JPH0411657A - Thermoplastic graft copolymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic graft copolymer which is highly heat- resistant and melt moldable at high temp. and shows excellent properties as a rubberlike elastomer over a wide temp. range from room temp. to high temp. by selecting a thermoplastic graft copolymer comprising a specific main chain and specific side chains. CONSTITUTION:A thermoplastic graft copolymer comprising a main chain consisting of a polymer having a glass transition point of 10 deg.C or lower (e.g. an ethylene-methyl acrylate-glycidyl methacrylate terpolymer) and side chains consisting of an arom. oligomer having a specifically defined flow temp. of 100 deg.C or higher, e.g. a compd. of the formula (having an average degree of polymn. of 3.5) obtd. by the polycondensation of benzoic acid with p- hydroxybenzoic acid in the presence of acetic anhydride.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermoplastic graft copolymer that can be used as a thermoplastic elastomer, particularly a thermoplastic elastomer having high heat resistance, and a method for producing the same.

[Prior art 1] Thermoplastic elastomers (hereinafter abbreviated as TPE) currently used industrially are made of TPE consisting of a block copolymer of soft segments and hard segments, and a partially crosslinked rubber called elastomer alloy. Separated plasti1. It is broadly divided into TPE, which consists of evening. The former includes block copolymers called polyester elastomers, which consist of an aliphatic polyether part such as polytetramethylene glycol and a polyester part such as polyethylene terephthalate and polybutylene terephthalate, and a block copolymer called a polyester elastomer, which consists of an aliphatic polyether part such as polytetramethylene glycol and a polyester part such as polyethylene terephthalate and polybutylene terephthalate, and a block copolymer called a polyester elastomer, which is composed of an aliphatic polyether part such as polytetramethylene glycol and a polyester part such as polyethylene terephthalate and polybutylene terephthalate. Block copolymers called polyamide elastomers, which are composed of polyamide moieties such as lactam, are known. Also known as the latter is an elastomer alloy formed by dynamic vulcanization of an alloy of polypropylene and an ethylene-propylene-diene terpolymer.

Furthermore, European Patent Publication No. 0287233 discloses that a copolymer having an aromatic polyester as a side chain, that is, a copolymer in which an aromatic polyester is covalently bonded to an acrylic resin or a polyester resin, is used as a polymer solution for coating. It is characterized by the ability to form a coating with high hardness. However, the specification does not contain any suggestion regarding thermoplastic resins or TPE.

[Problem to be solved by the invention]

However, TPE consisting of a block copolymer of soft segments and heart segments has a hardness of about 4
Only relatively hard elastomers with a Shore A hardness of 0 or more can be made, and these TPEs have a large compression set and do not have very high heat resistance.In addition, elastomer alloys can be made with soft elastomers with a Shore A hardness of about 30. Although it is possible, the reality is that the heat resistance is not excellent.

[Means to solve the problem]

In view of these circumstances, the inventors of the present invention have conducted extensive research and have found that
We have discovered a thermoplastic graft copolymer in which the main chain is a polymer with a glass transition temperature of 10°C or lower, and the side chain is an aromatic oligomer with a flow temperature of 100°C or higher, and a method for producing the same; They discovered that it has excellent properties as a thermoplastic elastomer and completed the present invention.

Furthermore, as a result of intensive research, the present inventors found that the main chain is a polymer with a glass transition temperature of 10°C or lower, the side chain is an aromatic oligomer with a flow temperature of 100°C or higher, and the glass transition temperature is 10°C or lower. We have discovered a graft copolymer and a method for producing the same, in which the polymer is partially crosslinked and the obtained graft copolymer melt-flows, and furthermore, the graft copolymer has excellent properties as a thermoplastic elastomer. The present invention was completed based on the discovery that the present invention has the following properties.

The thermoplastic graft copolymer of the present invention has a compression set of 90% or less at 706C for 22 hours, a Shore D hardness of 50 or less, and a permanent elongation of 50% at 23°C. These are as follows.

Further, the thermoplastic graft copolymer of the present invention is characterized in that it is insoluble in a good solvent for the polymer having a glass transition temperature of 100 C or less that constitutes the graft copolymer.

Further, the thermoplastic graft copolymer of the present invention is preferably a polymer having a glass transition temperature of 10° C. or lower, or a crystalline polymer, which constitutes the graft copolymer.

Further, the thermoplastic graft copolymer of the present invention is characterized in that a physical crosslink is formed by the grafted aromatic oligomer.

Furthermore, the thermoplastic graft copolymer of the present invention is obtained by grafting a polymer having a glass transition temperature of 10°C or lower as a main chain and an aromatic oligomer having a flow temperature of 100°C or higher as a side chain. It is preferably obtained by performing a graft reaction by melt-kneading and cooling.

The backbone polymer (main chain) constituting the graft copolymer of the present invention has a glass transition temperature of 10° C. or lower, preferably 0° C. or lower, particularly preferably 100° C. or lower.

This glass transition temperature is measured using a differential scanning calorimeter (DSC).
This is the second-order transition point at which an endotherm is observed at a heating rate of 10° C./min. If the glass transition temperature (hereinafter abbreviated as Tg) of the backbone polymer (main chain) exceeds 10°C, the graft copolymer will not exhibit rubber elasticity in the operating temperature range above room temperature, which is not preferable.

The backbone polymer (main chain) having a Tg of 10°C or less that constitutes the graft copolymer of the present invention is preferably an acrylic ester polymer, a styrene-butadiene copolymer and its hydrogenated product, or a styrene-isoprene polymer. Copolymers and their hydrogenated products, polybutadiene, polyisoprene, ethylene/propylene copolymers, ethylene/propylene/diene copolymers, acrylonitrile/butadiene copolymers and their hydrogenated products, polychloroprene, ethylene/acrylic acid esters Examples include copolymers, homopolymers such as chlorosulfonated polyethylene, olefin polymers such as random copolymers, vinyl polymers, polyorganosiloxanes, and polyphosphazenes. Furthermore, a copolymer of a monomer having an unsaturated double bond that can be copolymerized with the monomer constituting the above-mentioned homopolymer or random copolymer can also be used. However, in any copolymer, the copolymer composition must be controlled so that the Tg is 10° C. or less.

Furthermore, the Tg constituting the graft copolymer of the present invention is 10
Examples of the backbone polymer (main chain) having a temperature of 0.degree. Examples of the reactive functional group include an amino group, an epoxy group, and a hydrogen atom bonded to a silicon atom.

The side chains constituting the graft copolymer of the present invention are aromatic oligomers having a flow temperature of 100°C or higher, preferably 150°C or higher, and more preferably 170°C or higher. Further, the flow temperature of the aromatic oligomer is preferably 400°C or lower. More preferably 150°C to 350°C1 and even 170°C
~300°C is preferred.

This flow temperature was determined to be 100 kg/cr using a capillary rheometer with a nozzle of 1 mm inner diameter and 10 mm length.
This is the temperature at which the melt viscosity is 48,000 poise when the heated melt is extruded from the nozzle at a heating rate of 4° C./min under a load of 1. The flow temperature of the aromatic oligomer is 100
When the temperature is lower than 0.degree. C., the temperature range in which the obtained graft copolymer exhibits rubber elasticity becomes narrow, that is, the heat resistance of the graft copolymer becomes insufficient, which is not preferable.

Furthermore, the aromatic oligomer is used in a solvent for monomer and dimer components in order to improve thermal decomposition resistance and to form physical crosslinking points and develop sufficient rubber elasticity when used as a graft copolymer. Preferably, it is removed by washing.

The solvent is preferably a polar solvent that is inert to aromatic oligomers. Particularly preferred is a solvent having a solubility parameter of 9.0 to 15.0 at 25°C.

(Solubility parameters are Encycl, Polym
, Sci.

Technol, 3. 833. (1965). ) The aromatic oligomer having a flow temperature of 100° C. or higher, which constitutes the graft copolymer of the present invention, is an oligomer having a benzene ring in its main skeleton, and preferably has a structural unit represented by the following maximum (I). It is an oligomer containing 50% by weight or more, preferably 60% by weight or more.

(XAr-C→- (I) (wherein, X is selected from O and S, and one oligomer may contain a structural unit containing 0 and a structural unit containing S at the same time.

(R').

R1 and R2 are selected from alkyl groups having 1 to 3 carbon atoms and phenyl groups, and R,, R, may be the same or different groups. Different groups may be attached to one benzene ring. p
lq is an integer from 0 to 2. ) The oligomer preferably has a number average molecular weight in the range of 300 to 1500,
More preferably, it is in the range of 400 to 1000. If the number average molecular weight is less than 1,300, the polycondensate will be easily thermally decomposed, and the flow temperature will drop significantly, resulting in a decrease in the heat resistance of the resulting graft copolymer, which is undesirable. Exceeding this is not preferable because the flow temperature will approach the thermal decomposition temperature of the oligomer and the moldability of the resulting graft copolymer will deteriorate.

In addition, in order to control the properties such as the melting point, the oligomer has a structure in which monomers such as hydroxyalkylcarboxylic acid, aminoalkylcarboxylic acid, aminoarylcarboxylic acid, etc. are polycondensed, and a monofunctional carboxylic acid compound, It may include a structure in which a phenol compound and an amino compound are condensed.

The thermoplastic graft copolymer of the present invention can be used as a thermoplastic elastomer that exhibits rubber elasticity in a wide temperature range above room temperature.

It is presumed that the repeating structural unit (I) of the aromatic oligomer functions as a hard segment in the obtained graft copolymer, forms a microdomain structure, and becomes a physical crosslinking point.

The resulting copolymer or thermoplastic elastomer with excellent heat resistance can be used as follows:
It is presumed that this is due to the above reasons. However, this estimation does not limit the present invention in any way.

Furthermore, the graft copolymer of the present invention has a three-dimensional network structure when the polymer having a glass transition temperature of 10° C. or lower constituting the graft copolymer is partially crosslinked by covalent bonds. As a result, it exhibits excellent comb elasticity in a wide temperature range above room temperature, and can be used as a thermoplastic elastomer by providing a degree of crosslinking that allows it to melt and flow.

The melt flow referred to here means that the obtained graft copolymer
40 to 100°C from the flow temperature of the aromatic oligomer used
Indicates that the melt index measured under lokg load conditions at high temperature is 011 or higher. If the melt index measured under these conditions is less than 0.1, melt molding becomes difficult, which is not preferable. The graft copolymer may be used alone, or the graft copolymer and the main chain (stem polymer) constituting the graft copolymer may be the same or different from each other.
A mixture of a polymer having a g of 1,000 or less and/or an oligomer having the same side chain as the graft copolymer exhibits properties as a thermoplastic elastomer.

