JP2002080529A - Thermoplastic polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic polymer capable of exhibiting fluidity at molding temperatures of conventional thermoplastic resins, capable of forming a stable crosslinked structure at ordinary temperatures, having rubber elasticity, and capable of reversibly conducting crosslink-formation and crosslink- dissociation repeatedly in accordance with temperature changes. SOLUTION: This thermoplastic polymer has side chains composed of carbonyl-containing groups and five-membered heterocyclic ring-containing groups the each ring of which contains nitrogen, or has a main chain composed of an ethylene-propylene copolymer(EPM), ethylene-butene copolymer(EBM), ethylene-propylene-diene terpolymer(EPDM), butyl rubber or halogenated butyl rubber and side chains composed of the carbonyl-containing groups and heterocyclic ring-containing groups the each ring of which contains nitrogen.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic polymer capable of repeatedly reproducing crosslink formation and crosslink dissociation by a change in temperature, a method for producing the same, and a composition using the same.

[0002]

2. Description of the Related Art In recent years, reuse of used materials has been desired from the standpoint of environmental protection and resource saving. Vulcanized rubber has a stable three-dimensional network structure in which a polymer substance and a vulcanizing agent are covalently bonded, and exhibits extremely high strength, but is difficult to re-mold due to strong covalent cross-linking. On the other hand, thermoplastic elastomers
It utilizes physical crosslinking, and can be easily molded by heating and melting without requiring complicated vulcanization and molding steps including preliminary molding. A typical example of such a thermoplastic polymer includes a resin component and a rubber component, and at normal temperature, the microcrystalline resin component becomes a hard segment serving as a crosslinking point of a three-dimensional network structure, and a rubber component (soft segment). There is known a thermoplastic elastomer which prevents plastic deformation and softens or melts a resin component when the temperature rises. However, since such a thermoplastic elastomer contains a resin component, the rubber elasticity tends to decrease. Therefore, a material that can impart thermoplasticity without containing a resin component is required.

[0003] In order to address this problem, the present inventors have firstly developed an elastomer having a reactive site capable of forming a hydrogen bond,
It has been disclosed that an elastomer composition containing a reaction site of the elastomer and a compound having a reaction site capable of forming a hydrogen bond can repeat cross-link formation and cross-link dissociation by a temperature change utilizing a hydrogen bond ( JP-A-11-209524). The elastomer composition can exhibit sufficient melt fluidity at the molding temperature of a thermoplastic resin such as an unmodified olefin resin, and has excellent mechanical strength such as excellent breaking strength due to crosslinking at a low temperature. However, cross-link formation and cross-link dissociation (softening) can be repeatedly reproduced by a change in temperature. The thermoplastic elastomer having such properties has extremely high industrial utility value and environmental protection value, and can obtain higher crosslink strength, and does not change its physical properties even after repeated crosslink formation and crosslink dissociation. Materials with excellent recyclability are expected.

[0004]

DISCLOSURE OF THE INVENTION The present invention shows sufficient melt fluidity at ordinary molding temperature of thermoplastic resin, forms a stable crosslinked structure at ordinary temperature, has rubber elasticity, It is an object of the present invention to provide a thermoplastic polymer which can repeatedly reproduce curing and fluidization by change.

[0005]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have found that an elastomeric polymer is used as a main chain, and a carbonyl-containing group and a nitrogen-containing 5-membered cyclic hetero-chain are added to the side chain. By having a ring-containing group, the tensile strength at the time of cross-linking is very high, and it has rubber elasticity, can be easily softened at about 120 ° C, and repeatedly performs cross-link formation and cross-link dissociation. Also found that physical properties did not decrease and recyclability could be imparted. Also, the diene part is 5 mo as an elastomeric polymer.
up to 1% of an elastomeric polymer such as EPM, E
Using BM or EPDM, or butyl rubber or halogenated butyl rubber, and having a carbonyl-containing group and a nitrogen-containing heterocyclic-containing group at a specific ratio in the side chain, regardless of the number of ring members of the cyclic heterocyclic-containing group It has been found that excellent mechanical strength and recyclability can be imparted even if it is not a five-membered ring. The term "mol%" used herein indicates a value based on a monomer unit forming a polymer.

That is, a first aspect of the present invention is a thermoplastic polymer having a carbonyl-containing group and a nitrogen-containing 5-membered cyclic heterocyclic-containing group in a side chain. A second aspect of the present invention provides
A main chain of an elastomer having a diene portion of 5 mol% or less, a carbonyl-containing group and a nitrogen-containing heterocyclic-containing group in a side chain, and a side chain portion of 0.1 to 50 mol% based on 100 mol% of the main chain portion. Is a thermoplastic polymer having a ratio of The third embodiment of the present invention relates to an ethylene-propylene copolymer (EPM), an ethylene-butene copolymer (EB
M) or ethylene-propylene-diene copolymer (E
(PDM) as a main chain, a carbonyl-containing group and a nitrogen-containing heterocyclic group-containing group in a side chain, and a side chain portion in a ratio of 0.1 to 50 mol% to 100 mol% of the main chain portion. It is a polymer. In addition, a fourth aspect of the present invention,
A butyl rubber or a halogenated butyl rubber as a main chain, having a carbonyl-containing group and a nitrogen-containing heterocyclic group in a side chain,
0.1 to 100 mol% of the main chain portion
It is a thermoplastic polymer having a proportion of 50 mol%.
In the second, third and fourth aspects, the nitrogen-containing heterocyclic ring is preferably a 5-membered ring or a 6-membered ring. In the above first, second, third and fourth embodiments, the carbonyl-containing group is preferably at least one selected from amide, ester, imide and carboxyl groups.
Further, the side chain preferably has at least one of the formulas (1), (2) and (3) so as to bond to the main chain at the α-position or the β-position.

[0007]

Embedded image Here, R represents a nitrogen-containing 5-membered cyclic heterocyclic ring. Further, in the above first, second, third and fourth aspects, the thermoplastic polymer preferably has a glass transition point (Tg) of 25 ° C. or lower. Also, the present invention provides a method wherein the polymer having a cyclic acid anhydride group in a side chain and a nitrogen-containing 5-membered cyclic heterocyclic compound are chemically bonded to the cyclic acid anhydride group. A method for producing the thermoplastic polymer according to the first aspect, wherein the reaction is carried out at a temperature that is possible.
Further, in the method for producing a thermoplastic polymer according to the second, third, and fourth aspects, the nitrogen-containing heterocyclic compound is a polymer having a cyclic acid anhydride group in a side chain. With butyl rubber or halogenated butyl rubber at a temperature at which the nitrogen-containing heterocyclic compound can chemically bond with the cyclic anhydride group. The present invention also provides a rubber composition containing the thermoplastic polymer according to the first, second, third, and fourth aspects.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. <First Embodiment> The thermoplastic polymer according to the first embodiment of the present invention is characterized in that it has a carbonyl-containing group and a nitrogen-containing 5-membered cyclic heterocyclic-containing group in a side chain. The elastomeric polymer serving as the main chain of the thermoplastic polymer according to the first embodiment is a natural polymer or a synthetic polymer generally known as a rubber elastic material for vulcanization (crosslinking, curing). Specific examples of such an elastomeric polymer include natural rubber, isoprene rubber, butadiene rubber, 1,
Diene rubbers such as 2-butadiene rubber, styrene-butadiene rubber, nitrile rubber, chloroprene rubber, butyl rubber, ethylene-propylene rubber (EPDM, EP
M), ethylene-butene rubber (EBM), chlorosulfonated polyethylene, olefin rubber such as acrylic rubber and fluororubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, urethane rubber and the like. Further, it may be a thermoplastic elastomer containing a resin component, for example, a polystyrene-based elastomeric polymer (SBS, SIS, SE
BS), a polyolefin-based elastomeric polymer, a polyvinyl chloride-based elastomeric polymer, a polyurethane-based elastomeric polymer, a polyester-based elastomeric polymer or a polyamide-based elastomeric polymer.

