maleic anhydride are preferred.

(Ii) The heterocyclic amine-containing group is preferably a heterocyclic ring having two or more nitrogen atoms in the skeleton, more preferably a heterocyclic ring having three or more nitrogen atoms, particularly preferably a group derived from a triazole ring. preferable. Specifically 3-
Amino-1,2,4-triazole, 3-hydroxy-
1,2,4-triazole, 3-aminomethyl-1,
2,4-triazole, 3-methylamino-1,2,4
Preferred are groups derived from -triazole, 3-methylol-1,2,4-triazole and the like.

Further, as shown above as the thermoplastic resins (D) and (E), (i) a heterocyclic amine-containing group is bonded to a main chain via a (i) carbonyl group-containing group to form one side chain. Is preferred. In a structure in which (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group form one side chain, (ii) a heterocyclic amine-containing group and a carbonyl group in the (i) carbonyl group-containing group It is preferable that at least one kind of bond of amide, amide, ester and imide, or at least one kind of bond and a carboxyl group are formed. In particular, the side chain formed by the bond between the cyclic acid anhydride and (ii) the heterocyclic amine-containing group has a carboxyl group together with an amide, ester or imide. Such bonds, amides,
As a specific example of a side chain having an ester or an imide,
In the first embodiment of the present invention, specific examples of the side chain having an amide, ester, or imide (amide: the following formulas (1) and (2), ester: the following formulas (3) and (4); A bond similar to the bond exemplified in the following formula (5) is exemplified. Specific examples are shown below.

[0059]

Embedded image

The heterocyclic amine represented by R is not particularly limited, but is exemplified by the heterocyclic amine represented by R in the formulas (1) to (5) in the first embodiment of the present invention. And the same groups as those described above.

When (i) the carbonyl group-containing group is a group derived from a cyclic acid anhydride and / or (ii) the heterocyclic amine-containing group is a group derived from a triazole compound, these groups are Those independently bonded to the main chain are also preferred.

The thermoplastic resin of the present invention as described above can be produced by a method having the above-mentioned structure having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in the side chain of the plastic polymer. Is not particularly limited. For example, during the production of a plastic polymer, a monomer capable of forming the main chain of the polymer and a copolymerizable monomer capable of introducing the above group are copolymerized, and (i) a carbonyl group-containing group and (ii) A thermoplastic resin having a structure having a cyclic amine-containing group may be directly produced, or a main chain (plastic polymer) is formed in advance by polymerization or the like, and then (i)
It may be graft-modified with a compound capable of introducing a carbonyl group-containing group and (ii) a heterocyclic amine-containing group.

Among the thermoplastic resins of the present invention, those having both (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in one side chain include, for example, (i) a carbonyl group-containing group. Group-modified plastic polymer, (i
It can be obtained by reacting (i) a compound capable of introducing a heterocyclic amine-containing group and bonding (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group. (i) The modified plastic polymer having a carbonyl group-containing group is, for example, a toluene solution containing an α-olefin such as polypropylene and mercaptoacetic acid is stirred at room temperature under a nitrogen atmosphere for 1 hour, and the reaction mixture is dissolved in methanol. It can be obtained by precipitating and drying under reduced pressure.

Further, (i) a carbonyl group-containing group and (i)
i) Compounds capable of introducing a heterocyclic amine-containing group may be bonded to each other, and then bonded to a side chain of a plastic polymer. In each of the above-mentioned production methods, whether each group of the side chain of the plastic polymer is independently bonded or bonded to each other can be confirmed by conventional analysis means such as an NMR spectrum. it can.

In the second embodiment of the present invention, among the above, the groups of (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group are added to the side chain of the preformed plastic polymer (main chain). It is preferable to bond, in particular, a plastic polymer having a cyclic acid anhydride group in a side chain and a heterocyclic amine-containing compound at a temperature at which the heterocyclic amine-containing compound can chemically bond to the cyclic acid anhydride group. It is preferred to react below. By this reaction, the acid anhydride may be opened. The temperature at which the heterocyclic amine-containing compound can chemically bond varies depending on the type of the compound, but is usually from room temperature to 1 ° C.
It is about 50 ° C.