However, in any case, the polymer having a Tg of 10° C. or less accounts for 50% by weight or more and 99% by weight or less, preferably 65% by weight or more and 97% by weight or less of the total polymer. If the polymer with a Tg of 10°C or less is less than 50% by weight of the total polymer, the resulting thermoplastic elastomer will be difficult to exhibit rubber elasticity in the temperature range above room temperature, which is undesirable. If it exceeds 99% by weight, the physical properties of the side chains This is undesirable because the number of crosslinking points decreases and the resulting polymer undergoes significant plastic deformation even at room temperature.

Furthermore, the graft copolymer which is the thermoplastic elastomer of the present invention may be suitably used in carbon bra, tsuku, silica, calcium carbonate, mica, diatomaceous earth, zinc white, basic magnesium carbonate, aluminum silicate, titanium dioxide, talc, glass. Fillers such as fibers, plasticizers, anti-aging agents, colorants, ultraviolet absorbers, flame retardants, oil resistance improvers, scorch inhibitors, tackifiers and the like can be optionally mixed and used.

The method for producing the thermoplastic graft copolymer of the present invention involves using a polymer having a reactive functional group and/or modified with a reactive functional group and having a glass transition temperature of 10°C or less, and a polymer having a glass transition temperature of 10°C or less, An example is a method of reacting an aromatic oligomer having a functional group capable of reacting with a functional group of a polymer.

That is, in the method for producing the thermoplastic graft copolymer of the present invention, the structural unit represented by the following formula (I) is contained in an amount of 50% by weight.
The present invention relates to a method for producing a thermoplastic graft copolymer according to claim 1, characterized in that the aromatic oligomer containing the above-mentioned aromatic oligomers is grafted.

zuX-Ar-Csu (I) (wherein, X is selected from O and S, and one oligomer may contain a structural unit containing 0 and a structural unit containing S at the same time.

R' and R2 are selected from alkyl groups having 1 to 3 carbon atoms and phenyl groups, and R1 and R2 may be the same or different groups. Different groups may be attached to one benzene ring.

p and q are integers of 0 to 2. ) used in the present invention,
Reactive functional groups in polymers with a glass transition temperature of 10°C or lower include epoxy groups, amino groups, hydroxyl groups, carboxylic acid groups, thiol groups, isocyanate groups, halogen groups, alkylsilyl ether groups, silyl halide groups, and acid anhydrides. group, a group having an unsaturated double bond, and the like.

In addition, the functional groups of the aromatic oligomer reacted with the polymer used in the present invention include an epoxy group, a hydroxyl group, a carboxylic acid group, a thiol group, a halokene group, an alkylsilyl ether group, a silyl halide group, and an acid anhydride group. , a group having an unsaturated double bond, and the like.

The combination of the reactive functional group on the main chain and the functional group on the side chain that can react with the reactive functional group on the main chain can be appropriately selected within the range that does not impair the object of the present invention.

For example, the method for producing the thermoplastic graft copolymer of the present invention involves using a polymer that has a glass transition temperature of 10°C or lower and has a functional group that can react with a carboxylic acid group, and a polymer that has a flow temperature of 100°C or higher and has a functional group that can react with a carboxylic acid group. Examples include a method of reacting with an aromatic oligomer having a carboxylic acid group at one end.

In addition, a polymer having a glass transition temperature of 10°C or less and a functional group capable of reacting with an acid anhydride group and a flow temperature of 10°C or less are used.
Examples include a method of reacting with an aromatic oligomer having an acid anhydride group at one end at 0° C. or higher.

Furthermore, there is a method in which a polymer having a glass transition temperature of 0° C. or lower and having radical reactivity is reacted with an aromatic oligomer having a flow temperature of 100° C. or higher and having a radically reactive functional group at one end. I get kicked.

In addition, polymers with a glass transition temperature of 10°C or less and an unsaturated double bond in their structure and a flow temperature of 100°C or less
A method may be mentioned in which an aromatic oligomer having C or more and having a functional group capable of reacting with an unsaturated double bond at one end is reacted.

In addition, a polyorganosiloxane having a glass transition temperature of 10°C or lower and partially modified with a reactive functional group, and a polyorganosiloxane having a flow temperature of 100°C or higher and having a functional group capable of reacting with the functional group of the polysiloxane at one end. A method of reacting an aromatic oligomer with an aromatic oligomer having an aromatic oligomer.

Hereinafter, the method for producing the thermoplastic graft copolymer of the present invention will be described in more detail.

The method for producing the thermoplastic graft copolymer of the present invention involves using a polymer having a glass transition temperature of 10°C or lower and having a functional group capable of reacting with a carboxylic acid group, and a polymer having a flow temperature of 10°C or lower.
One example is a method in which an aromatic oligomer having a carboxylic acid group at one end is reacted at 0° C. or higher. Preferred functional groups capable of reacting with the carboxylic acid group include glycidyl groups, epoxy groups, isocyanate groups, hydroxyl groups, and acetoxy groups. Particularly preferred are glycidyl and epoxy groups.

Examples of polymers containing glycidyl groups and/or epoxy groups include methyl acrylate/glycidyl methacrylate copolymer, ethyl acrylate/glycidyl methacrylate copolymer, propyl acrylate/glycidyl methacrylate copolymer, butyl acrylate/glycidyl methacrylate copolymer, and butyl acrylate/glycidyl methacrylate copolymer.
Glycidyl methacrylate copolymer, hexyl acrylate/glycidyl methacrylate copolymer, dodecyl acrylate/glycidyl methacrylate copolymer, methyl acrylate/glycidyl styrene copolymer, ethyl acrylate/glycidyl styrene copolymer, propyl acrylate/glycidyl styrene copolymer , butyl acrylate/glycidyl styrene copolymer, hexyl acrylate 1 note/glycidyl styrene copolymer, todenol acrylate, -k/glycidyl styrene copolymer, methyl acrylate/N-[4-(2,3-epoxypropoxy) 3.5 dimethylbenzylcoacrylamide copolymer, ethyl acrylate/N-C4-(2,3 epoxypropoxy)-3,5 dimethylbenzylcoacrylamide copolymer, propyl acrylate/N-C4-(2,
3-epoxypropoxy)-3,5 dimethylbenzylcoacrylamide copolymer, butyl acrylate/Il-
C4-(2,3-epoxypropoxy)-3,5-dimethylbenzylcoacrylamide copolymer, hexyl acrylate/N-[1-(2,3-epoxypropoxy)3.
5 dimethylbenzyl coacrylamide copolymer, dodecyl acrylate/N-C4-(2゜3-epoxypropoxy)-3,5 dimethylbenzyl coacrylamide copolymer, acrylonitrile/butadiene/glycidyl methacrylate copolymer, acrylonitrile/butadiene/
Clidinorstyrene copolymer, acryloni]/lyl/butadiene/N-[4-(2,3-epoxypropoxy)
3.5-methylhensyl: □Acrylamide copolymer,
Ethylene/vinyl acetate/glycidyl methacrylate copolymer, ethylene/vinyl acetate/clidinol styrene copolymer, ethylene/vinyl acetate/N-C4-(2,3-epoxypropoquine) 3.5 dimethylbenzylcoacrylamide copolymer Polymer, ethylene/methyl acrylate/glycidyl methacrylate copolymer, ethylene/ethyl acrylate/glycidyl methacrylate copolymer, ethylene/propyl acrylate/glycidyl methacrylate copolymer, ethylene/butyl acrylate/glycidyl methacrylate copolymer, ethylene/hexyl Acrylate/glycidyl methacrylate copolymer, ethylene dodecyl acrylate/glycidyl methacrylate copolymer, ethylene/methyl acrylate/cridinorstyrene copolymer, ethylene/ethyl acrylate/cridinorstyrene copolymer, ethylene/propyl acrylate/crystalline copolymer Dinorstyrene copolymer, ethylene/butyl acrylate/cridinorstyrene copolymer, ethylene/hexyl acrylate/cridinorstyrene copolymer, ethylene/dodecyl acrylate/glycidylstyrene copolymer, ethylene/methyl acrylate/N -[4-(
2゜3-Epoxypropoquine 1)-3,5 dimethylbenzylcoacrylamide copolymer, ethylene/ethyl acrylate/N-C4-(2,3-epoxypropoxy)
-3,5 dimethylbenzylcoacrylamide copolymer,
Ethylene propyl acrylate N-C4-(2,3
-Epoxypropoxy) 3.5 dimethylbenzyl 1 acrylamide copolymer, ethylene/butyl acrylate/
N-[4-(2,3-epoxypropoxy)-3,5 dimethylbenzylcoacrylamide copolymer, ethylene/
Hexyl acrylate/N-C4,-(2,3-epoxypropoxy)-3,5 dimethylbenzylcoacrylamide copolymer, ethylene/dodecyl acrylate/N-
(4-(2,3-epoxypropoquine)-3,5-dimethyl): acrylamide copolymer, styrene-butanene-glycidyl methacrylate copolymer, styrene-butanene-cridinorstyrene copolymer, styrene-butadiene-N -C4-(2,3-epoxypropoxy)-3,5-dimethyl; various copolymers such as acrylamide copolymers can be mentioned.

These various copolymers can be obtained by generally well-known Rancal polymerization. In addition, epoxy groups and/or
Alternatively, polyorganosiloxane having a chrysyl group may be mentioned.

Further, the double bonds of a polymer having double bonds can be epoxidized by a known method, for example, the method described in U.S. Pat. No. 3,155,638, etc., and the polymer can be used as the main chain of the present invention. .

For example, there is a method in which a peracid such as metachloroperbenzoic acid is applied to a toluene solution of an ethylene-propylene-diene monomer terpolymer (hereinafter referred to as EPDM).

Furthermore, the introduction of chrysyl group into a polymer having a double bond can be carried out by various methods. For example, polymerization of a monomer having a polymerizable double bond and a cricidyl group, such as cricidyl methacrylate or allyl cricidyl ether or glycidyl acrylate, in the presence of EPDM in a suitable organic solvent, or co-polymerization with the above monomers, such as butyl acrylate. Grafting can also be achieved by copolymerization with polymerizable monomers.

The aromatic oligomer used in the present invention, which has a flow temperature of 100° C. or higher, preferably 150° C. or higher, and has a carboxylic acid group at one end, is preferably one represented by the following maximum (II).

R10-CgoX-Ar-C+VOH-(II) (wherein, X is selected from O and S, and one oligomer may contain a structural unit containing O and a structural unit containing S at the same time.

Rlo is an alkyl group having 5 or more carbon atoms, an aryl group or an aralkyl group having 6 or more carbon atoms, and R', R
" is selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group, and R1 and R2 may be the same or different groups. Different substituents may be attached to the same benzene ring. pXq
is an integer from 0 to 2. n is 2 to IO on average.

) It is also possible to copolymerize and use a hydroxycarboxylic acid having 2 to 6 carbon atoms in the oligomer. The number average molecular weight of the aromatic oligomer having a carboxylic acid group at one end shown above is preferably in the range of 300 to 1500, and the number average degree of polymerization is 2 to 10, depending on the selected species of Ro, R1, and R2Ar. Preferably it is 3-8, more preferably 4-7.