The elastomeric polymer as described above is:
It may be either liquid or solid. The molecular weight is not particularly limited and can be appropriately selected depending on the purpose of use, crosslink density, and the like. However, convenience in producing a thermoplastic polymer, and fluidity during heating (decrosslinking) of a thermoplastic polymer It is preferably a liquid rubber. Further, it is preferable that the molecular weight is such as to show a liquid, for example, a diene rubber such as isoprene rubber and butadiene rubber has a weight average molecular weight of preferably from 1,000 to 100,000, and particularly preferably from about 1,000 to 50,000. preferable. On the other hand, when importance is placed on strength, solid rubber is particularly preferable. For example, in a diene rubber such as isoprene rubber and butadiene rubber, the weight average molecular weight is preferably 100,000 to 2,000,000, and 500,000 to 1,500,000 is preferable. Particularly preferred.

The thermoplastic polymer of the present invention is obtained by introducing a carbonyl-containing group and a nitrogen-containing 5-membered cyclic heterocyclic-containing group into the side chain of the above-mentioned elastomeric polymer.
Examples of the carbonyl-containing group include amide, ester, imide and carboxyl groups.
The compound into which such a group can be introduced is not particularly limited, and examples thereof include carboxylic acid compounds and derivatives thereof. 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 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 , Glutaric acid ester, aliphatic ester such as ethyl acetate, phthalic acid ester, isophthalic acid ester, terephthalic acid ester, ethyl-m-aminobenzoate, methyl-
Aromatic esters such as p-hydroxybenzoate, ketones such as quinone, anthraquinone and naphthoquinone, glycine, tricine, bicine, alanine, valine, leucine, serine, threonine, lysine, aspartic acid, glutamic acid, cysteine, methionine, proline, N-
Amino acids such as (p-aminobenzoyl) -β-alanine, maleamide, maleamic acid (malemonoamide), succinic monoamide, 5-hydroxyvaleramide, N-acetylethanolamine, N, N′-hexamethylenebis ( Acetamide), malonamide, cycloserine, 4-acetamidophenol, amides such as p-acetamidobenzoic acid, and imides such as maleimide and succinimide. Among these, the carbonyl-containing group of the present invention is preferably derived from cyclic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, and phthalic anhydride, and particularly preferably derived from maleic anhydride. Is more preferred.

The nitrogen-containing 5-membered cyclic heterocyclic-containing group according to the first embodiment of the present invention is not particularly limited as long as it contains a nitrogen atom in the heterocyclic ring. It may have another hetero atom, for example, a sulfur atom, an oxygen atom, a phosphorus atom and the like. The heterocyclic ring may have a substituent. Examples of the substituent include an alkyl group such as a methyl group, an ethyl group, an (iso) propyl group, and a hexyl group, a methoxy group, an ethoxy group, and an (iso) propoxy group. Such as alkoxy groups, fluorine, iodine, groups consisting of halogen atoms such as chlorine, cyano groups, amino groups, aromatic hydrocarbon groups, ester groups, ether groups, acyl groups, thioether groups, and the like. There may be.
These substitution positions are not particularly limited, and the number of substituents is not limited. The heterocyclic ring may or may not have aromaticity, but is preferably aromatic because it increases the tensile strength at the time of crosslinking. Also,
The nitrogen-containing five-membered heterocyclic ring-containing group may be bonded by directly covalently bonding the nitrogen-containing five-membered heterocyclic ring to the main chain. And a chemical bond (covalent bond) to the main chain via the bonding group.
Preferably. Preferred examples of such a bonding group include an amide group, a methylene group, an ethylene group, and an ester group. Among these, the amide group is preferable because it forms a complementary hydrogen bond. The bonding position between the nitrogen-containing 5-membered heterocyclic ring and the bonding group is not particularly limited, and the heterocyclic ring and the bonding group may be bonded to each other,
The substituent of the heterocyclic ring and the bonding group may be bonded. When bonded at the 3- and 4-positions of the nitrogen-containing 5-membered heterocyclic ring,
The one bonded at the 2-position forms a hydrogen bond in the molecule, whereas the one bonded in the molecule forms a hydrogen bond. Position 3 is particularly preferred. The number of nitrogen atoms in the heterocyclic ring is preferably 2 or more, and particularly preferably 3. In particular, it is preferable that the intervening group with the main chain is an amide group and is bonded at the 3- or 4-position of the nitrogen-containing 5-membered cyclic heterocyclic ring having 3 nitrogen atoms.

As typical examples of the nitrogen-containing 5-membered cyclic heterocycle of the present invention, the following compounds are preferably exemplified. These may have various substituents, or may be hydrogenated or eliminated.

[0014]

Embedded image Further, a benzene ring condensed to the monocyclic heterocycle,
Those obtained by condensing the above-mentioned monocyclic heterocycles can also be used, and examples thereof include the following condensed rings.

[0015]

Embedded image

The nitrogen-containing 5-membered cyclic heterocyclic-containing group of the present invention is
A nitrogen-containing 5-membered cyclic heterocyclic ring containing a nitrogen-containing 5-membered heterocyclic ring and a group capable of covalently bonding to an elastomeric polymer constituting a main chain;
Introduced by membered heterocyclic compounds. Such groups include, for example, amino groups, hydroxyl groups, carboxyl groups,
A thiol group or a sulfide group;

The thermoplastic polymer according to the first aspect of the present invention is a thermoplastic polymer having a carbonyl-containing group and a nitrogen-containing 5-membered cyclic-containing group in the side chain as described above.
These groups are covalently bonded to the side chain of the elastomeric polymer, and may be bonded to the main chain as side chains independent of each other.
It may have a membered cyclic-containing group in the same side chain in a branched manner. In particular, from the viewpoint of synthesis, it is preferable to have them in the same side chain, for example, the following formulas (1), (2) and (3)
Having the structure shown in the following.

[0018]

Embedded image Here, R represents a nitrogen-containing 5-membered heterocyclic ring, and examples thereof include the 5-membered heterocyclic rings exemplified above. Formulas (1) to (3) above
Is preferably bonded to the above-mentioned elastomeric polymer at the α-position or the β-position in the formula.