As such a modified plastic polymer, a commercially available product can be used. For example, as a plastic polymer having a carbonyl group-containing group in the side chain, a maleic anhydride-modified product such as Eumex 1010 (manufactured by Sanyo Chemical Industries, Ltd.) can be used. Polyethylene, maleic anhydride-modified ethylene ethyl acrylate resin such as AR201 (manufactured by Du Pont-Mitsui Polychemicals Co., Ltd.), and ethylene acrylate ester / maleic anhydride such as Bondyne TX8030 (manufactured by Sumitomo Chemical Co., Ltd.) And the like.

More specifically, for example, in the reaction of maleic anhydride-modified polypropylene with 3-amino-1,2,4-triazole as a heterocyclic amine-containing compound,
When the reaction temperature is about 150 to 180 ° C., maleic anhydride and 3-amino-1,2,4-triazole are chemically bonded to form an amide bond as shown in the above formula (D). To form side chains. The reaction time is usually 0.5
About 2 hours. In the reaction of maleic anhydride-modified polypropylene with aminopyridine (γ-form) as a heterocyclic amine-containing compound, the reaction temperature is 150 to 1
At about 80 ° C., maleic anhydride and aminopyridine chemically bond to form a side chain having an amide bond as shown in the above formula (E). The reaction time is usually about 0.5 to 2 hours.

Next, self-crosslinking of the thermoplastic elastomer of the present invention and the thermoplastic resin of the present invention by hydrogen bonding will be described. The above-mentioned thermoplastic elastomer and thermoplastic resin of the present invention can be self-crosslinked by hydrogen bonding. At the time of hydrogen bonding, any of the (i) carbonyl group-containing group and (ii) heterocyclic amine-containing group in the side chain may act as a donor (proton donor) or an acceptor (proton acceptor). In the (ii) heterocyclic amine-containing group, the amine in the heterocyclic ring forms a hydrogen bond with the OH (donor) of the (i) carboxyl group-containing group as an acceptor. Such a (i) carbonyl group-containing group and (i
i) In the thermoplastic elastomer of the present invention having a heterocyclic amine-containing group in the side chain, the main chain of the elastomeric polymer may further participate in hydrogen bonding. Also like this
In the thermoplastic resin of the present invention having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in a side chain, the main chain of the plastic polymer may further participate in hydrogen bonding.

Specifically, (i) a carbonyl group-containing group,
(ii) In the thermoplastic elastomer and thermoplastic resin of the present invention having a heterocyclic amine-containing group, when a hydrogen bond is represented by (donor) -H ... (acceptor), at least O
Hydrogen bonds represented by —H—O, NH—O, OH—N, and NH—N are possible. Such a hydrogen bond may occur between molecules or within a molecule. For example, in the thermoplastic elastomer represented by the structure (B) and the thermoplastic resin represented by the structure (D) or (E), (ii) a carboxyl group of a heterocyclic amine-containing group and a carboxyl group of another side chain. It is presumed that the hydrogen bond.

The hydrogen bond of the thermoplastic elastomer and thermoplastic resin of the present invention having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group as described above is thermotropic and has a cross-linked structure when used at room temperature. Is formed, and when heated at a high temperature, it decrosslinks to show fluidity. Moreover, it is possible to repeatedly reproduce this crosslinking / decrosslinking. Therefore,
In the thermoplastic elastomer of the present invention, the rubber can be easily recycled by melting the rubber, which is practically impossible with a conventional chemically vulcanized rubber using a peroxide or the like. In addition, cold flow of the elastomeric polymer can be prevented by crosslinking. In the thermoplastic resin of the present invention, a crosslinked product obtained by subjecting a conventional organic peroxide to compounding, irradiation of radiation, or a crosslinking treatment by utilizing a silanol condensation reaction, and further, a carboxylic acid anhydride-modified olefin resin And a hydroxyl group-containing compound having no hydroxyl group bonded to a primary carbon atom and having two or more hydroxyl groups bonded to a secondary carbon atom, which is thermoreversible crosslinkable but has a particularly high crosslink dissociation temperature. (About 230 ° C.), it is possible to easily recycle the thermoplastic resin by melting, which is practically impossible with the olefin resin composition.