Hydroquine arylcarboxylic acid polymers are mainly composed of hydroxyarylcarboxylic acids and optionally small amounts of monomers copolymerizable therewith, such as hydroquine alkylcarboxylic acids having 2 to 6 carbon atoms, aminoalkylcarboxylic acids, aminoarylcarboxylic acids. Any method may be used as long as it produces a polycondensate using an acid, a monofunctional phenol compound, a carboxylic acid compound, an amino compound, etc. as a raw material, but it is preferably produced by the following method.

That is, acetoxyarylcarboxylic acid is obtained by adding an acetylating agent such as acetic anhydride or acetyl chloride to hydroxyarylcarboxylic acid, followed by heating and stirring. In the above reaction, when acetylating a hydroxyarylcarboxylic acid etc. with acetic anhydride, the reaction is carried out at 100°C or higher for 15 minutes or more, and in the reaction with acetyl chloride, the acetylation is carried out at room temperature or higher for 30 minutes or more. achieved. In any reaction, acetic anhydride and acetyl chloride are preferably added in excess, preferably about 1.1 times the number of moles of hydroxyl groups to be reacted. After the acetylation is completed, the temperature in the system is raised,
The polycondensation reaction is allowed to proceed by removing acetic acid while stirring. The temperature within the system preferably needs to be 200°C or higher. The number average molecular weight can be controlled by the amount of acetic acid to be distilled off, and in order to control the desired degree of polymerization, it is necessary to calculate the amount of monomers such as hydroxyaryl carboxylic acid charged and the amount of acetic acid to be distilled off. or is necessary. In addition,
Mercaptoarylcarboxylic acid can also be produced in the same manner as described above.

Further, in order to improve the thermal stability of the aromatic oligomer obtained, it is preferable to wash the obtained aromatic oligomer with a solvent such as methanol, ethanol, acetone, tetrahydrofuran, N-methylpyrrolidone, chloroform, or pyridine to remove monomers and dimers.

The aromatic oligomer having a carboxylic acid group at one end includes a monocarboxylic acid and a hydroxyarylcarboxylic acid having an alkyl group having 5 or more carbon atoms, preferably 5 to 20 carbon atoms, or an aryl group having 6 or more carbon atoms, preferably 6 to 15 carbon atoms. and, if necessary, a mixture of a hydroxycarboxylic acid having 2 to 6 carbon atoms, which is acetylated with acetic anhydride or acetyl chloride in the same manner as the above-mentioned method for producing a hydroxyarylcarboxylic acid polymer, and then By removing acetic acid, a polycondensate can be obtained. In this reaction, the number average molecular weight is determined by the molar ratio of monocarboxylic acid and hydroxycarboxylic acid.

Further, the obtained oligomer having a carboxylic acid group at one end is preferably washed with a solvent such as methanol, ethanol, acetone, tetrahydrofuran, N-methylpyrrolidone, chloroform, or pyridine, as described above.

The graft copolymer of the present invention has a Tg of 10°C or less and a polymer having a functional group capable of reacting with a carboxylic acid group;
It can be obtained by reacting an aromatic oligomer having a flow temperature of 100° C. or higher and having a carboxylic acid group at one end. Although the reaction method is not particularly limited, a method of reacting by melt mixing is preferred.

This melt-kneading is carried out by mixing the aromatic oligomer with the polymer having a Tg of 10° C. or less above the flow temperature of the aromatic oligomer using a conventional kneading machine, such as a Banbury mixer-screw extruder.
Any device that can apply a high shearing force at high temperature, such as a twin-screw extruder, roll, or kneader, may be used.

The reaction temperature is preferably at least higher than the flow temperature of the aromatic oligomer used, and lower than the thermal decomposition temperature of the polymer, which has a Tg of 10° C. or lower. If the reaction temperature is lower than the flow temperature of the aromatic oligomer used, it is not preferable that the carboxylic acid of the aromatic oligomer and the polymer having a Tg of 10°C or less will hardly react, making it difficult to obtain a graft copolymer. If the temperature exceeds the thermal decomposition temperature of the polymer, which is 10° C. or less, it is not preferable because the polymer decomposes during kneading or has adverse effects such as a significant decrease in molecular weight.

In order to promote grafting, a higher temperature within the above temperature range is preferred, a longer reaction time is preferred, and a larger shearing force is preferred. Furthermore, it is preferable to add triphenylphosphine, tertiary amine, etc. to promote grafting.

Next, as a method for producing the thermoplastic graft copolymer of the present invention, a polymer having a glass transition temperature of 10°C or lower and having a functional group capable of reacting with an acid anhydride group, and a polymer having a flow temperature of 100°C or higher and having a functional group capable of reacting with an acid anhydride group are used. An example is a method of reacting with an aromatic oligomer having an acid anhydride group at one end.

Examples of functional groups that can react with acid anhydride groups include glycidyl groups, epoxy groups, and amino groups.

The above-mentioned polymers containing an epoxy group and/or an epoxy group include the above-mentioned polymers containing an epoxy group and/or a glycidyl group that can react with an aromatic oligomer having a carboxylic acid group at one end. It can be mentioned here as well. That is, various copolymers of glycidyl methacrylate, glycidyl styrene, allyl glycidyl ether, etc. mentioned above may be mentioned. Further examples include polymers having double bonds in which the double bonds are epoxidized, polyorganosiloxanes having glycidyl groups and/or epoxy groups in side chains, and the like. Furthermore, the above-mentioned polymers having an amino group include various copolymers obtained by copolymerizing monomers having an unsaturated double bond and an amine group in the same molecule, such as aminostyrene and allylamine, and modified polymers by grafting the monomers onto side chains. There are various polymers that have been used.

The aromatic oligomer used in the present invention, which has a flow temperature of 100°C or higher, preferably 150°C or higher, and has an acid anhydride group at one end, is preferably one represented by the following maximum (I[[). It is.

(In the formula, X is selected from 0 and S, and R20 is hydrogen, a structural unit containing O and a structural unit containing S in one oligomer,
It is selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and R20 is selected from a kyl group and an aryl group having 6 to 20 carbon atoms.

It can be obtained by mixing diarylcarboxylic acids in a molar ratio of 1/1 to 1/10 and condensing the mixture. In addition, when X in formula (I) is S, it can be manufactured according to this method.

The acetoxyarylcarboxylic acids used in the present invention include acetylated hydroxyarylcarboxylic acids having 7 or more carbon atoms, preferably 7 to 20 carbon atoms. Specifically, R' and R2 are selected from alkyl groups having 1 to 3 carbon atoms and phenyl groups, and R1 and R2 may be the same or different groups. Different substituents may be attached to the same benzene ring. p and q are integers of 0 to 2. n is a number average of 2 to I
It is O. ) The aromatic oligomer is trimellitic anhydride or
-acetoquine phthalic anhydride and acetoquine (in the formula, R1,
R2 is selected from an alkyl group having 1 to 3 carbon atoms and a phenyl group, and R1 and R2 may be the same or different. Different substituents may be attached to the same Hensen ring. p, q
is an integer between O and 2. ).

Among these, paraacetquin benzoic acid is preferably used.

The aromatic oligomer having an acid anhydride at one end in the present invention can be obtained by deaceticating a mixture of trimellitic anhydride or 4-acetoquinphthalic anhydride and acetoxyarylcarboxylic acid.

In the above reaction, acetoxyarylcarboxylic acid is obtained by acetylating hydroxyarylcarboxylic acid with acetic anhydride or acetyl chloride, but when hydroxyarylcarboxylic acid is acetylated with acetic anhydride, the reaction is carried out at 100°C or higher for 15 Acetylation can be achieved by carrying out the reaction for 30 minutes or more at room temperature or higher in the case of a reaction using acetyl chloride.

In any reaction, acetic anhydride and acetyl chloride are preferably added in excess, preferably about 1.1 times the number of moles of hydroxyl groups to be reacted.

After the acetylation is complete, add trimellitic anhydride or 4 to the system.
- Acetoxyphthalic anhydride is mixed and acetic acid is removed while the system is heated and stirred, thereby allowing the polycondensation reaction to proceed.

The temperature within the system preferably needs to be 200°C or higher.

The number average degree of polymerization of the aromatic oligomer obtained by this reaction is determined by the molar ratio of the charged hydroxyarylcarboxylic acid and trimellitic anhydride or 4-acetoxyphthalic anhydride.

In order to react the aromatic oligomer used in the present invention with a thermoplastic polymer material having a glass transition temperature of 10°C or lower to obtain a graft copolymer and obtain TPE, the flow temperature of the aromatic oligomer must be 100°C or higher and 400°C or lower. The temperature is preferably 150°C or higher and 350°C or lower, and the molar ratio of trimellitic anhydride or acetoxyphthalic anhydride to acetoxyarylcarboxylic acid is 1/1.
Polycondensation may be carried out by mixing in a ratio of 1 to 1/10, preferably 1/1.5 to 1/8.

When the number of moles of acetoxyarylcarboxylic acid is smaller than that of trimellitic anhydride or acetoxyphthalic anhydride, the resulting aromatic oligomer has a low molecular weight, is easily thermally decomposed, and has a significantly lower flow temperature, making it difficult to use as a hard segment of TPE. If it is, the heat resistance of the resulting TPE will be lowered, which is not preferable.

Also, the number of moles of acetoxyarylcarboxylic acid is 1 per trimellitic anhydride or acetoxyphthalic anhydride.
When polycondensation is carried out by mixing the aromatic oligomer in excess of 0 times, the flow temperature of the resulting aromatic oligomer exceeds 400°C, which is close to the thermal decomposition temperature of the aromatic oligomer, resulting in poor moldability of the resulting TPE when used as a hard segment of TPE. This is not desirable because it worsens the

Furthermore, after pulverizing the obtained aromatic oligomer, using a solvent selected from acetone, tetrahydrofuran, N-methylpyrrolidone, chloroform, toluene, and pyridine,
After stirring and washing, filtration is preferred because monomers and dimers contained in the aromatic oligomer after polycondensation are mainly washed away and the thermal stability of the aromatic oligomer is improved.

The aromatic oligomer used in the present invention, that is, the aromatic oligomer having an acid anhydride at one end, is reacted as a grafting agent with various polymeric materials having a functional group capable of reacting with the acid anhydride. It is possible to improve the performance and functionality of.

In particular, it is 1/9 by weight of a thermoplastic polymer material with a glass transition temperature of 10°C or less and a functional group that can react with acid anhydrides.
A thermoplastic elastomer having high heat resistance can be produced by reacting at a ratio of 9 to 50/50 and synthesizing a graft copolymer.

The reaction method is not particularly limited, but a method of reacting by melt-kneading is preferred.