The side chain composed of these groups preferably has a ratio of 0.1 to 50 mol%, preferably 1 to 15 mol%, based on 100 mol% of the main chain. Is more preferable. When the main chain portion is isoprene rubber, the ratio is preferably about 0.1 to 35 mol% of the monomer into which the side chain portion is introduced per unit mole of isoprene monomer. Within this range, the interaction between these side chains is well balanced between molecules or within the molecule, and the thermoplastic polymer has a very high tensile strength at the time of crosslinking and has rubber elasticity. . When the thermoplastic polymer is heated to 120 ° C. or higher, a three-dimensional crosslinked structure is dissociated, and fluidity is imparted. It is considered that the interaction between side chains is weakened. If the ratio of the side chain portion to the main chain portion is 100 mol% is less than 0.1 mol%, the strength at the time of crosslinking is not sufficient, and if it exceeds 50 mol%, rubber elasticity is lost, which is not preferable. Carbonyl-containing groups and nitrogen-containing 5
Although the ratio with the member-containing group is not particularly limited, it is preferable that the ratio is 2: 1 because a complementary interaction is easily formed. The glass transition point of the thermoplastic polymer according to the first aspect of the present invention is preferably 25 ° C. or lower when desired rubber elasticity is desired at room temperature.

The method for producing the thermoplastic polymer according to the first aspect of the present invention is not particularly limited, and it can be synthesized by an ordinary method. Among the thermoplastic polymers according to the first aspect of the present invention, the carbonyl-containing group and the nitrogen-containing 5
The one having a membered heterocyclic ring-containing group on the same side chain can be obtained, for example, by reacting an elastomeric polymer modified with a carbonyl-containing group with a compound capable of introducing a nitrogen-containing 5-membered heterocyclic ring-containing group. It can be obtained by covalently bonding the containing group and the nitrogen-containing 5-membered cyclic heterocyclic-containing group. An elastomeric polymer modified with a carbonyl-containing group can be obtained, for example, by adding a diene-based rubber such as butadiene rubber and a toluene solution containing maleic anhydride or mercaptoacetic acid at room temperature or under heating in a nitrogen atmosphere.
It is obtained by stirring for an hour, precipitating the reaction mixture in methanol, and drying under reduced pressure. As such a modified elastomeric polymer, commercially available products can also be used, for example, LIR-403A (manufactured by Kuraray Co., Ltd.), LIR
Maleic anhydride-modified isoprene rubber such as -410A (produced by Kuraray), carboxyl-modified isoprene rubber such as LIR-410 (manufactured by Kuraray), Clinac 11
Carboxyl-modified nitrile rubber such as 0, -221, -231 (manufactured by Policer), CPIB (manufactured by Nisseki Chemical),
Examples thereof include carboxyl-modified polybutenes such as HRPIB (produced by Nisseki Chemical Lab), Nuclell (manufactured by Mitsui DuPont Polychemicals), and Yucalon (manufactured by Mitsubishi Chemical Corporation). Alternatively, the compounds capable of introducing the carbonyl-containing group and the nitrogen-containing five-membered cyclic heterocyclic-containing group may be previously bonded to each other, and then bonded to the side chain of the elastomeric polymer.

In the case where a thermoplastic polymer having a carbonyl-containing group and a nitrogen-containing 5-membered cyclic heterocyclic-containing group in the side chain independently of each other is synthesized, when the elastomeric polymer is produced, the polymer The above-mentioned thermoplastic polymer may be directly produced by copolymerizing a monomer capable of forming a chain and a copolymerizable monomer capable of introducing the above-mentioned group, and the main chain (elastomeric polymer) is formed in advance by polymerization or the like. Then, it may be graft-modified with a compound capable of introducing the above group. In each of the above-mentioned production methods, whether each group of the side chain of the elastomeric polymer is independently bonded or bonded to each other is determined by NMR,
It can be confirmed by a commonly used analysis means such as an IR spectrum.

In the first aspect of the present invention, it is preferable that a carbonyl-containing group and a nitrogen-containing 5-membered cyclic heterocyclic-containing group are bonded to the same side chain of the preformed elastomeric polymer. In particular, a modified elastomeric polymer having a cyclic acid anhydride in the side chain and a nitrogen-containing 5-membered cyclic heterocyclic compound are combined with a nitrogen-containing 5-membered cyclic heterocyclic compound by a chemical bond (for example, a covalent bond, Ionic bond)
It is preferable to combine them by reacting at a possible temperature. (The acid anhydride is ring-opened by this reaction.) The temperature at which the nitrogen-containing 5-membered cyclic heterocyclic compound can chemically bond to the cyclic acid anhydride group varies depending on the type of the compound, but is usually from room temperature to about 200 ° C. is there. The reaction time is usually about 3 to 5 hours.

Next, a second embodiment of the present invention will be described. In a second aspect of the present invention, an elastomer having a diene moiety of 5 mol% or less has a main chain, a carbonyl-containing group and a nitrogen-containing heterocyclic-containing group in a side chain, and a main chain portion of 100 mol
% Is a thermoplastic polymer having a side chain portion in a ratio of 0.1 to 50 mol%. 5 mol of diene moiety
% Of the thermoplastic polymer according to the second aspect of the present invention, which has an elastomer of not more than 10% by weight, has the above-mentioned specific side chain. A crosslinked product of a thermoplastic polymer having high mechanical strength can be obtained. In particular, tensile strength, breaking strength, and breaking elongation are high. This is a remarkable improvement as compared with the case where an elastomer having a large content of a diene moiety such as isoprene is used as the main chain, and has not been conventionally expected. That is, in the second embodiment of the present invention, the side chain of the elastomer has a diene moiety of 5 mol% or less, the carbonyl-containing group and the nitrogen-containing heterocycle-containing group being 100 mol% of the main chain part, and the side chain part being 0.1 mol%. Introduced at a rate of 1 to 50 mol%, the breaking strength,
Provided is a method for increasing elongation at break and imparting thermoreversible plasticity to an elastomer having a diene portion of 5 mol% or less. As a typical example of an elastomer having a diene portion of 5 mol% or less, an ethylene-propylene copolymer (EPM), an ethylene-butene copolymer (EBM), or an ethylene-propylene-diene copolymer (EPDM) is used as a main chain. In the following, the case where the main chain is butyl rubber or halogenated butyl rubber will be described, but the elastomer of the second embodiment of the present invention is not limited to these main chains. For example, in addition to these, acrylic rubber, multi-flow rubber, silicone rubber, and urethane rubber may be used. Hereinafter, the third and fourth embodiments will be described as examples of the second embodiment of the present invention. The specific description of the second aspect of the present invention is the same as that described in the following third and fourth aspects.

The thermoplastic polymer according to the third aspect of the present invention mainly comprises an ethylene-propylene copolymer (EPM), an ethylene-butene copolymer (EBM) or an ethylene-propylene-diene copolymer (EPDM). It is characterized by having a carbonyl-containing group and a nitrogen-containing heterocyclic-containing group in a side chain. As the diene, dicyclopentadiene, 5-ethylidene-2-norbornene, 1,1,
4-hexadiene or the like is used. In addition, 1-butene may be used in addition to propylene. When EPM or EPDM is used as the main chain, the tensile strength at the time of crosslinking becomes higher as compared with the case where the other polymer mentioned in the first embodiment is used. EPM and EPDM may be liquid or solid, and the molecular weight is not particularly limited, but solid is preferred because of its high physical properties. EPM and EPDM have a weight average molecular weight of 1,000 to 2,000,000.
0, preferably about 100,000 to 1,000,000.