The thermoplastic elastomer of the present invention and the thermoplastic resin of the present invention have high crosslinkability by having a specific group, (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in a side chain. , The crosslinked product shows excellent heat resistance,
When used, a stable hydrogen bond can be maintained. That is, the hydrogen bond is maintained up to a high temperature that can be used. Specifically, for example, in a thermoplastic elastomer as shown in the above (B), the collapse temperature of hydrogen bond is 100 ° C.
As described above, hydrogen bonds are formed extremely stably at ordinary temperature. In the thermoplastic resin as shown in the above (D), the collapse temperature of the hydrogen bond is 110 to 150 ° C., the hydrogen bond is formed very stably at room temperature, and the hydrogen bond is maintained to a high temperature that can be used. ing. The effective formation of hydrogen bonds can be confirmed by observing the gelation phenomenon (increase in viscosity), and the collapse of hydrogen bonds is observed as a decrease in viscosity (increase in fluidity) or a decrease in hardness. .

The thermoplastic elastomer and thermoplastic resin of the present invention have the above-mentioned specific groups, (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group, so that they can form a hydrogen bond (crosslinking). The solid-liquid change between the curability and the decrease in viscosity at the time of hydrogen bond collapse (decrosslinking) at high temperature is large, and the recyclability is excellent. That is, it becomes extremely soft at the time of high-temperature heating exceeding the heat-resistant temperature, and when the temperature becomes about 130 ° C. or more, the fluidity becomes remarkably large, and recycling and use becomes easy. In particular, the thermoplastic resin of the present invention, when the plastic polymer that is the main chain of the thermoplastic resin has no side chain and is not modified, easily exhibits good melt fluidity at a temperature around the molding temperature. You. Therefore, reshaping,
Easy to recycle. In addition, it has a group capable of hydrogen bonding and has a feature of high adhesion to various adherends.

The effects of the thermoplastic elastomer and the thermoplastic resin of the present invention are exhibited by having (i) a carbonyl group-containing group and (ii) a heterocyclic amine-containing group in a side chain. In particular, it is considered that the heterocyclic amine is more easily hydrogen-bonded than an amine which does not form a ring structure.

In the thermoplastic elastomer according to the first aspect of the present invention, when (ii) a group derived from an amine compound other than the heterocyclic structure is used instead of the heterocyclic amine-containing group, hydrogen bonds are not formed. Weak, the thermoplastic elastomer remains liquid. Further, in the thermoplastic elastomer of the present invention, the inherent properties of the elastomer can be easily expressed as compared with a thermoplastic elastomer having a conventional thermoplastic resin as a constrained phase, but a specific group, (i) a carbonyl group-containing group, and (ii) a complex group. By appropriately selecting the crosslink density due to the cyclic amine-containing group, sufficient mechanical strength and rubber elasticity comparable to those of conventional vulcanized rubber made of a peroxide or the like can be obtained. The crosslink density varies depending on the purpose of use, application, molecular weight of the main chain, etc., and cannot be determined unconditionally. However, it is desirable that the crosslink density at the time of crosslinking be sufficient rubber elasticity and excellent mechanical strength. For example, when a conjugated diene rubber such as isoprene or butadiene is used as a main chain, a side chain group is used.
It is desirable to contain (i) and (ii) in an amount of about 0.1 to 30% by weight, preferably about 1 to 10% by weight, respectively. (i) and (ii) may be usually about 0.5 to 2 in a molar ratio of (i) / (ii).

In the thermoplastic resin according to the second embodiment of the present invention, when (ii) a group derived from an amine compound other than the heterocyclic structure is used instead of the heterocyclic amine-containing group, hydrogen bonding And has heat resistance and strength equal to or lower than that of a thermoplastic resin that has not been modified. In the thermoplastic resin of the present invention, a specific group, (i) a carbonyl group-containing group and (ii)
By appropriately selecting the crosslinking density and the like by the heterocyclic amine-containing group, it is possible to have excellent mechanical strength.
The crosslink density varies depending on the purpose of use, application, molecular weight of the main chain and the like, and cannot be determined unconditionally. However, it is desirable that the crosslink density exhibit excellent mechanical strength at the time of crosslinking. For example, when the main chain is polypropylene, the side chain group (i) the carbonyl group-containing group and (ii) the heterocyclic amine-containing group are each about 0.1 to 30 mol% based on the monomer unit,
Preferably, it is contained in an amount of about 1 to 10 mol%. (i) The carbonyl group-containing group and (ii) the heterocyclic amine-containing group may generally be (i) / (ii) in a molar ratio of about 0.5 to 2.