Next, as a method for producing the thermoplastic graft copolymer of the present invention, a polymer having a glass transition temperature of 10°C or lower and having a radical reactivity, and a polymer having a flow temperature of 100°C or higher and having a radical reactivity at one end. For example, a method of reacting an aromatic oligomer with an aromatic oligomer having a functional group.

Polymers containing radically reactive structural units used in the present invention include ethylene/propylene copolymer, ethylene/propylene/butadiene copolymer, ethylene/propylene/imprene copolymer, ethylene/propylene/1 , 5-hexadiene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene-dicyclopentadiene copolymer,
Examples include propylene/methylene norbornene copolymer, ethylene/propylene/ethylidene norbornene copolymer, and the like.

The aromatic oligomer used in the present invention, which has a flow temperature of 100° C. or higher, preferably 150° C. or higher, and has a functional group having radical reactivity at one end, is represented by the following maximum.

R"-COfX-Ar CO+TOR" (wherein, X is selected from O, S, Ar is a divalent arylene group,
When RIO is a radically reactive functional group, R20 is selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 20 carbon atoms, and when R20 is a radically reactive functional group, R20 is a radically reactive functional group. is an alkyl group of 1 to 10, carbon number of 6 to
selected from 20 aryl groups. n is 2 to 10 on average
It is. ) Examples of the functional group having radical reactivity include a group having an arylmaleimide structure. Preferably, (wherein R10, R40, and R50 are hydrogen and have 1 to 4 carbon atoms)
selected from the alkyl groups of ).

The aromatic oligomer can be produced by a polycondensation reaction using carboxyarylmaleimide or hydroxyarylmaleimide and hydroxyarylcarboxylic acid as raw materials. Preferably, it is produced by polycondensation by acetylating a hydroxyl group with an acetylating agent such as acetic anhydride or acetyl chloride, followed by deacetic acid removal. Note that even when X in the above formula is S, it can be manufactured in accordance with this method.

The aromatic oligomer used in the present invention, that is, the aromatic oligomer having a radically reactive functional group at one end, is reacted with various radically reactive polymeric materials as a grafting agent to improve the high performance of the polymeric material. It is not possible to improve the performance and functionality of the product.

In particular, a thermoplastic elastomer having high heat resistance can be produced by reacting with a thermoplastic polymer material having radical reactivity and a glass transition temperature of 10° C. or less to synthesize a graft copolymer.

The reaction method is not particularly limited, but a method of reacting by melt-kneading is preferred. In order to promote grafting, a radical initiator that is effective at the reaction temperature can be appropriately selected. Examples of the radical initiator include tertiary butyl hydroperoxide and cumyl hydroperoxide.

Next, as a method for producing the thermoplastic graft copolymer of the present invention, a polymer having a glass transition temperature of 10°C or lower and having an unsaturated double bond in its structure and a flow temperature of 1.
Examples include a method of reacting an aromatic oligomer having a functional group capable of reacting with an unsaturated double bond at one end at a temperature of 00° C. or higher.

Polymers with a glass transition temperature of 10°C or lower and having unsaturated double bonds in their structure used in the present invention include ethylene-propylene-butadiene copolymers, ethylene-propylene-butadiene copolymers, and ethylene-propylene-butadiene copolymers.
Examples include propylene/isoprene copolymer, ethylene/propylene/1,5 hexadiene copolymer, ethylene/propylene/dicyclopentadiene copolymer, ethylene/propylene/ethylidenenorbornene copolymer, and the like.

The aromatic oligomer used in the present invention, which has a flow temperature of 100°C or higher, preferably 150°C or higher, and has a functional group capable of reacting with an unsaturated double bond at one end, is preferably represented by the following general formula. It is something that

R'' -CO+X -A r -CO-□ R20 (wherein, X is selected from O, S, Ar is a divalent arylene group, and when R10 is a radically reactive functional group, R2
0 is hydrogen, alkyl group having 1 to 10 carbon atoms, 6 to 2 carbon atoms
When R21 is a radically reactive functional group, R10 is selected from an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms. n is 2 to 2 on average
It is IO. ) Preferred examples of the group having a functional group capable of reacting with an unsaturated double bond include a halomethylaryl group and a tertiary haloalkyl group. Particularly preferred is a halomethylaryl group.

The aromatic oligomer can be produced by a polycondensation reaction using halomethylarylcarboxylic acid and acetoxyarylcarboxylic acid as raw materials. Preferably, it is produced by polycondensation by acetylating a hydroxyl group with an acetylating agent such as acetic anhydride or acetyl chloride, followed by deacetic acid removal. Note that even when X in the above formula is S, it can be manufactured in accordance with this method.

The aromatic oligomer used in the present invention, that is, the aromatic oligomer having a functional group capable of reacting with an unsaturated double bond at one end, can be used as a grafting agent with various polymeric materials having an unsaturated double bond in its structure. By causing the reaction, it is possible to improve the performance and functionality of the polymer material.

In particular, it is possible to produce a thermoplastic elastomer with high heat resistance by reacting it with a thermoplastic polymer material having an unsaturated double bond in its structure and having a glass transition temperature of 10°C or lower to synthesize a graft copolymer. can.

Furthermore, the case where the main chain of the present invention is polyorganosiloxane will be described in detail.

The combinations of the reactive functional group of the main chain polyorganosiloxane and the reactive functional group of the side chain include a silicon-bonded amino group-containing organic group and an acid anhydride, and a silicon-bonded organic group containing an epoquine group. and a carboxylic acid group, a silicon-bonded hydrogen atom, and an unsaturated double bond-containing organic group.

The modified polyorganosiloxane used in the present invention is represented by the following general formula (IV).

R2R": In the formula, R', R2 and R3 have 1 to 3 carbon atoms, R is a hydrocarbon having 1 to 3 carbon atoms, and n=o to 2. R
4 is hydrogen, -X, -R' -X.

It is a group selected from NH-X3-R' -X2-0-X, -R'. Here, R' is selected from an amino group and an epoxy group, Xl is a hydrocarbon having 1 to 20 carbon atoms, and
2 and X3 are hydrocarbons having 1 to 10 carbon atoms. Further, m and n are selected so that the equivalent weight of the functional group is about 500 to 10,000, preferably about 2000 to 4000. ) Among these, preferable polyorganosiloxanes include those in which R', R2 and R8 are -CH,, C2H5,4
selected from, R4 is -X 2-NH-X , -
Examples include NH2.

Next, when the main chain is polyorcasiloxane, the aromatic oligomer that becomes the side chain is represented by the maximum (V) below.

(In the formula, X is selected from 03S, and one oligomer may contain a structural unit containing 0 and a structural unit containing S at the same time. Ar is a divalent arylene group. n is a number average of 2 to (10) Here, when the main chain polyorganosiloxane has an epoxy group as a reactive functional group, the side chain aromatic oligomer preferably has a carboxylic acid group at one end.

That is, in the formula (V), R'' is hydrogen, and the formula (V
) corresponds to the above-mentioned formula (II), and R', Ar, and n are also preferably those shown in formula (n).

Further, when the main chain polyorganosiloxane has an amino group as a reactive functional group, the side chain aromatic oligomer preferably has an acid anhydride group at one end.

That is, it is preferable that the formula (V) corresponds to the above-mentioned formula (III). Regarding R', R'', Ar, n, etc., the formula (
Those shown in II[) are preferred.

Furthermore, when the main chain polyorganosiloxane has a silicon-bonded hydrogen atom as a reactive functional group, the side chain aromatic oligomer used has an unsaturated double bond at one end.

That is, formula (V) is an organic group in which RIQ or R20 has an unsaturated double bond, has 3 to 20 carbon atoms, and may contain a heteroatom, in addition to the formula (III) described above. . When RIO is an unsaturated double bond-containing organic group, R20 is a group inert to the reaction, and when R'' is an unsaturated double bond-containing organic group, R10 is a group inert to the reaction.

To promote grafting, platinum or a platinum compound is added when the functional group of the polysiloxane is a silicon-bonded hydrogen atom and the functional group of the selected aromatic polymer is an unsaturated double bond. In the case of a combination of an epoxy group and a carboxylic acid group, it is preferable to add a phosphine catalyst, a tertiary amine, or the like. Also, 1-methyl-2-
General organic solvents such as pyrrolidone may be used if necessary.

Next, the case where the polymer having a glass transition temperature of 10° C. or lower is partially crosslinked will be described in detail.

Here, as the main chain having a glass transition temperature of 10° C. or lower and the aromatic oligomer having a flow temperature of 100° C. or higher, those described above can be used.

The method for producing the thermoplastic graft copolymer of the present invention involves using a polymer having a glass transition temperature of 10° C. or less and having a functional group capable of reacting with an aromatic oligomer with an organic peroxide and/or the functional group. Partially crosslinking with a compound having two or more functional groups in one molecule that can react with the polymer, and reacting with an aromatic oligomer having a flow temperature of 100°C or higher and having a functional group that can react with the polymer. It is characterized by:

As a particularly preferable manufacturing method, the glass transition temperature is 10
℃ or below, and a polymer having a functional group capable of reacting with a carboxylic acid group is partially treated in advance with an organic peroxide and/or a compound having two or more functional groups in one molecule capable of reacting with the functional group. After crosslinking, the flow temperature is 100℃
A method of reacting with an aromatic oligomer having a carboxylic acid group at one end, or a glass transition temperature of 10
℃ or below, and when reacting a polymer having a functional group capable of reacting with a carboxylic acid group with an aromatic oligomer having a carboxylic acid group at one end, organic peroxide and/or the functional group in one molecule may be reacted. Examples include a method of adding a compound having two or more reactive functional groups and partially crosslinking a polymer having a glass transition temperature of 10° C. or less to obtain a graft copolymer. Preferred functional groups that can react with this carboxylic acid group include the aforementioned glycidyl group, epoxy group, isocyanate group, hydroxyl group, and acetoxy group. Particularly preferred is a glycidyl group.

The organic peroxides used in the present invention have a decomposition temperature or a half-life of 100 to 220°C, and are succinic acid peroxide, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, p- -Chlorobenzoyl peroxide, 1-butylperoquine isobutyrate, t-butylperoxyisopropyl carbonate, t-butylperoxylaurate, 2,5-dimethyl-2°5-di(benzoylperoxy)hexane, t
-Butylperoxyacetate, di-t-butylshiba-
Oxyphthalate, t-butyl peroxymaleic acid,
Cyclohexanone peroxide, t-butylperoxybenzoate, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylperoxybenzoate
-butylcumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, 2,5 dimethyl-2,5-di(t-butylperoxy)hexyne 3, di-isopropylbenzene hydroperoxide,
Examples include p-menthane hydroperoxide and 2,5-dimethylhexane-2,5-dihydroquine peroxide.