The thermoplastic polymer according to the third aspect of the present invention is obtained by introducing a carbonyl-containing group and a nitrogen-containing heterocyclic-containing group into a side chain of the main chain constituted by the above-mentioned EPM, EBM or EPDM. It is. That is, the third embodiment of the present invention provides a polymer composed of EPM, EBM or EPDM, wherein a carbonyl-containing group and a nitrogen-containing heterocyclic-containing group are added to a side chain of a polymer composed of 100 mol% of a main chain portion and a side chain portion. The present invention provides a method of increasing the breaking strength and the breaking elongation by introducing the compound in a proportion of 0.1 to 50 mol% to impart thermoreversible plasticity to the EPM, EBM or EPDM. As the carbonyl-containing group according to the third embodiment, the same ones as exemplified in the first embodiment can be used, and the same applies to compounds into which the carbonyl group can be introduced, and preferable examples thereof. In the third aspect of the present invention, the main chain skeleton allows the nitrogen-containing heterocyclic ring contained in the nitrogen-containing heterocyclic group-containing group to be not limited to a 5-membered ring, but is not limited to a 5-membered ring. The strength at the time of crosslinking is sufficiently high,
A wide variety of 8-membered rings and condensed rings can be used.

The nitrogen-containing heterocyclic ring used in the third embodiment is
There is no particular limitation as long as the heterocyclic ring contains a nitrogen atom in addition to the 5-membered ring, and the heterocyclic ring contains other heteroatoms other than a nitrogen atom such as a sulfur atom, an oxygen atom, and a phosphorus atom. Is also good. For example, the nitrogen-containing 5-membered cyclic heterocyclic ring and the nitrogen-containing 6-membered cyclic heterocyclic ring exemplified in the first embodiment, pyrrololine, pyrrolidone, oxindole (2-oxindole), indoxyl (3-oxindole), dioxy Indole, isatin, indolyl, phthalimidine, β-isoindigo, monoporphyrin, diporphyrin, triporphyrin, azaporphyrin, phthalocyanine, hemoglobin, uroporphyrin, chlorophyll, phyloerythrin, imidazole, pyrazole, triazole, tetrazole, benzimidazole, benzopyrazole , Benzotriazole, imidazoline, imidazolone, imidazolidone, hydantoin, pyrazoline, pyrazolone, pyrazolidone, indazole, pyridoindole, purine, cinnoline, Roll, pyrroline, indole, indoline, oxylindole, carbazole, phenothiazine, indolenine, isoindole, oxazoles, thiazoles, isoxazoles, isothiazole, oxadiazole, thiadiazole, oxatriazole, thiatriazole, phenanthroline, oxazine, Benzoxazine, phthalazine, pteridine, pyrazine, phenazine, tetrazine, benzoxazole, benzisoxazole, anthranil, benzothiazole, benzofurazan, pyridine, quinoline, isoquinoline, acridine, phenanthridine, anthrazolin, naphthyridine, thiazine,
Pyridazine, pyrimidine, quinazoline, quinoxaline,
Triazine, histidine, triazolidine, melamine,
Adenine, guanine, thymine, cytosine and the like can be mentioned. The nitrogen-containing heterocyclic ring may include another hetero atom in the ring. The heterocyclic ring may have a substituent. Examples of the substituent include a methyl group, an ethyl group, an (iso) propyl group, an alkyl group such as a hexyl group, a methoxy group,
Alkoxy groups such as ethoxy group and (iso) propoxy group, groups consisting of halogen atoms such as fluorine, iodine and chlorine, cyano groups, amino groups, aromatic hydrocarbon groups, ester groups, ether groups, acyl groups, thioether groups, etc. And a combination thereof. These substitution positions are not particularly limited, and the number of substituents is not limited. The heterocyclic ring may or may not have aromaticity, but preferably has aromaticity as in the first embodiment. The use of a nitrogen-containing 5-membered heterocyclic ring has the advantage of exhibiting a strong hydrogen bond. Further, in the nitrogen-containing heterocyclic group-containing group according to the third aspect of the present invention, the heterocyclic ring may be directly bonded to the main chain, but the heterocyclic ring may be bonded to EPM, EBM or EPDM constituting the main chain. It is preferable to have a bonding group between them. As the bonding group, those exemplified in the first embodiment are preferable, and examples thereof include an amide group, a methylene group, an ethylene group, and an ester group. Among these, an amide group is particularly preferable because a complementary hydrogen bond is formed. . Note that, similarly to the first embodiment, the bonding position between the heterocyclic ring and the bonding group is not particularly limited, and the heterocyclic ring and the bonding group may be bonded to each other, and The bonding group may be bonded.

The nitrogen-containing heterocyclic group is introduced by a nitrogen-containing heterocyclic compound containing a nitrogen-containing heterocyclic ring and a group capable of covalently bonding to EPM, EBM or EPDM constituting the main chain. Examples of the group capable of covalently bonding to the elastomeric polymer constituting the main chain include an amino group, a hydroxyl group,
Examples thereof include a carboxyl group, a thiol group and a sulfide group. The nitrogen-containing heterocyclic ring is the nitrogen-containing 5 as exemplified above.
A membered heterocyclic ring is preferable because the obtained thermoplastic polymer has a particularly high tensile strength at the time of crosslinking. Nitrogen containing 5
When bonded at the 3- and 4-positions of the membered heterocyclic ring, those bonded at the 2-position are hydrogen-bonded in the molecule, whereas hydrogen-bonded between the molecules, so that the cured product has high mechanical properties and is therefore preferable. Position 3 is particularly preferred. The number of nitrogen atoms in the heterocyclic ring is preferably 2 or more, and particularly preferably 3. In particular, it is preferable that the intervening group with the main chain is an amide group and is bonded at the 3- or 4-position of the nitrogen-containing 5-membered cyclic heterocyclic ring having 3 nitrogen atoms.

In the thermoplastic polymer according to the third aspect of the present invention, the carbonyl-containing group and the nitrogen-containing heterocyclic-containing group may be bonded to the main chain as independent side chains, respectively. It may have a branched shape in the chain. Also in the third embodiment, it is preferable to have them in the same side chain because they can be easily synthesized. In particular, as shown in the first embodiment, the above formulas (1), (2) and (3) It is preferable to have the structure shown in FIG. Here, R represents a nitrogen-containing heterocyclic ring, and the nitrogen-containing heterocyclic ring exemplified above is preferably exemplified,
Among them, a 5-membered nitrogen-containing heterocyclic ring,
It is more preferable because it has particularly excellent strength characteristics. The binding site is preferably at the α or β position.