The thermoplastic elastomer of the present invention as described above can be used for various uses. For example, it can be used for various vulcanized rubber applications by utilizing rubber elasticity. In addition, when included in the hot melt adhesive, heat resistance and recyclability can be improved. As a rubber modifier, for example, as an anti-flow agent, when included in a resin or rubber that causes cold flow at room temperature,
Extrusion flow and cold flow can be prevented.

The thermoplastic resin of the present invention can be used for various applications, and can be used, for example, as a hot melt adhesive, a film, a fiber, various composites, a paint, a sealant, and the like. In particular, the thermoplastic resin of the present invention, a specific group in the side chain, (i) a carbonyl group-containing group, by introducing a (ii) heterocyclic amine-containing group, such as unmodified general polypropylene and the like. When used as an adhesive, the adhesiveness is improved as compared with a thermoplastic resin. Furthermore, by using the thermoplastic resin of the present invention, heat resistance and recyclability of a hot melt adhesive, a coating agent, and the like can be improved. In addition, as an anti-flow agent,
When included in a resin that causes cold flow at room temperature, flow during extrusion and cold flow can be prevented.

[0078]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

<In the side chain, (i) a carbonyl group-containing group and (i)
i) Synthesis of Hydrogen-Bonding Thermoplastic Elastomer Containing Elastomer Polymer Having Heterocyclic Amine-Containing Group> (Example 1) Maleic anhydride-modified liquid isoprene rubber (1) having a modification ratio of 4% by weight (Kuraray, LIR -410M) 1
61.08 g (0.0829 g in terms of maleic anhydride skeleton)
Mol), 3-amino-1,2,4-triazole
97 g (2) (0.0829 mol) was added, and the mixture was heated and stirred at 120 ° C. for 3 hours. After confirming that the solution became a homogeneous solution, the solution was allowed to stand overnight to obtain a gel-like reaction product (3). This reaction was confirmed by ¹ H-NMR spectrum measurement.

[0080]

Embedded image

FIG. 1 shows the ¹ H-NMR spectrum of maleic anhydride-modified liquid isoprene rubber (1), and FIG. 2 shows the ¹ H-NMR spectrum of 3-amino-1,2,4-triazole (2). FIG. 3 shows the ¹ H-NMR spectrum of the product (3). ^{The 1} H-NMR spectrum is 27
The measurement was performed at 0 MHz and room temperature. Gel reaction product (3)
Was measured by dissolving in CDCl ₃ .

As is apparent from the ¹ H-NMR spectrum (FIG. 3) of the 3-amino-1,2,4-triazole (2) (FIG. 2) and the reaction product (3), FIG. 3-
2H (δ = 1.9 ppm) of the amino group bonded to the
It disappears in FIG. 3 due to the bond with maleic anhydride, and δ =
An amide peak was found at 2.9 ppm, and a carboxyl group peak was found at δ = 8.3 ppm, confirming that maleic anhydride and 3-amino-1,2,4-triazole were bonded.

The hydrogen bonding property was evaluated by measuring the temperature (flow start temperature) indicating the fluidity of the thermoplastic elastomer (3) obtained in the examples. Table 1 shows the results. <Measurement of outflow start temperature> The outflow start temperature was measured using a Koka type flow tester. Capillary (D = 1m
m, length = 10 mm), the temperature was increased at 1 ° C./min under a pressure of 10 MPa, and the temperature at which the sample began to flow from the capillary was measured.

Example 2 In Example 1, 3-amino-1,2,4-triazole was used instead of 4-amino-
Except that pyridine (4) (0.0829 mol) was added,
The following reaction was carried out in the same manner as in Example 1 to obtain a gel-like reaction product (5). ^{The 1} H-NMR spectrum is 270
MHz at room temperature. The gel-like reaction product (5)
It was dissolved in CDCl ₃ and measured.

[0085]

Embedded image

¹ H-NM of 4-amino-pyridine (4)
FIG. 4 shows the ¹ H-NM of the reaction product (5).
The R spectrum is shown in FIG. In the same manner as in Example 1, 2H of the amino group bonded to the 2-position of pyridine in the ¹ H-NMR spectrum of 4-amino-pyridine (4) (δ = 1.1
ppm) disappears due to bonding with maleic anhydride, and δ
= 2.9 ppm and δ = 8.7p
A peak of a carboxyl group was confirmed in pm, and it was confirmed that maleic anhydride and 4-amino-pyridine were bonded. The hydrogen bonding property was evaluated by measuring the outflow starting temperature of the thermoplastic elastomer (5). Table 1 shows the results.