The amount of organic peroxide used in the present invention is generally 10
The amount is 0.1 parts by weight or more and 5 parts by weight or less relative to 0 parts by weight. If it is less than 0.1 part by weight, partial crosslinking may not be sufficient;
Exceeding the weight part is not preferred because partial crosslinking will become significant and the resulting graft copolymer will not melt and flow, making melt molding impossible even at temperatures higher than the flow temperature of the aromatic polymer used.

In addition, when the amount of organic peroxide used in the present invention is used in combination with a compound containing two or more functional groups in one molecule that reacts with a carboxylic acid group for partial crosslinking, the amount of the organic peroxide to be used in the graft copolymer obtained is It is necessary to reduce the amount added to the extent that the aromatic oligomer melts and flows at a temperature higher than the flow temperature of the aromatic oligomer used in the above.

In the present invention, compounds having two or more functional groups capable of reacting with a functional group capable of reacting with a carboxylic acid group used in partially crosslinking a polymer having a glass transition temperature of 108C or lower include carboxylic acid Compounds having two or more functional groups in one molecule of at least one selected from a group, a hydroxyl group, and an amino group, such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimethenoic acid, hydroquinone, p-hydroxybenzoic acid acids, low molecular weight compounds such as m-hydroquinebenzoic acid, p-phenylenediamine, p-aminephenol, m-aminophel, p-aminobenzoic acid, m-aminobenzoic acid, and aromatic compounds represented by the following - maximum One or more compounds are selected from polyester oligomers and the like depending on the type of the functional group.

H is selected from 1 to 3 alkyl groups and phenyl groups, X is selected from O and S, and R1 and R2 may be the same or different. Different substituents may be attached to one benzene ring. p and q are integers of O to 2.

n is 2 to 10 on average. ) This aromatic polyester oligomer is produced using the same method as the aromatic oligomer having a carboxylic acid group at one end.
It can be synthesized by polycondensing n moles of hydroxyarylcarboxylic acid with (n-1) moles of acetic anhydride followed by deacetic acid removal.

Additionally, for the purpose of improving thermal stability, this aromatic polyester oligomer can be washed with a solvent such as methanol, ethanol, acetone, tetrahydrofuran, N-methylpyrrolidone, chloroform, or pyridine to remove monomers and dimers. preferable.

It is preferable to use these compounds in an amount that satisfies the degree of crosslinking such that the obtained graft copolymer melts and flows at a temperature higher than the flow temperature of the aromatic oligomer used.

The reaction method is not particularly limited, but a method of reacting by melt-kneading is preferred.

In either case, the kneading is carried out using a conventional kneading machine such as a Banbury mixer, a screw extruder, a twin screw extruder, a roll, a kneader, etc. as long as it can apply a high shear force at high temperature. It doesn't matter.

The reaction temperature is higher than the temperature at which the system is completely melted, that is, the polymer whose glass transition temperature is 10°C or lower is set to react with a functional group capable of reacting with an organic peroxide and/or a carboxylic acid group. When partially crosslinking with a compound having two or more in one molecule, the temperature is higher than the temperature of the organic peroxide used and/or the compound having the highest melting point among the compounds, and the Tg used is 10°C or lower. The temperature is preferably below the thermal decomposition temperature of the polymer. If the reaction temperature is lower than the melting point or flow temperature of the compound used, partial crosslinking will not proceed, which is undesirable, and if it exceeds the thermal decomposition temperature of a polymer with a Tg of 100C or less, the polymer will decompose during kneading or the molecular weight will decrease significantly. It is not desirable as it may have negative effects.

In addition, polymers with a glass transition temperature of 10°C or lower can be used with compounds having two or more functional groups in one molecule that react with functional groups that can react with organic peroxides and/or carboxylic acid groups, and with carboxylic acid at one end. When reacting with an aromatic oligomer having a group to simultaneously proceed with partial crosslinking and grafting, the temperature must be higher than the flow temperature of the aromatic oligomer used and lower than the thermal decomposition temperature of the polymer whose Tg is 10°C or lower. is preferred.

When the reaction temperature is below the flow temperature of the aromatic oligomer,
It is not preferable that the carboxylic acid of the aromatic oligomer and the polymer having a Tg of 10°C or less react with each other, making it difficult to obtain a graft copolymer. This is not preferable since the polymer decomposes during kneading and has adverse effects such as a significant decrease in molecular weight.

In order to promote grafting, a higher temperature within the above temperature range is preferred, a longer reaction time is preferred, and a larger shearing force is preferred. Furthermore, it is preferable to add triphenylphosphine, tertiary amine, etc. to promote grafting.

〔Effect of the invention〕

The graft copolymer of the present invention can be melt-molded at high temperatures, and exhibits good behavior as a rubber elastic body in the range from room temperature to extremely high temperatures, making it extremely useful as a thermoplastic elastomer with excellent heat resistance. be.

Therefore, oil cooler hose, air duct hose,
Various hose materials such as power steering hoses, control hoses, oil return hoses, heat-resistant hoses, various oil seals, sealing materials such as O-rings, packings, and gaskets, as well as various diaphragms, rubber plates, belts, oil level gauges, It has a wide range of applications and is useful for hose masking, sound insulation, etc.

〔Example〕

The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

Note that the measurement conditions for each physical property are as follows.

Tensile Test - Measurement was performed according to ASTM D638 using a tensile tester Tensilon EM-500 manufactured by Toyo Baldwin. However, regarding permanent elongation, when the elongation at break exceeded 600%, the film was held for IO minutes after being stretched by 300%, and the elongation was measured after 10 minutes of shrinkage.

Compression set test °--Measurement was carried out using a constant strain compression tester manufactured by Toyo Seiki Seisakusho in accordance with JIS K-6301.

Shore hardness ------- 1. Measurement was performed according to ASTM D-2240 using a Shore hardness meter manufactured by Toyo Seiki Seisakusho. The thickness of the sample was 4.2 plates, and measurements were taken at intervals of 15 seconds.

Flow temperature - Koka type flow tester C manufactured by Netakaguruma Seisakusho
F
The temperature at which the temperature reached 8000 poise was defined as the flow temperature.

Melt index -°°°-rpa Measured using a melt indexer manufactured by Lumi Toyo Seiki Seisakusho. (The conditions are shown in the table.) Example 1 According to the method described in Example 5 of JP-A-61-127709, an ethylene/methyl acrylate/crindyl methacrylate terpolymer (ethylene/methyl Acrylate/glycidyl methacrylate-1-= 35/63
/2 (weight ratio), M at 190℃ under 12.16kg load
I-8,7g/10min) was obtained.

The glass transition temperature of this polymer was measured using a stand-alone differential scanning calorimeter DSC-50 manufactured by Koguruma Seisakusho in a nitrogen atmosphere at a heating rate of 10,667 minutes.

From the obtained diagram, the endothermic start temperature was determined by the tangential method according to a conventional method and was taken as the glass transition temperature. Glass transition temperature is -33
,7℃. In addition, the heating loss curve of this polymer is
Stand-alone thermogravimetric measuring device TGA- manufactured by Takaguruma Seisakusho
The temperature was measured at a heating rate of IO'C/min under a nitrogen atmosphere at 50°C. This measurement revealed that this polymer was thermally stable up to around 350°C.

Next, an aromatic oligomer having a carboxylic acid group at one end was synthesized as follows. A 500-sized separable flask was equipped with an Ikari-type stirring blade, a three-way condenser, and a Dimroth cooling tube, and 0.4 mol (48.8 g) of benzoic acid was added.
Rose hydroxybenzoic acid 0.8 mol, (110,4 g)
, 0.88 mol (90 g) of acetic anhydride was charged. A cutout of a Teflon sheet was used for the packing between the top and bottom. Rotate the Ikari-type stirring blade at 120 rpm, introduce nitrogen from the three-way cock to create a nitrogen atmosphere, and with cooling water flowing through the Dimroth cooling tube, place the separable flask in an oil bath and heat the oil bath to 160°C. The temperature rose to . 2 while refluxing acetic anhydride while keeping the oil bath at 160°C.
A time acetylation reaction was performed. After the acetylation reaction was completed, the Dimroth condenser was quickly replaced with a Liebig condenser, and the temperature of the oil bath was raised to 260°C. 160℃ to 260℃
The time required to raise the temperature to 0C was about 40 minutes.

Thereafter, the temperature of the oil bath was maintained at 260° C., and acetic acid and acetic anhydride distilled from the system were collected through a Liebig condenser tube.

Recovery of acetic acid, etc. was carried out after replacing the beam with a Bitzchi cooling tube, and the polycondensation was terminated when 104 g of acetic acid, etc. were recovered in about 1 hour.

After the polycondensation was completed, the oligomer was taken out and finely pulverized using a pulverizer. The powder obtained weighed 130 g. This powder was washed with 10 times the amount (1300 g) of methanol in the following manner to remove low molecular weight components soluble in methanol. Add the above powder 13 to the 2β separable flask.
Pour 0 g and 1300 g of methanol, attach an Ikari-type stirring blade and a Simroth cooling tube, place the separable flask in an oil bath at 80°C so that the methanol refluxes within the system, and wash for 1 hour under methanol reflux. went. Immediately after washing, the oligomer was collected by filtration. The recovered oligomer was further dried in a vacuum dryer at 80° C. for 10 hours to obtain an aromatic oligomer having only a carboxylic acid group at one end. The amount of polymer obtained was 85.8 g, and the yield was 66%.

When the flow temperature of this purified oligomer was measured, it was 182
It was ℃. Next, the heating loss of this purified oligomer was measured at 10°C/10°C under a nitrogen atmosphere using the TGA-50 type device mentioned above.
The temperature was measured at a heating rate of 1 minute. This indicates that this purified oligomer is stable up to around 300°C. Also,
The oligomer exhibited optical anisotropy.

Next, the results of measuring the molecular weight distribution of this purified oligomer are shown. The measurement was carried out using Tosoh Corporation (HLC-8020) with a column size of 7.8 mm ID x 30 cm.The sample was prepared by dissolving the oligomer of 5μ in 5-tetrafluorophenol. was diluted to twice the volume with chloroform and pre-filtered with a 0645 μm filter.As the mobile phase, a mixture of tetrafluorophenol and chloroform (volume ratio of tetrafluorophenol/chloroform = 1/2.72) was used.
1) was used. The molecular weight of each peak was determined by preparative fractionation according to a conventional method and mass spectrometry, and the retention time was 54.
．． The peak at 48 minutes is as follows - up to n=1, and 52.
It was found that the peaks at 57 minutes, 51.35 minutes, 50, 47 minutes, and 49.85 minutes correspond to n=2.3.4.5, respectively.

By this measurement, the number average degree of polymerization of the oligomer is determined as -
The maximum was n=3.5. In addition, the Q value of the polymer (
Weight average molecular weight/number average molecular weight) was about 1.55.

However, in the above-mentioned molecular weight distribution measurement, since the high molecular weight component of the oligomer is not dissolved in tetrafluorophenol, the molecular weight distribution of only the portion dissolved in the filtered tetrafluorophenol is measured.