In the thermoplastic polymer according to the third aspect of the present invention having such a constitution, the side chain (moiety) comprising the carbonyl-containing group and the nitrogen-containing heterocyclic group is EP
0.1 to 50 mol%, preferably 1 to 20 mol, based on 100 mol% of the main chain portion composed of M or EPDM
%. Within this range, a thermoplastic elastomer having excellent balance of the interaction between these side chains between molecules or within the molecule, having a very stable crosslinked structure, and having rubber elasticity can be obtained. When the thermoplastic polymer is heated to 120 ° C. or higher, the crosslinked structure is broken and fluidity is imparted. Main chain part 100
If the ratio of the side chain portion to the mol% is less than 0.1 part by weight, the tensile strength at the time of crosslinking is not sufficient, and if it exceeds 50 mol%, rubber elasticity is lost, which is not preferable. The ratio between the carbonyl-containing group and the nitrogen-containing heterocyclic group is not particularly limited, but is preferably 2: 1 from the viewpoint of complementary hydrogen bonding. Further, also in the thermoplastic polymer according to the third aspect of the present invention, the glass transition point (Tg) is preferably 25 ° C. or lower in order to obtain desired rubber elasticity.

The method for producing the thermoplastic polymer according to the third aspect of the present invention is not particularly limited, and can be synthesized in the same manner as in the method described in the first aspect. That is, those having a carbonyl-containing group and a nitrogen-containing heterocyclic-containing group on the same side chain include, for example, E modified by a carbonyl-containing group.
It is obtained by reacting PM, EBM or EPDM with a compound capable of introducing a nitrogen-containing heterocyclic group-containing group. Here, EPM, EBM or EPDM modified with a carbonyl-containing group can be obtained by reacting with a toluene solution containing mercaptoacetic acid as in the first embodiment. As the modified EPM, EBM or EPDM, commercially available products can also be used, and examples thereof include Tuffmer MP0610 and MP0620 manufactured by Mitsui Chemicals, Inc.
Further, after the compounds capable of introducing a carbonyl-containing group and a nitrogen-containing heterocyclic group-containing group are previously bonded to each other, EPM, EBM
Alternatively, it can be combined with EPDM. Further, when a thermoplastic polymer having a carbonyl-containing group and a nitrogen-containing heterocyclic-containing group in a side chain independently of each other is synthesized, the thermoplastic polymer can be produced in the same manner as in the first embodiment.

In the third embodiment of the present invention, the EPM,
It is preferable that the carbonyl-containing group and the nitrogen-containing heterocyclic-containing group are bonded in the same side chain of EBM or EPDM, and in particular, EPM or EP having a cyclic acid anhydride in the side chain.
It is preferable that DM and the nitrogen-containing heterocyclic compound are bonded by reacting at a temperature at which the nitrogen-containing heterocyclic compound can chemically bond to the cyclic acid anhydride group. The temperature at which the nitrogen-containing heterocyclic compound can chemically bond to the cyclic acid anhydride group is usually from room temperature to about 150 ° C., and the reaction time is usually about 3 to 5 hours.

Next, a fourth embodiment of the present invention will be described. The thermoplastic polymer according to the fourth aspect of the present invention,
A butyl rubber or a halogenated butyl rubber as a main chain, having a carbonyl-containing group and a nitrogen-containing heterocyclic group in a side chain,
0.1 to 100 mol% of the main chain portion
It is a thermoplastic polymer having a proportion of 50 mol%.
Butyl rubber is a copolymer of isobutylene and a small amount of isoprene. Halogenated butyl rubber is obtained by halogenating the isoprene portion of butyl rubber, and chlorinated butyl rubber and brominated butyl rubber are commercially available. As special butyl rubber, there are partially cross-linked butyl rubber, liquid butyl rubber, butyl rubber containing a star-branched high molecular weight substance, and the like, and any butyl rubber or halogenated butyl rubber used in the third embodiment of the present invention is used. You can also. The butyl rubber or halogenated butyl rubber may be liquid or solid, and its molecular weight is not particularly limited, but solid is preferable because of high physical properties. Weight average molecular weight of 1,000 to 2,000,000
0, preferably about 100,000 to 1,000,000.

The carbonyl-containing group and the nitrogen-containing heterocyclic ring used in the fourth embodiment are the same as those already explained in the second embodiment. Further, as in the third embodiment, the structure of the side chain is represented by the formulas (1), (2), and (3) shown in the first and second embodiments.
It is preferable to have the structure shown in (3). Further, the nitrogen-containing heterocyclic ring may be a 5-membered heterocyclic ring,
It is preferable because the obtained thermoplastic polymer has a particularly high tensile strength at the time of crosslinking. In addition, 3, 4 of the nitrogen-containing 5-membered cyclic heterocyclic ring
When bonded at the position, the one bonded at the second position is hydrogen-bonded in the molecule, whereas the one bonded at the position is hydrogen-bonded between the molecules. Position 3 is particularly preferred. The number of nitrogen atoms in the heterocyclic ring is preferably 2 or more, and particularly preferably 3. In particular, it is preferable that the intervening group with the main chain is an amide group and is bonded at the 3- or 4-position of the nitrogen-containing 5-membered cyclic heterocyclic ring having 3 nitrogen atoms.

In the thermoplastic polymer according to the fourth embodiment of the present invention, the side chain portion (moiety) comprising the carbonyl-containing group and the nitrogen-containing heterocyclic group is 100 mol% of the main chain portion comprising butyl rubber or halogenated butyl rubber. 0.1 to 50 mol%, preferably 1 to 20 mol
%. Within this range, the interaction between these side chains within the molecule or within the molecule is excellent, and the crosslinked structure is very stable, and the vulcanized butyl rubber or the vulcanized butyl rubber having no side chain used in the present invention is used. A thermoplastic polymer exhibiting higher breaking strength and breaking elongation than halogenated butyl rubber is obtained. That is, in the fourth embodiment of the present invention, the side chain of the butyl rubber or the halogenated butyl rubber has a carbonyl-containing group and a nitrogen-containing heterocyclic group-containing group in an amount of 0.1 to 50 m with respect to 100 mol% of the main chain.
ol%, to increase the breaking strength and breaking elongation,
Provided is a method for imparting thermoreversible plasticity to butyl rubber or halogenated butyl rubber. When the thermoplastic polymer is heated to 120 ° C. or higher, the crosslinked structure is broken and fluidity is imparted. If the ratio of the side chain portion to the main chain portion is 100 mol% is less than 0.1 mol%, the strength at the time of crosslinking is insufficient, and if it exceeds 50 mol%, rubber elasticity is lost, which is not preferable. The ratio between the carbonyl-containing group and the nitrogen-containing heterocyclic group is not particularly limited, but is preferably 2: 1 from the viewpoint of complementary hydrogen bonding. Further, also in the thermoplastic polymer according to the third aspect of the present invention, the glass transition point (Tg) is preferably 25 ° C. or lower in order to obtain desired rubber elasticity.

The method for producing the thermoplastic polymer according to the fourth aspect of the present invention is not particularly limited, and can be synthesized in the same manner as in the method described in the second aspect. That is, those having a carbonyl-containing group and a nitrogen-containing heterocycle-containing group on the same side chain can be obtained, for example, by reacting a butyl rubber or a halogenated butyl rubber modified with a carbonyl-containing group with a compound capable of introducing a nitrogen-containing heterocycle-containing group. To be obtained. Further, other manufacturing methods can be used in the same manner as described in the second and third embodiments.