Example 3 A gel-like reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed to 150 ° C. and the mixture was heated and stirred at this temperature for 3 hours. A product (6) was obtained. Table 1 shows the outflow starting temperature of the gelled reactant (6).

Example 4 Example 4 was repeated, except that 4-hydroxy-pyridine (0.0829 mol) was added in place of 3-amino-1,2,4-triazole. To give a gelled reaction product (7). Table 1 shows the outflow starting temperature of the gelled reactant (7).

Example 5 The procedure of Example 1 was repeated, except that 4-methylol-pyridine (0.0829 mol) was used instead of 3-amino-1,2,4-triazole. To give a gelled reaction product (8). Table 1 shows the outflow starting temperature of the gelled reactant (8).

Comparative Example 1 Maleic anhydride-modified liquid isoprene rubber (1) (Kuraray, LIR) used in Example 1
Table 1 shows the outflow start temperature of −410 M).

Comparative Example 2 In Example 1, 3-amino-1,2,4-triazole was used in place of 3-amino-1,2,4-triazole.
The reaction was carried out in the same manner as in Example 1 except that the α-olefin of No. 8 was used. However, no gel-like reaction product was obtained, and the elastomer remained liquid.

[0092]

[Table 1]

<In the side chain, (i) a carbonyl group-containing group and (i)
i) Synthesis of Hydrogen-Bonding Thermoplastic Resin Consisting of a Plastic Polymer Having Heterocyclic Amine-Containing Group> (Example 6) Maleic anhydride-modified polypropylene having a modification ratio of 3.8 mol% (acid value: 52 mg / KOH) , Weight average molecular weight of about 30,000 (GPC method), manufactured by Sanyo Chemical Industries, Ltd.
Umex 1010) 100 parts by weight of 3-amino-
3.9 parts by weight of 1,2,4-triazole (0.5 equivalent to 1 equivalent of a group derived from maleic anhydride) was added, and the mixture was heated and mixed at 170 ° C. for 0.5 hour using a small tabletop kneader. . After confirming the uniformity, the desired thermoplastic resin was obtained. The hydrogen bonding property was evaluated by measuring the temperature (flow start temperature) indicating the fluidity of the obtained thermoplastic resin. The evaluation method is the same as the method in Examples 1 to 5. Further, the strand shape was observed. The breaking strength was measured using the obtained strand. Table 2 shows the results.

<Strand Shape> Under the above-mentioned conditions for measuring the outflow start temperature, the shape of the outflow strand was visually evaluated. In the table, ○ indicates that the surface of the strand was smooth, and x indicates that the strand was uneven. <Breaking strength> A tensile test was performed at a tensile speed of 50 mm / min using the outflowing strand under the conditions for measuring the outflow start temperature described above, and the breaking strength was measured.

Example 7 In Example 6, 7.8 parts by weight of a group derived from maleic anhydride was used instead of 3.9 parts by weight of 3-amino-1,2,4-triazole. Example 6 except that 1.0 equivalent was used for 1 equivalent).
The reaction was carried out in the same manner as described above to obtain the desired thermoplastic resin. Temperature indicating the fluidity of the obtained thermoplastic resin (outflow start temperature)
Was measured to evaluate the hydrogen bonding property. Also,
The strand shape and breaking strength were measured and evaluated. Table 2 shows the results.

Example 8 The procedure of Example 6 was repeated, except that the amount of 3-amino-1,2,4-triazole was changed to 3.9 parts by weight and 11.7 parts by weight (a group derived from maleic anhydride). The reaction was carried out in the same manner as in Example 6 except that 1.5 equivalents were used per 1 equivalent, to obtain a target thermoplastic resin. The hydrogen bonding property was evaluated by measuring the temperature (flow start temperature) indicating the fluidity of the obtained thermoplastic resin. In addition, the strand shape and the breaking strength were measured and evaluated. Table 2 shows the results.

Comparative Example 3 Table 2 shows the outflow starting temperatures of maleic anhydride-modified polypropylene (Umex 1010, manufactured by Sanyo Chemical Industries, Ltd.) used in Example 6.