In order to more precisely measure the number average molecular weight of the aromatic oligomer, the number average molecular weight was determined by the chemical decomposition method described below. The chemical decomposition method referred to here refers to the aromatic oligomer being decomposed into monomer units by chemically cleaving the ester bonds of the oligomer using n-butylamine as a decomposition reagent in N-methylpyrrolidone solvent, and then using liquid chromatography to decompose the oligomer into monomer units. This method involves fixing and quantifying the decomposed components and determining the number average degree of polymerization from the number of end groups.

Specifically, 50 mg of the oligomer was put into an eggplant-shaped flask containing 40-N-methylpyrrolidone and 101 nl of n-butylamine, and a cooling tube was attached and the mixture was stirred with a magnetic cooler in an 80°C oil bath for 12 hours. Decomposition is carried out to convert the oligomer into N-butylbenzoic acid amide and N-butyl p-hydroxybenzoic acid amide, p
After removing excess n-butylamine with an evaporator, it was filtered through a membrane filter with a pore size of 0.45 microns, and this was used as a sample.

Measurement was carried out using a Tosoh high performance liquid chromatography system [pump is TO3OHCCPM, pump controller is TO3OHPX-8010, gradienter is TO3
OHGE-8000, dynamic mixer is TO3O
HMX-8010UV detector is TO3OHMX-
8010 (used at detection wavelength 254 nm), recorder is System Instruments Chroma Recorder 12
The column was TO5OHTSK-Gel 0DS-
120T], each component was eluted and quantified by a water-methanol gradient elution method.

The water used as a solvent was ion-exchanged water/acetic acid = 100015
(volume ratio), methanol used was Sumitomo Chemical (electronic industry grade methanol/acetic acid = 100015 (volume ratio)).Furthermore, the grand end conditions were that the concentration of the aqueous system was 75vo1% at 0 minutes and 60vo1% at 30 minutes. %, 0% in 50 minutes,
75% in 60 minutes (all concentrations were changed linearly)
The measurement was carried out.

When quantifying the amount of each component contained in the above sample under the above measurement conditions, parahydroxybenzoic acid/N-n-
Butyl p-hydroxybenzoic acid amide/N-n-butylbenzoic acid amide-1,0/3.2/1.0 (molar ratio), and the number average degree of polymerization of the oligomer is as follows - n=4. It was 2.

The ethylene/methyl acrylate/glycidyl methacrylate terpolymer described above and the above-mentioned having a carboxylic acid group at one end - the number average degree of polymerization expressed by the maximum n
= 3.5 (n = 4.2 by chemical decomposition method) aromatic oligomer was converted into ethylene/methyl acrylate/glycidyl methacrylate terpolymer/above aromatic oligomer/
Triphenylphosphine-90/1010.1 (
= 45g/15g/50mg), a new Rahoplast Mill model ME-15 manufactured by Toyo Seiki was equipped with an R-60 type mixer and a roller-type blade at 280°C under a nitrogen atmosphere at 120+p++n for 15%.
A graft copolymer was obtained by carrying out a melt crosstalk reaction for a minute. The graft copolymer thus obtained at 230°C and 10k
Ml at g load was 4.5 g/10 min.

Furthermore, the grafting efficiency of the obtained graft copolymer was analyzed and calculated by the method described below. 500 mg of the obtained graft copolymer was placed in 401 nl of N-methylpyrrolidone IO-n~dbutylamine by the chemical decomposition method described above to partially decompose the aromatic oligomer to form an ethylene/methyl acrylate/glycidyl methacrylate copolymer. To remove components, the mixture was precipitated in 500 ml of methanol and separated by filtration. The filtrate was concentrated using an evaporator to remove methanol and excess n-butylamine, and then filtered through a membrane filter with a pore size of 0.45 microns to prepare a sample.

This sample was analyzed by high performance liquid chromatography using the same method as described above, and each decomposed component was quantified. Calculations can be performed based on the ratio of N-n-butylbenzoic acid amide and p-hydroxybenzoic acid amide, which are decomposed from a portion of the aromatic oligomer.

Specifically, n is the number average degree of polymerization of the aromatic polymer used for N-n-butylbenzoic acid amide and p-hydroxybenzoic acid, which are determined as decomposition components, and y is the amount of aromatic oligomer reacted (wt%). ), the grafting efficiency is calculated as follows.

The proportion of aromatic oligomer reacted with the ethylene/methyl acrylate/glycidyl methacrylate copolymer is G,
Then, G, = (1-x) xloo (%), and when the reaction rate of the epoxy group of the ethylene-methyl acrylate-glycidyl methacrylate copolymer is G2, it is expressed as follows.

The grafting efficiency thus determined is shown in Table 1.

280'C150kg/cr of this graft copolymer
A press sheet with a thickness of 2.1 mm was created under a pressure of
Test pieces for measuring various physical properties were cut out from this press sheet, and the physical properties were measured. The results are shown in Table 1.

Examples 2 to 4 and Comparative Example 1 The ethylene/methyl acrylate/crine methacrylate terpolymer, aromatic oligomer having a carboxylic acid group at one end, and triphenylphosphine used in Example 1 are shown in Table 1. After obtaining a graft copolymer with the same composition as in Example 1, a press sheet was created,
Various physical properties were measured in the same manner as in Example 1. Table 1 shows the results.
Expressed in

Furthermore, the graft efficiency of the graft copolymers obtained in Examples 2 to 4 was determined by the method described in Example 1. The results are shown in Table 1.

The melt index (260'C, 10 kg) of the graft copolymers obtained in Example 3.4 was 81.
It was 1.15.3.

Example 5 An oligomer having a carbonic acid group at one end was synthesized using the same method as in Example 1. 0.4 mol of benzoic acid, 1.2 mol of parahydroxybenzoic acid, and 1.32 mol of acetic anhydride were charged, and acetylation and polycondensation were carried out.

The obtained oligomer was washed with methanol in the same manner as in Example 1, and vacuum dried to obtain a purified oligomer. The flow temperature of the purified oligomer was 202°C, and the number average degree of polymerization measured by GPC was n=3.9 according to the formula shown in Example 1. Moreover, the Q value was 1246. Moreover, the oligomer exhibited optical anisotropy.

Further, when the number average degree of polymerization of the oligomer was determined by the chemical decomposition method described in Example 1, n=4.8 at the maximum.

This purified oligomer and the ethylene/methyl acrylate/cricidyl methacrylate ternary copolymer used in Example 1 were mixed into ethylene/methyl acrylate/glycidyl methacrylate ternary copolymer/purified oligomer/triphenylphosphine-90/1. 010.1 (=45g1
A graft copolymer was obtained by melt-kneading the mixture at a weight ratio of 5 g (150 mg) under the same conditions as in Example 1. A press sheet was prepared from this graft copolymer in the same manner as in Example 1, and various physical properties were measured.

The results are shown in Table I.

Example 6 Using the ethylene/methyl acrylate/glycidyl methacrylate terpolymer used in Example 1 and the aromatic oligomer having a carboxylic acid group at one end used in Example 5, ethylene/methyl acrylate/glycidyl methacrylate was produced. Ternary copolymer/aromatic oligomer/triphenylphosphine=90wt%/lOwj%10.
At a mixing ratio of 1 phr, Ikegai Iron Works 30th generation twin screw extruder P
Using CM-30, the reaction was repeated five times at a cylinder temperature of 290° C., a screw rotation speed of 20 rpm, and a feed rate of 3 kg/hr (residence time of about 1 minute) to obtain a graft copolymer.

A press sheet was prepared from this graft copolymer in the same manner as in Example 1, and various physical properties were measured in the same manner as in Example 1.

The results are shown in Table 2.

Furthermore, this graft copolymer was applied to Toshiba Machine injection molding machine 1.
Using s-25EP-IA, a flat sheet of 35 mm x 110 mm x 2 mm was made by injection molding at a cylinder temperature of 280°C, and test pieces for measuring various physical properties were cut from this sheet and treated in the same manner as in Example 1. Physical properties were measured. The results are shown in Table 2.

Example 7 100 parts of the graft copolymer obtained in Example 6 and 50 parts of carbon black were mixed, and the same conditions were used except that the twin screw extruder described in Example 6 was used, except that the cylinder temperature was changed to 250 ° C. and melt blended. This graft copolymer composition was press molded and injection molded in the same manner as in Example 6, and various physical properties were measured in the same manner as in Example 1. The results are shown in Table 2.

Example 8 An aromatic oligomer having a carboxylic acid at one end was synthesized using the same method as in Example 1. Acetylation was carried out by preparing 0.3 mol of benzoic acid, 0.6 mol of parahydroxybenzoic acid, 0.3 mol of metahydroxybenzoic acid, and 1 mol of acetic anhydride.
Polycondensation was performed, and the resulting oligomer was pulverized, washed with methanol in the same manner as in Example 1, and vacuum dried to obtain a purified oligomer.

The flow temperature of the purified oligomer was 141°C, and the oligomer exhibited optical anisotropy.

The degree of polymerization was determined by the chemical decomposition method described in Example 1 and was found to be n=7.6 at maximum. Also, the para bond and meta bond of the hydroxybenzoic acid unit are p/m = 6.1
/1.5.

This purified oligomer and the ethylene/methyl acrylate/glycidyl methacrylate terpolymer used in Example 1 were mixed into ethylene/methyl acrylate/glycidyl methacrylate ternary copolymer/purified oligomer/triphenylphosphine=86/1410. 1 (=43
The mixture was melt-kneaded under the same conditions as in Example 1 at a weight ratio of 7g/7g150cm) to obtain a graft copolymer. A press note was prepared using this graft copolymer in the same manner as in Example 1, and various physical properties were measured. The results are shown in Table 2.

Example 9 An aromatic oligomer synthesized by the method described below was prepared as an aromatic oligomer having a carbonic acid group at one end. 4-Mercaptobenzoic acid copolymerized with rosehydroquine benzoic acid A11en, C.

F.H., McKay, D.D. Synthetic method for notothiosalicylic acid (Org, 5ynth, 1943.58
0~) and purified by sublimation to obtain 4-mercaptobenzoic acid.

Next, 0.1 mol (15.7 g) of 4-mercaptobenzoic acid
).

0.1 mol (13.8 g) of rosehydroquinobenzoic acid,
0.1 mole (12.2 g) of benzoic acid was dissolved in 300 moles of pyridine. Separately from this, 0.24 mol (49.44 g) of N,N'-dicyclohexylcarbosiimide,
2.5 g of para-toluenesulfonic acid and 200 ml of pyridine
and these solutions were mixed at room temperature.

While stirring this at room temperature, the reaction solution became cloudy in about 5 minutes. After stirring this for 24 hours, the precipitated aromatic oligomer and N,N synchlohexyl urea were collected by filtration. This was thoroughly washed with methanol using a Soxhlet extractor and dried. The amount of aromatic oligomer obtained was 21.2 g.