The thermoplastic polymer according to the first, second, third, and fourth embodiments obtained as described above has a carbonyl group and a nitrogen-containing heterocyclic group-containing group in the side chain.
Once crosslinked, recyclability can be imparted to the elastomeric polymer that is the main chain component that could not be reshaped. These groups can interact between molecules or within a molecule, and a three-dimensional crosslinked structure can be formed by this intermolecular interaction. Below 120 ° C., the crosslinked structure is kept very stable and has rubber elasticity. However, when the temperature is raised to 120 ° C. or higher, the crosslinked structure is dissociated, and comes to exhibit fluidity. This is considered to be due to the fact that the molecular movement is so active that the hydrogen bonding site collapses and the crosslinked structure cannot be maintained. Thus, the thermoplastic polymer of the present invention has thermoplasticity, and the tensile strength at the time of crosslinking is particularly high when the nitrogen-containing heterocyclic group is a 5-membered ring. Even if the nitrogen-containing heterocyclic group is not a 5-membered ring, the main chain may be EPM, EBM or EPD.
When M is used, a thermoplastic polymer having a similarly high tensile strength can be obtained, and when butyl rubber or halogenated butyl rubber is used for the main chain, butyl rubber having a breaking strength and breaking elongation having no specific side chain is used. Or higher than vulcanizates of halogenated butyl rubber. As described above, the thermoplastic polymers according to the first, second, third, and fourth aspects of the present invention have a very stable crosslinked structure and have rubber elasticity. The thermoplastic polymer is extremely excellent in recyclability because even after softening by heating to 120 ° C. or more, physical properties such as moldability and tensile properties do not decrease and strength after remolding is maintained. ing.

The thermoplastic polymer according to the first, second, third and fourth aspects of the present invention having such properties can be used for various vulcanized rubber applications by utilizing, for example, rubber elasticity. it can. Also, when included in a hot melt adhesive, heat resistance and recyclability can be improved. Especially around automobiles, for example, tire treads, carcass; exterior radiator grills, side moldings, garnishes (pillars, rear, cowl tops), aero parts (air dams, spoilers), wheel covers, weather strips, cow belt grills, air outlets・
Louvers, air scoops, food bulges, vent parts,
Anti-touch parts (over fenders, side seal panels, moldings (windows, hoods, door belts), marks; doors, lights, wiper weather strips,
Interior window frame parts such as glass run, glass run channel; air duct hose, radiator hose, brake hose; crankshaft seal, valve stem seal,
Lubricating oil parts such as head cover gaskets, A / T oil cooler hoses, transmission oil seals, P / S hoses, P / S oil seals; fuel parts such as fuel hoses, emission control hoses, inlet filler hoses, tire flams, etc. Components for anti-vibration such as engine mount and in-tank pump mount; CVJ boots;
Boots such as rack & pinion boots; A / C hose,
Suitable for air conditioning components such as A / C seals; belt components such as timing belts and accessory belts; sealers such as windshield sealers, vinyl plastisol sealers, anaerobic sealers, body sealers, spot weld sealers, etc. Can be used. Further, when the resin or rubber which causes cold flow at room temperature is contained as a rubber modifier, for example, as a flow-preventing agent, flow during extrusion and cold flow can be prevented.

Further, the thermoplastic polymer of the present invention can be used as a composition by mixing with carbon black. Carbon black is appropriately selected depending on the application. Generally, carbon black is classified into hard carbon and soft carbon based on the particle diameter. Soft carbon has low reinforcement to rubber, and hard carbon has high reinforcement to rubber. In the present invention, it is particularly preferable to use hard carbon having a strong reinforcing property, and 10 to 70 parts by weight with respect to 100 parts by weight of the thermoplastic polymer.
Preferably 20 to 60 parts by weight, more preferably 30 to 5 parts by weight.
It is good to contain 0 parts by weight.

Further, other reinforcing agents such as silica, an antioxidant, an antioxidant, a pigment and the like can be added within a range not to impair the object of the present invention. Other reinforcing agents include fumed silica, calcined silica, precipitated silica, ground silica, fused silica, diatomaceous earth, iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate And clay, kaolin clay, calcined clay and the like, and it is preferable to add 20 to 80 parts by weight, more preferably 30 to 60 parts by weight, based on 100 parts by weight of the thermoplastic polymer. Examples of the anti-aging agent include compounds such as hindered phenols, aliphatic and aromatic hindered amines, and 0.1 to 100 parts by weight of the thermoplastic polymer.
It is preferable to add 10 parts by weight, more preferably 1 to 5 parts by weight. Examples of the antioxidant include, for example, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), and the like, based on 100 parts by weight of the thermoplastic polymer.
It is preferable to add 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight. Pigments include titanium dioxide, zinc oxide, ultramarine blue, red iron, lithopone, lead, cadmium, iron,
Cobalt, aluminum, hydrochloride, inorganic pigments such as sulfates, azo pigments, organic pigments such as copper phthalocyanine pigments, and the like, based on 100 parts by weight of the thermoplastic polymer,
It is preferable to add 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight.

The thermoplastic polymer of the present invention can self-crosslink. However, a vulcanizing agent, a vulcanization aid, a vulcanization accelerator and the like can be used in combination as long as the object of the present invention is not impaired. As a vulcanizing agent, sulfur-based vulcanizing agents such as powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, alkylphenol disulfide, zinc white, magnesium oxide, litharge, p-Quinone dioxime, p-dibenzoylquinone dioxime, tetrachloro-p-benzoquinone, poly-p-dinitrosobenzene, methylin dianiline and the like. As vulcanization aids, acetyl acid,
Propionic acid, butanoic acid, stearic acid, acrylic acid,
Fatty acids such as maleic acid; and zinc fatty acids such as zinc acetylate, zinc propionate, zinc butanoate, zinc stearate, zinc acrylate, zinc maleate, and the like.
Examples of the vulcanization accelerator include tetramethylthiuram disulfide (TMTD) and tetraethylthiuram disulfide (T
Thiurams such as ETD); aldehydes and ammonia such as hexamethylenetetramine; guanidines such as diphenylguanidine: dibenzothiazyl disulfide (D
M) and the like; sulfenamides such as cyclohexylbenzothiazylsulfenamide; and the like. Further, an alkylphenol resin or a halide thereof may be used.

The composition containing the thermoplastic polymer of the present invention contains carbon black or the like, so that the composition has a tensile strength,
The tear strength and the bending strength are further improved, and particularly, it can be suitably used for applications such as tires, hoses, belts, sheets, anti-vibration rubber, rollers, linings, rubber cloths, sealing materials, gloves, and anti-glare materials.

[0042]

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. <Synthesis of thermoplastic polymer according to first embodiment> Commercially available maleic anhydride-modified isoprene rubber (modification ratio 2.7 mo)
1%, LIR-410A, manufactured by Kuraray Co.) 12.73 g
(6.55 mmol) was added with 0.551 g (6.55 mmol) of 3-amino-1,2,4-triazole,
The mixture was heated and stirred at 150 ° C. for 4 hours.