Comparative Example 4 In Example 6, 2.8 parts by weight of hexanediol (group 1 derived from maleic anhydride) was used in place of 3-amino-1,2,4-triazole.
The reaction was carried out in the same manner as in Example 6 except that 0.5 equivalent was used for the equivalent. However, the obtained reaction product had a rough surface, and a strand that could be subjected to a tensile test was not obtained. Was.

Comparative Example 5 In Example 6, 5.5 parts by weight of hexanediol (group 1 derived from maleic anhydride) was used in place of 3-amino-1,2,4-triazole.
The reaction was carried out in the same manner as in Example 6, except that 1.0 equivalent was used for the equivalent, but a strand that could be subjected to a tensile test as in Comparative Example 5 was not obtained.

[0100] Compounds are in parts by weight. Figures in parentheses are equivalents. × ^* : ^{Indicates that} measurement was not possible.

[0101]

The thermoplastic elastomer of the present invention has a hydrogen-bonding group of a specific structure capable of self-crosslinking in the molecule, and can repeatedly reproduce crosslinking at room temperature and expression of fluidity by heating. . The thermoplastic elastomer can become a rubber elastic body by a hydrogen bond, and forms a hydrogen bond up to a high temperature, is excellent in heat resistance, and hardly causes cold flow. Also, when heated at a high temperature exceeding the heat resistance temperature, it exhibits remarkable fluidity due to decrosslinking, and can be molded and processed, and is easily recycled. This thermoplastic elastomer is novel and can be used for various applications. The thermoplastic resin of the present invention has a hydrogen-bonding group having a specific structure capable of self-crosslinking in the molecule, and can repeatedly reproduce crosslinking at room temperature and expression of fluidity by heating. The thermoplastic resin of the present invention forms hydrogen bonds up to high temperatures, has excellent breaking strength, excellent heat resistance, and is unlikely to be cold-flowed.
Also, when heated above the heat resistant temperature, it shows remarkable fluidity due to decrosslinking. The temperature at which remarkable fluidity is exhibited is a relatively low heating temperature, which is about the molding temperature of an unmodified olefin resin, and can be easily molded and processed, and is easily recycled. This thermoplastic resin is novel and can be used for various applications.

[Brief description of the drawings]

[Fig. 1] Maleic anhydride-modified liquid isoprene rubber ¹
1 H-NMR spectrum.

FIG. 2. ^{1 of} 3-amino-1,2,4-triazole
1 H-NMR spectrum.

FIG. 3 ¹ H-NMR of thermoplastic elastomer (3)
Spectrum.

FIG. 4 ¹ H-NMR spectrum of 4-amino-pyridine.

FIG. 5 ¹ H-NMR of thermoplastic elastomer (5)
Spectrum.

Claims (8)

[Claims] (1) a side chain comprising (i) a carbonyl group-containing group, and (ii)
A hydrogen bonding thermoplastic elastomer comprising an elastomeric polymer having a heterocyclic amine-containing group. 2. The method according to claim 1, wherein (i) the carbonyl group-containing group is an amide,
The thermoplastic elastomer according to claim 1, which is at least one of an ester, an imide, and a carboxyl. 3. The following formulas (1), (2), (3), (4),
3. The composition according to claim 1, which has at least one group of (5).
The thermoplastic elastomer according to 1. Embedded image 4. A reaction between an elastomeric polymer having a cyclic acid anhydride group in a side chain thereof and a heterocyclic amine-containing compound at a temperature at which the heterocyclic amine-containing compound can chemically bond to the cyclic acid anhydride group. A method for producing a thermoplastic elastomer, comprising obtaining the thermoplastic elastomer according to any one of claims 1 to 3. 5. A side chain comprising (i) a carbonyl group-containing group, and (ii)
A hydrogen bonding thermoplastic resin comprising a plastic polymer having a heterocyclic amine-containing group. 6. The thermoplastic resin according to claim 5, wherein (i) the carbonyl group-containing group is at least one of amide, ester, imide and carboxyl. 7. The formula (1), (2) according to claim 3,
7. The thermoplastic resin according to claim 5, which has at least one group of (3), (4) and (5). 8. A reaction between a plastic polymer having a cyclic acid anhydride group on a side chain thereof and a heterocyclic amine-containing compound at a temperature at which the heterocyclic amine-containing compound can chemically bond to the cyclic acid anhydride group. A method for producing a thermoplastic resin, wherein the thermoplastic resin according to any one of claims 5 to 7 is obtained.