Elemental analysis of the aromatic oligomer obtained revealed that C
= 65.5wt%, H=3.6wt%, S=9.
fitvt%, O=21.1wt%, and the structure was determined to be the following formula.

When the flow temperature of the aromatic oligomer was measured, it was 193
．． The temperature was 1°C. Furthermore, when the heating loss of this polymer was measured in the same manner as in Example 1, it was found to be stable up to around 280°C. Moreover, the oligomer exhibited optical anisotropy.

Using the kneader described in Example 1, 2.5 g of the above aromatic oligomer, 2.5 g of the aromatic oligomer used in Example 1, 45 g of ethylene methyl acrylate glycidyl methacrylate, and 100 μg of triparatolylphosphine, A melt-kneading reaction was performed at 270° C. and 120 rpm for 5 minutes to obtain a graft copolymer.

A press sheet was prepared using this graft copolymer in the same manner as in Example 1, a test piece for compression set test was cut out, and the compression set was measured at 100°C for 170 hours, and it was found to be 62.5%. there were.

Example 10 An aromatic oligomer having a carboxylic acid group at one end was synthesized using the same method as in Example 9. First, 4-mercaptobenzoic acid 0.2 mol (31.4 g), benzoic acid 0.1
mol (12.2 g) was dissolved in pyridine 300-. Separately, 0.24 mol (49.44 g) of N,N'-dicyclohexylcarbodiimide and 2.5 g of para-toluenesulfonic acid were dissolved in pyridine 200- and these solutions were mixed at room temperature.

After stirring this reaction solution for 24 hours, it was filtered, washed with methanol, and dried in the same manner as in Example 9 to obtain an aromatic oligomer. Elemental analysis of the obtained aromatic oligomer revealed that C = 63.2 wt%, H = 3.7 wt%, S =
18.8 wt%, O=13.9 wt%, and the structure was determined to be the following formula.

When the flow temperature of the aromatic oligomer was measured, it was 195
．． It was 0°C. Moreover, the oligomer exhibited optical anisotropy.

5 g of the aromatic oligomer and the ethylene used in Example 1.
45 g of methyl acrylate/glycidyl methacrylate terpolymer and 50 μm of triparatolylphine were mixed at 280° C. at 12 rpm using the kneader described in Example 1.
A graft copolymer was obtained by performing a melt-kneading reaction for 4 minutes.

This graft copolymer was press-molded in the same manner as in Example 1, and the compression set (70° C., 22 hours) was measured and found to be 39.8%.

The graft copolymers obtained in Examples 1 to 10 were insoluble in chloroform, which is a good solvent for the ethylene/methyl acrylate/glycidyl methacrylate copolymer constituting the graft copolymer.

Example 11 Ethylene-propylene-diene monomer terpolymer (
EPDM (hereinafter referred to as EPDM) includes Nisprene E-301A (ethylene: 46 wt%, propylene + 49 wt%, synchropentadiene 5 wt%) manufactured by Sumitomo Chemical Co., Ltd.
%; iodine value=IO) was used. A 5,000 ml separable flask was equipped with a Teflon stirring blade, a 500-ml dropping funnel, and a Dimroth cooling tube, and 330 g of EPDM and 3,000 ml of toluene were charged therein. For the packing between the top and bottom,
A cutout of a Teflon sheet was used. Cooling water was poured into the Dimroth cooling tube, and the mixture was placed in an oil bath at 100° C. and heating was started to dissolve the EPDM.

After the EPDM was completely dissolved, the separable flask was lifted from the oil bath and cooled to room temperature. A solution of 0.15 mol (25 g) of metachloroperbenzoic acid dissolved in 500 g of toluene was added dropwise to the solution from the dropping funnel over a period of 1 hour.

After reacting at room temperature for 12 hours, the mixture was diluted with acetone until just before EPDM was precipitated (the amount of acetone required for this was approximately 500 mm), and this was poured into 301 mm of acetone with stirring to precipitate the polymer. I let it happen. The obtained crude product was heated and redissolved in 3,000 ml of toluene and precipitated again in acetone to purify the polymer. The obtained epoxidized EPDM was air-dried and then vacuum-dried. The amount of epoxidized EPDM obtained was 300 g, and the yield was 90%.

The epoxy equivalent of the epoxidized EPDM was measured by back titration. The epoxy equivalent of the epoxidized EPDM determined as a result was 5,000.

An aromatic oligomer having an acid anhydride group at one end was synthesized as follows. A 500-liter separable flask was equipped with an Ikari-type stirring blade, a three-way cock, and a Dimroth cooling tube, and 0.8 mol of parahydroxybenzoic acid (110,4
g) and 0.88 mol (90 g) of acetic anhydride were charged. A cutout of a Teflon sheet was used for the packing between the top and bottom. Rotate the Ikari-type stirring blade at 12 rpm, introduce nitrogen from the three-way cock to create a nitrogen atmosphere, and with cooling water flowing through the Dimroth cooling tube, place the separable flask in an oil bath and heat the oil bath to 160°C. The temperature rose to . Do not reflux the acetic anhydride while keeping the oil bath at 160°C.
A time acetylation reaction was performed. After the acetylation reaction was completed, in order to prevent acetic acid vapor, 0.4 mol (76.8 g) of trimellitic anhydride was quickly added under the oil bath, and the Dimroth condenser was quickly replaced with a Liebig condenser.
The oil bath was heated to 260°C. Thereafter, the temperature of the oil bath was maintained at 260° C., and acetic acid and acetic anhydride flowing out from the system were collected through a Liebig condenser. Recovery of acetic acid, etc. is carried out after replacing the Liebig cooling tube, and it takes about 1 hour to collect 98% of the
．． The polycondensation was terminated when 2 g of acetic acid and the like were recovered.

After the polycondensation was completed, the oligomer was taken out and finely pulverized using a pulverizer. The resulting powder weighed 142 g. This powder was washed with 5 times the amount (710 g) of dehydrated acetone as follows to remove low molecular weight components soluble in acetone. 2
142g and 710g of the above powder in a separable flask
Dehydrated acetone was charged, an Ikari-type stirring blade and a Simroth cooling tube were attached, and the separable flask was placed in an oil bath at 80'C so that the acetone was refluxed within the system, and the flask was washed under refluxing acetone for 1 hour. Immediately after washing was completed, the oligomers were collected. The recovered oligomer was further dried in a vacuum dryer at 80° C. for 10 hours to obtain an aromatic oligomer having only an acid anhydride group at one end. The obtained oligomer weighed 98 g and the yield was 69%.

The flow temperature of this purified oligomer was measured. 17
The temperature was 7°C. Next, the weight loss on heating of this purified oligomer was measured using a stand-alone thermogravimeter TGA-5 manufactured by Rotsu Seisakusho.
Measurement was carried out using Type 0 at a heating rate of 10° C./min under a nitrogen atmosphere. From this, it was found that this purified oligomer was stable up to around 280°C. Moreover, the oligomer exhibited optical anisotropy.

In order to confirm that one end of this purified oligomer was an acid anhydride derived from trimellitic anhydride, an infrared absorption spectrum was measured using the KBr method.

As a result, it was confirmed that the absorption was due to an acid anhydride near 1783 cm-', and one end was shown to be an acid anhydride.

Next, a method for estimating the number average degree of polymerization of this purified oligomer will be shown.

According to the method for producing parahydroquinobenzoic acid oligomer having a carbonic acid group at one end described in Example 1, benzoic acid/parahydroquinobenzoic acid-172 (molar ratio) to 1/
An aromatic oligomer was synthesized at a molar ratio of 4 (molar ratio), and the flow temperature was measured.

Furthermore, each aromatic polymer was dissolved in n-methylpyrrolidone.
Butylamine N-n-butylbenzoic acid amide, N-n
After decomposition into -butyl p-hydroxybenzoic acid amide and p-hydroxybenzoic acid, each decomposed component was quantified by high performance liquid chromatography according to a conventional method to determine the number average molecular weight. As a result, the number average degree of polymerization n expressed by - maximum
It has been found that the following relational expression holds between an aromatic oligomer having a carboxylic acid at one end and the flow temperature (FT+) of the aromatic oligomer.

FTin+ (0C) = 32n + 50 Applying this relational expression to the following reactive oligomer synthesized here and estimating the number average degree of polymerization, n = 3
．． 97 was obtained.

The epoxidized EPDM described above and the aromatic oligomer represented by the above formula having a trimellitic anhydride group at one end are epoxidized EPDM/the above aromatic oligomer=
At a weight ratio of 40g/10g, an R-60 type mixer and a roller-type blade were installed on a Laboplastomill model R-20 manufactured by Toyo Seiki Seisakusho, and the mixture was heated at 150°C for 2 hours.
Mixing was performed for 1 minute at 0 rpm.

The resulting mixture was further melt-kneaded using the same plastomill at 200° C. and 20 rpm for 3 minutes to obtain a graft copolymer. 260 of the graft copolymer thus obtained
'C, melt index at 10kg load is 3.0
g/10 minutes.

This graft copolymer was heated at 260°C at 150kg/cnr.
A press sheet with a thickness of 2.1 mm was prepared under the pressure of
Compression set was measured under the condition of time. In addition, tensile test pieces and Nyoar hardness test pieces were cut from the same press sheet, and 100% modulus, elongation at break, strength at break, permanent elongation, and Shore hardness were measured.

The results are shown in Table 3.

Example 12 A 5000-inch separable flask with a Teflon stirring blade,
Install nitrogen introduction pipe and Simroth cooling pipe, and install EPDM
150g (double bond is 0.06 equivalent), hexane 30
I prepared 00-. Pour cooling water into the Shimroth cooling pipe,
While nitrogen was introduced from the nitrogen introduction tube at a flow rate of 30-7 minutes, it was placed in an 80° C. oil bath and heating was started to dissolve the EPDM. After EPDM was completely dissolved, the mixture was further heated under reflux for 2 hours and then degassed.

Glycidyl methacrylate 0.12 mol (17.2 g)
, after adding 0.12 mol (15,2 g) of butyl acrylate, azobis(2,4-methylhaleronitrile)
A solution of 0.0032 mol (0.80 g) in 20-hexane was added. After reacting at hexane reflux temperature for 10 hours, it was diluted with acetone until just before EPDM was precipitated (the amount of acetone required for this was about 30 W). This was poured into 3M acetone with stirring. , the polymer was precipitated. The obtained crude product was heated and redissolved in 3000 °C of toluene and precipitated again in acetone to purify the polymer. The obtained epoxidized EPDM was air-dried and then vacuum-dried.

The amount of epoxidized EPDM obtained was 120 g, and the yield was 80%.

The epoxy equivalent of this glycidyl-modified EPDM was determined in Example 1.
It was measured in the same manner as in 1 and found to be 3070.