After confirming that the solution became a homogeneous solution, it was left overnight to obtain a gel-like reaction product. Reactant is N
By MR and IR, it was confirmed that the thermoplastic polymer 1 had the following structure. Hereinafter, thermoplastic polymers 2 to 8 were synthesized using the corresponding nitrogen-containing heterocyclic-containing compound in the same ratio. Further, as a comparative compound, the above maleic anhydride-modified isoprene rubber and 4-aminopyridine were reacted at the same ratio to obtain a thermoplastic polymer 9. further,
As a comparative compound, the above maleic anhydride-modified isoprene rubber and furan were reacted at the same ratio to obtain a thermoplastic polymer 10. Thermoplastic polymers 1 to 10 obtained
Is as shown below.

[0044]

Embedded image Here, l: m ≒ 358: 10.

Examples 1 to 8 Regarding the obtained thermoplastic polymers 1 to 8, JIS A
The hardness was measured, and the state when heated at 120 ° C. was observed. The results are shown in Table 1.

Comparative Example 1 With respect to the obtained thermoplastic polymer 9, the JIS A hardness and the state when heated at 120 ° C. were observed in the same manner as in the example. Comparative Example 2 Regarding the obtained thermoplastic polymer 10, the JIS A hardness and the state when heated at 120 ° C. were observed in the same manner as in the example.

[0047]

[Table 1]

As can be seen from Table 1, the compounds of Examples of the present invention having a 5-membered cyclic nitrogen-containing heterocyclic group-containing compound are represented by 6
It can be seen that JIS A hardness is significantly higher in the case of having a membered pyridyl group or in the case of a furan ring having no nitrogen than in the case of a 7-membered ring. In addition, the nitrogen-containing heterocyclic 2
Other than the polymer 3,4,6,7 linked at the position 3,
The effect of the polymer bonded at the 4-position is high.

<Synthesis of Thermoplastic Polymer According to Third Embodiment> Maleic anhydride-modified EPDM (modification ratio: 0.8 mol%, maleic anhydride introduction amount: 6.63 g, DSM Company test) was placed in a pressure kneader heated to 120 ° C. Work) 301.2g
(0.0676 mol: the amount of acid anhydride) was added, and after mastication for a short time, 5.68 g (0.0676 mol) of 3-amino-1,2,4-triazole was added, and the mixture was mixed for 20 minutes. . IR analysis confirmed that the polymer 12 had a triazole ring introduced therein.

[0050]

Embedded image (Where n + o + p: q ≒ 99.2: 0.8 R = hydrocarbon group having 1 to 12 carbon atoms)

Similarly, a thermoplastic polymer 13 according to the third embodiment of the present invention was synthesized. A maleic anhydride-modified EPM (denaturation rate of 0.1%) was placed in a pressure kneader heated to 150 ° C.
2mol%, maleic anhydride introduction amount 1.50 g, Tuffmer M0610, manufactured by Mitsui Chemicals, Inc.) 300.0 g (0.0
153 mol: amount of acid anhydride), and after a short mastication, 3-amino-1,2,4-triazole 1.29
g (0.0153 mol) was added and mixed for 20 minutes. By performing IR analysis, it was confirmed that the polymer 13 had a triazole ring introduced therein.

[0052]

Embedded image (Here, r + s: t ≒ 99.8: 0.2 R = hydrocarbon group having 1 to 12 carbon atoms)

Example 9 A flat plate sample was prepared for the obtained thermoplastic polymer 12 in the same manner as described above, and a test was conducted. The results are shown in Table 2. In addition, the evaluation test of the Example and the comparative example was performed on condition of the following.

1. Tensile test The sheet was hot-pressed at 150 ° C. for 25 minutes to produce a sheet having a thickness of 2 mm. A No. 3 dumbbell-shaped test piece was punched out of the sheet, and the tensile speed was 500 in accordance with JIS K6251.
A tensile test was performed at mm / min. 50% modulus (M
_50), 100% modulus (M _100), 200% modulus (M _200), 300% modulus (M _300), 40
The 0% modulus (M ₄₀₀ ), breaking strength (T _B ), breaking elongation (E _B ), and breaking energy (ENG) were measured at room temperature. 2. Repetitive molding test After press molding at 160 ° C. for 20 minutes in a cylindrical mold having a diameter of 2.8 mm and a height of 1.2 mm, the sample is cut into small pieces and pressed again to form a seamless integrated sample. It was evaluated whether it could be produced. Also 5
A sample was prepared in the same manner even after repeated molding, and the above-mentioned tensile test was performed and compared with the initial value. 3. Hardness test After hot-pressing at 150 ° C. for 5 minutes to produce a sheet having a thickness of 2 mm, the sheets were overlapped and hot-pressed at 150 ° C. for 30 minutes to produce a Lupke sample. The hardness was measured at room temperature using a JIS A type hardness tester. JIS K 62
According to 53. 4. High Temperature Tensile Test A hot press was performed at 150 ° C. for 5 minutes to produce a sheet having a thickness of 2 mm. The prepared sheet was punched out with a dumbbell No. 3, and a tensile test was performed at a tensile speed of 500 mm / min. Breaking strength (TB) and breaking elongation (EB) were measured in a constant temperature bath at 100 ° C. According to JIS K6251. 5. Compression set (C-Set) After hot-pressing at 150 ° C for 5 minutes to prepare a sheet having a thickness of 2 mm, the sheets were overlapped and hot-pressed at 150 ° C for 30 minutes to prepare a lupke sample. The Lupke sample was compressed by 25% with a special jig and left at 70 ° C. for 22 hours to measure compression set. According to JIS K 6262. 6. Outflow start temperature Using a Koka type flow tester, the outflow start temperature was measured by the temperature raising method. The diameter of the die was 1 mm and the length was 10 mm. The sample amount is 2 g, the load is 100 kgf,
The heating rate was 5 ° C./min. 7. Melt flow rate (MFR) Measured with a melt indexer. Die diameter is 2.0
95 mm and the die length was 8 mm. Measurement temperature is 230
° C, sample amount 5g, residual heat time 6 minutes, load 10k
gf.

Example 10 To a thermoplastic polymer 12 (100 parts by weight) was added 50 parts by weight of carbon black (N330, manufactured by Tokai Carbon Co., Ltd.), and the mixture was kneaded with a Banbury mixer at 160 ° C. until the mixture became sufficiently uniform. . The obtained composition was evaluated for tensile strength and repetitive moldability in the same manner as in Example 9.

Example 11 A thermoplastic polymer 13 was used in place of the thermoplastic polymer 12.
The tensile strength and the repetitive moldability were evaluated in the same manner as in Example 9 except for using.

Comparative Example 3 EPDM (KELTA) was used in place of the thermoplastic polymer 12.
N312 (manufactured by DSM), unmodified, and at the quantitative ratios shown in Table 2, Zinc Hua No. 3 (manufactured by Seido Chemical Co., Ltd.), stearic acid (beads stearic acid, manufactured by NOF Corporation), sulfur (powder sulfur) , Made by Karuizawa Refinery), Noxeller T as an accelerator
S (tetramethylthiuram monosulfide) and Noxeller M (2-mercaptobenzothiazole, manufactured by Ouchi Shinko Chemical Co., Ltd.) were mixed and kneaded with a Banbury mixer to obtain a uniform composition. The obtained composition was evaluated for tensile strength and repetitive moldability in the same manner as in Example 9.