The aromatic oligomer having only a carboxylic acid group at one end was prepared by the method described in Example 1, with benzoic acid/parahydroxybenzoic acid = 0.4 mol/1.0 mol, and acetic anhydride 1.1 mol.
The same procedure was carried out except that moles were used. The flow temperature of the purified oligomer after methanol washing was 195°C. Also,
The oligomer exhibited optical anisotropy.

The glycidi-modified EPDM described above, the aromatic oligomer having only benzoic acid at one end, and triparatolylphosphine as a catalyst, the clincil-modified EPDM
/ aromatic oligomer / triparatolylphosphine
At a weight ratio of 40g/'10g10.05g, an R-60 type mixer and a roller-type plate were installed on a Laboplastomill model R20 manufactured by Toyo Seiki Seisakusho.
Melt kneading was performed at 230° C. and 200 rpm for 3 minutes.

The graft copolymer obtained in this way was
Melt index at kg load is 0.5 g/
It was 10 minutes.

A press sheet with a thickness of 2.1 nm was prepared from this graft copolymer at 260° C. under a pressure of 150 kg/cnf, and test pieces for measuring various physical properties were cut from this press sheet and the physical properties were measured. The results are shown in Table 3.

Example I3 Glycidyl-modified EPDM used in Example 12/aromatic oligomer/triparatolylphosphine 40g/
After obtaining a graft copolymer in the same manner as in Example 12 at a weight ratio of 10 g/O, lOg, a press sheet was prepared, and various physical properties were measured in the same manner as in Example 11. The results are shown in Table 3.

As described above, the graft copolymers obtained in Examples 11 to 13 were mixed with EPDM and epoxidized EPDM used in this example.
, was insoluble in toluene, which is a good solvent for glycidyl-modified EPDM.

Comparative Example 2 A press sheet was prepared from the ethylene/propylene/dicyclopentadiene terpolymer used in Example 11 in the same manner as in Example 11, and test pieces for measuring various physical properties were cut from this press sheet and the physical properties were measured. measurements were taken. The results are shown in Table 3.

Example 14 As the amino-modified polyorcasiloxane, BY16-872 (amino equivalent weight: 2000) manufactured by Toshi Dow Corning Silicone ■ was used.

It has the structure shown below.

CH3C1 (3CH3CH3) The aromatic oligomer used in Example 11 was used as the aromatic oligomer having an acid anhydride group at one end.

Next, a reaction was performed using the above amine-modified polysiloxane and an aromatic oligomer having an acid anhydride at one end. A 300TI separable flask was equipped with an Ikari-type stirring blade, a three-way cock, and a Dimroth cooling tube, and 25.0 g of the modified polysiloxane, 9 g of the aromatic oligomer,
8 g, lithium chloride 3.9 mg and I-methyl-2-
Pyrrolidone (NMP) 80- was charged. Nitrogen was introduced from a three-way cock, and the separable flask was placed in an oil bath and stirred so that NMP was refluxed in the system under a nitrogen stream. After 3 hours, the separable flask was removed from the oil bath, allowed to cool, and the solvent was decanted. The product was then washed twice with methanol under reflux for 1 hour. After the washing was completed, it was filtered to recover the product, the graft copolymer. Furthermore, this recovered material was dried at 1008C in a vacuum dryer to obtain a copolymer in which an aromatic oligomer was grafted onto polyorcasiloxane.

2508C150kg/cnf of this graft copolymer
A press sheet with a thickness of 2.1 mm was prepared under the pressure of 2.1 mm, and a test piece for compression set measurement was cut from this press sheet and measured at 70°C for 122 hours, and the compression set was 88. It was 0%. In addition, the Shore hardness of this graft copolymer at this time was 260°C.
, 10 kg load t4) Mr was 0.21 g/IO min.

Examples 15 to 18 According to the method described in Example 5 of JP-A-61-127709, ethylene/methyl acrylate/glycidyl methacrylate terpolymer (ethylene/methyl acrylate/glycidyl methacrylate = 35/63/
2 (weight ratio), 190℃, M under 2.16kg load
I = 8.7 g/10 min) was obtained. This polymer is E
It is called MA-1.

Further, 100 parts by weight of this EMA-1 and 3 parts by weight of dicumyl peroxide were kneaded in a Banbury mixer at 150 DEG C. for 10 minutes to obtain a partially crosslinked sample. This polymer is called EMA-2.

Next, an aromatic oligomer having a carboxylic acid group at one end was synthesized according to Example 1.

Table 4 shows the weight ratios of EMA-1 and EMA-2 mentioned above, aromatic oligomer 4 having a carboxylic acid group at one end, and triphenylphosphine (the total weight is 50
A R-60 type mixer and a roller-type plate were installed on a Toyo Seiki Labo Plastomill model ME-15 under a nitrogen atmosphere at 280 g.
A melt-kneading reaction was performed at 120 rpm for 10 minutes at ℃ to obtain a graft copolymer. Table 4 shows the melt index (232° C., 10 kg load) of the obtained graft copolymer.

This graft copolymer is 2808C150kg/c
A press sheet with a thickness of 2.1 is made under pressure of RL,
Test pieces for measuring various physical properties were cut out from this press sheet, and the physical properties were measured. The results are shown in Table 4.

Examples 19 to 22 An aromatic polyester oligomer having a hydroxyl group and a carboxylic acid group at both ends that react with the glycidyl group represented by the following - maximum was synthesized as follows, and using the same apparatus as in Example 1, para. Hydroxybenzoic acid 1.0 mol (138 g
), acetylation, polycondensation, and washing with methanol were performed in the same manner except that 0.8 mol (81.6 g) of acetic anhydride was charged.

The flow temperature of this purified oligomer after methanol washing is 2
The number average degree of polymerization determined by GPC as shown in Example 1 at 50° C. was n=6.3 at the above-mentioned maximum. Moreover, the oligomer exhibited optical anisotropy.

The EMA-1 shown in Example 15, the aromatic oligomer having a carboxylic acid group at one end, and the above-mentioned aromatic polyester oligomer were mixed with triphenylphosphine at the weight ratio shown in Table 4 (total weight was 50 g). A R-60 mixer and a roller type blade were installed in a Labo Plastomill model ME-15 manufactured by Toyo Seiki Seisakusho, and a melt-kneading reaction was carried out at 280° C. and 120 rpm for 10 minutes in a nitrogen atmosphere to obtain a graft copolymer. Obtained. The physical properties of the obtained graft copolymer were evaluated in the same manner as in Example 15.

The results are shown in Table 4.

The graft copolymers obtained in Examples 15 to 22 above were:
It was insoluble in chloroform, which is a good solvent for HMA-1 constituting the graft copolymer.

Example 23 A modified polysiloxane having a silicon-bonded hydrogen atom as a reactive functional group was synthesized as follows.

1.48 mol (440 g) of octamethylcyclotetrasiloxane purified by distillation from calcium hydride and 13.5
．． 0.55 mol (13.2 g) of 7-titramethylcyclotetranoxane was added to a Shimroth cooling tube, a three-way cock,
The mixture was placed in a 1000-Mitsuro flask equipped with a stirrer, and 3.2 g of trifluoromethanesulfonic acid was added thereto, followed by stirring at room temperature under a nitrogen atmosphere.

After 71 hours, 8.8 g of sodium hydrogen carbonate was added and stirred for 3 hours. After adding hexane, solids such as unreacted sodium hydrogen carbonate were filtered from the solution and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off and heated to 80°C.
It was vacuum dried. The obtained modified polysiloxane is GP
The number average molecular weight is 411635 due to C, 'H-Nli
The 5i-H equivalent was 2329 from IR.

Next, a reactive oligomer with an unsaturated double bond at one end
was synthesized as follows.

In a 1000-cm separable flask equipped with a Simroth condenser, a dropping funnel, and an Ikari-type stirring blade, under a nitrogen atmosphere, 0.78 mol (150 g) of trimellitic anhydride and 250 mol of 1,4 dioxane distilled from lithium aluminum hydride were added.
d and allylamine 0.78 mol (44.6 g)
was added dropwise from the dropping funnel. When the heat generation subsided, the mixture was heated in an oil bath at a temperature of 80° C. for 1 hour.

Next, 0.79 mol (80.2 g) of acetic anhydride was added, and the mixture was heated and stirred at reflux temperature for 2 hours. Thereafter, the solvent was distilled off, 1.2 mol (162 g) of parahydroxybenzoic acid and 1.3 mol (133 g) of acetic anhydride were added, and one end of the unsaturated double An aromatic oligomer (A) having a group having a bond was obtained.

The flow temperature of the oligomer was 162°C, and the oligomer exhibited optical anisotropy.

In the chemical decomposition method using butylamine described above, n is 3.8.
Met. Furthermore, a 1000-separable flask equipped with a Dimroth cooling tube, a three-way cock, and an Ikari type stirring blade,
Under a nitrogen atmosphere, 135 g of the above oligomer (A) and 320 g of triphenyl phosphite were added, and the oil bath temperature was 200.
The mixture was heated and stirred at ℃ for 6 hours.

After cooling, it was washed with methanol and vacuum dried at 80°C to obtain the following oligomer phenyl ester compound (B).

Next, the modified polysiloxane was reacted with an aromatic oligomer (B) having an unsaturated double bond at one end. 50% in a 100-nitro flask with a three-way stopcock
19.1 mg of water-containing 1% platinum/carbon was added, heated and degassed to dryness, and then the system was purged with nitrogen. 13.0 g of the oligomer (B) was added thereto, and the mixture was degassed and replaced with nitrogen. In a Laboplastomill, 36.2 g of the polysiloxane and the contents of the Nituro flask were mixed at 200°C and 20 rpm.
A time melt crosstalk reaction was performed to obtain a rubbery product.

Claims (2)

[Claims] (1) A polymer whose main chain has a glass transition temperature of 10°C or less, and whose side chain has a flow temperature of 10°C as defined below.
A thermoplastic graft copolymer that is an aromatic oligomer with a temperature of 0°C or higher. Flow temperature: 100kg heated and melted at a heating rate of 4℃/min
The temperature at which the melt viscosity is 48,000 poise when extruded from a nozzle with an inner diameter of 1 mm and a length of 10 mm under a load of /cm^2. (2) The method for producing a thermoplastic graft copolymer according to claim 1, characterized in that an aromatic oligomer containing 50% by weight or more of a structural unit represented by the following formula (I) is grafted. ▲There are mathematical formulas, chemical formulas, tables, etc.▼......(I) (In the formula, X is selected from O and S, and one oligomer may contain a structural unit containing O and a structural unit containing S at the same time. . Ar is selected from ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and R^1 and R^2 have a carbon number of 1 ~3 selected from alkyl groups and phenyl groups, R^1 and R^2 may be the same or different groups. Different groups may be attached to one benzene ring. p, q
is an integer from 0 to 2. )