Comparative Example 4 Except that 50 parts by weight of carbon black was added,
A composition was obtained in the same manner as in Comparative Example 3, and the tensile strength was measured. The results are shown in Table 2. Table 2 and 3
In the table, “more than times” means that there was no change in physical properties even after repeating the forming up to times, and it is also possible to repeat reshaping. “X” indicates that reshaping was not possible.

[0059]

[Table 2]

Examples 12 to 17 and Comparative Examples 5 to 10 In the same manner as in Examples 8 to 11, the composition shown in Table 3 was used at 130 ° C.
Mix for about 30 minutes in a kneader at 200 ° C.
Seventeen thermoplastic polymers were synthesized and subjected to the tests shown in Table 3 in the same manner as in Examples 8 to 11. The results are shown in Table 3.
The configuration in Table 3 was as follows. In the example, all the strengths are higher than the comparative example (original polymer),
In addition, the moldability at the time of heating is ensured. Mitsui Chemicals Tuffmer MH7020: ethylene / butene system, density 0.872,
MH5020: ethylene / butene system, density 0.866, maleic anhydride introduction rate unknown but low
The rate of introduction of maleic anhydride is unknown but low. TX-1032: ethylene / butene system, density 0.87
4. The maleic anhydride introduction rate is unknown but high TX-1024: ethylene / propylene system, density 0.8
70, maleic anhydride introduction rate is unknown but low TX-1023: ethylene / propylene system, density 0.8
70, maleic anhydride introduction rate is unknown but high TX-1031: ethylene / propylene system, density 0.8
74, maleic anhydride introduction rate is unknown but high

[0061]

[Table 3]

<Synthesis of Thermoplastic Polymer According to Fourth Aspect> (Example 18) A pressurized kneader heated to 80 ° C. was charged with a brominated butyl rubber (bromobutyl × 2, Bayer Polysar BN).
V) (350.0 g; 6.07 mol; butyl unit), and after a short period of mastication, 3.5 g (1.0 phr) of N- (1,3 dimethylbutyl) -N'-phenyl-p-phenylenediamine. ), 35.1 g of maleic anhydride
(0.358 mol) and 38.0 g of xylene
(0.358 mol) was added and mixed for 10 minutes. Once the mixture was removed, the pressure kneader was set at 190 ° C. The removed mixture was placed in a kneader and kneaded for 40 minutes. Part of the obtained rubber is dissolved in toluene,
Purification was performed by performing a reprecipitation operation. By conducting IR analysis and ¹ H-NMR analysis using the purified product, the introduction of the acid anhydride skeleton was confirmed.
It was 0 mol%. This anhydrous maleated butyl rubber 3
57.7 g (0.113 mol; amount of acid anhydride), 3-
9.51 g of amino-1,2,4-triazole (0.1
13 mol) and N- (1,3 dimethylbutyl)-
3.54 g of N'-phenyl-p-phenylenediamine
(1.0 phr) was kneaded in a pressure kneader at a temperature of 100 ° C. for 20 minutes. IR analysis confirmed the introduction of the triazole ring. (Comparative Example 11) The brominated butyl rubber used in Example 18 was sulfur-vulcanized at 160 ° C for 20 minutes, and the thermoreversible polymer of Example 18 was compared with the tensile properties.

[0063]

[Table 4]

As shown in Table 4, a polymer in which 3-amino-1,2,4-triazole is supported on a butyl rubber having an acid anhydride skeleton exhibits thermoreversibility, and the polymer is a vulcanized butyl rubber. The above mechanical strength was shown. In particular, the modulus, elongation at break, and elongation at break of 200% or more are significantly improved.

[0065]

As described in detail above, according to the present invention,
By introducing a carbonyl-containing group and a nitrogen-containing 5-membered cyclic heterocyclic-containing group into a side chain of a non-recyclable elastomeric polymer, physical properties can be maintained even when cross-link formation and cross-link dissociation are repeated due to temperature changes. And excellent recyclability can be imparted without lowering. At room temperature, the crosslinked structure is extremely stable and has a very high tensile strength. In particular, when the diene part is 5 mol% or less, for example, EPM, EBM or EPDM, butyl rubber or halogenated butyl rubber is used as the elastomeric polymer, the effect is high.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tetsuji Kawamo 2-1 Oiwake, Hiratsuka-shi, Kanagawa Yokohama Rubber Co., Ltd. Inside Hiratsuka Factory (72) Inventor Katsuhiro Igawa 2-1 Oiwake, Hiratsuka-shi, Kanagawa Yokohama Rubber F-term in Hiratsuka Works (reference) 4J002 AC00W AC11X AC12X BB20X BB28X FD010 GJ02 GM00 GN00 GN01 4J100 AA02P AA03Q AA04Q AA06P AB02P AK32Q AK32R AK32 HA14 HA03 CA03 BC03 BC03 AS03HH HC30 HC63 HG31 HG32 JA28 JA29

Claims (11)

[Claims] 1. A thermoplastic polymer having a carbonyl-containing group and a nitrogen-containing 5-membered cyclic heterocyclic-containing group in a side chain. 2. An elastomer having a diene portion of 5 mol% or less as a main chain, a carbonyl-containing group and a nitrogen-containing heterocyclic-containing group in a side chain, and a side chain portion of 0% with respect to 100 mol% of the main chain portion. A thermoplastic polymer having a proportion of 1 to 50 mol%. 3. An ethylene-propylene copolymer (EP)
M), an ethylene-butene copolymer (EBM) or an ethylene-propylene-diene copolymer (EPDM) as a main chain, a carbonyl-containing group and a nitrogen-containing heterocyclic-containing group in a side chain, and a main chain portion. A thermoplastic polymer having a side chain portion in a ratio of 0.1 to 50 mol% with respect to 100 mol%. 4. A butyl rubber or a halogenated butyl rubber having a main chain, a carbonyl-containing group and a nitrogen-containing heterocyclic group-containing group in a side chain, wherein the side chain portion is 0.1 to 0.1 mol% based on 100 mol% of the main chain portion. A thermoplastic polymer having a proportion of 50 mol%. 5. The thermoplastic polymer according to claim 2, wherein said nitrogen-containing heterocyclic ring is a 5-membered ring or a 6-membered ring. 6. The thermoplastic polymer according to claim 1, wherein said carbonyl-containing group is at least one selected from amide, ester, imide and carboxyl groups. 7. The method according to claim 1, wherein the side chain is at least one of formulas (1), (2) and (3), which binds to the main chain at the α-position or the β-position. Thermoplastic polymer. Embedded image Here, R represents a nitrogen-containing heterocyclic ring. 8. The thermoplastic polymer according to claim 7, wherein said nitrogen-containing heterocyclic ring is a 5-membered ring or a 6-membered ring. 9. A glass transition point (T) of the thermoplastic polymer.
The thermoplastic polymer according to any one of claims 1 to 8, wherein g) is 25 ° C or lower. 10. A reaction between a polymer having a cyclic acid anhydride group in a side chain and a nitrogen-containing heterocyclic compound at a temperature at which the nitrogen-containing heterocyclic compound can chemically bond to the cyclic acid anhydride group. The method for producing a thermoplastic polymer according to claim 1. 11. A rubber composition containing the thermoplastic polymer according to claim 1.