CN1898272A - Ionomer, method for producing the same and molded article of the same - Google Patents

Abstract

An ionomer is characterized in that it is obtained by heat-treating metal compound particles having an average particle diameter of not more than 1 mum and a polymer having a functional group. The ionomer has rubber elasticity, flexibility and forming workability equivalent to those of conventional thermoplastic olefin elastomers, and also has good mechanical characteristics and good abrasion resistance. The ionomer is particularly excellent in tensile break strength, scratch resistance and glossiness. Also disclosed are a method for producing such an ionomer and a formed article made of such an ionomer.

Description

Ionomer and preparation method thereof and moulding product

Technical field

The present invention relates to mechanical properties, resistance to marring, glossiness, abrasion resistance, forming process, thermotolerances such as caoutchouc elasticity, flexibility, fracture tensile strength, have excellent weather resistance, be suitable as the ionomer and preparation method thereof and the moulding product of thermoplastic elastomer.

Background technology

In the past, the ethylene series thermoplastic elastomer is known have following several: ethylene series resin and olefin copolymer rubber mix are formed, and by linking agent make ethylene series resin and olefin copolymer rubber part crosslinked form etc.The thermotolerance of described ethylene series thermoplastic elastomer; weathering resistance; winter hardiness and forming process excellence; and be the cheaper material of cost; particularly in fields such as trolley parts; as the equivalent material that turns to the metal parts of main purpose with light weight; to improve component life and the equivalent material of the RIM polyurethane part that is main purpose of reducing cost; to simplify manufacturing procedure and the property of can be recycled and the equivalent material of the vulcanized rubber that is main purpose of reducing cost; perhaps to improve component life and the environment of preserving our planet is the attention that the equivalent material etc. of the soft PVC of main purpose is subjected to people, the demand of this ethylene series thermoplastic elastic also increases year by year.

Yet the anti-surface tear (resistance to marring) of ethylene series thermoplastic elastomer in the past is low, therefore is not suitable for making the material that needs skin materials such as the moulding of resistance to marring product, for example wainscot, Console.

Recently, someone proposes: the ethylene series thermoplastic elastomer of resistance to marring excellence is by the ethylene series random copolymers and the crosslinked metal ion of this ethylene series random copolymers is formed, and wherein the ethylene series random copolymers is (for example with reference to the patent documentation 1) that ethene, alpha-olefin and the unsaturated monomer copolymerization with functional group obtain.This ethylene series thermoplastic elastomer for example can obtain by above-mentioned ethylene series random copolymers and metallic compound are implemented dynamic thermal treatment.This ethylene series thermoplastic elastomer is to have and in the past same caoutchouc elasticity, flexibility and the forming process of ethylene series thermoplastic elastomer, and mechanical characteristics and abrasion resistance well, the ethylene series thermoplastic elastomer of resistance to marring excellence particularly.

But, even the ethylene series thermoplastic elastomer of above-mentioned excellence also will require its fracture tensile strength, resistance to marring and glossiness more excellent.

As mentioned above, ethylene series thermoplastic elastomer in the above-mentioned patent documentation 1 has excellent character, but by " unsaturated monomer " preparation ethylene series random copolymers of using as monomer the time, must shelter and take off and shelter with specific functional group, therefore should preparation cumbersome.

Patent documentation 1: TOHKEMY 2003-82023 communique

Summary of the invention

The present invention's problem is in view of the aforementioned technical background finished, its purpose be to provide ionomer and preparation method thereof with and the moulding product, described ionomer has and in the past same caoutchouc elasticity, flexibility and the forming process of ethylene series thermoplastic elastomer, and mechanical characteristics and abrasion resistance well, particularly fracture tensile strength, resistance to marring and glossiness excellence.

Another object of the present invention is to provide the preparation method of ionomer and the ionomer that obtains by above-mentioned ionomer preparation method, the preparation method of this ionomer has and same caoutchouc elasticity, flexibility and the forming process of ethylene series thermoplastic elastomer in the past, and mechanical characteristics and abrasion resistance well, the ethylene series process for preparation of thermoplastic elastomer of resistance to marring excellence particularly, can easily prepare the ethylene series random copolymers by employed monomer in the polymerization.

For solving above-mentioned problem, the invention provides following ionomer and preparation method thereof and moulding product.

[1] ionomer (first scheme of ionomer of the present invention), this ionomer is that 1 μ m or following metal compound particles obtain with the polymer reaction with functional group by making median size.

[2] ionomer of [1], wherein the ratio of above-mentioned metal compound particles is 0.01～10 mass parts with respect to the above-mentioned polymkeric substance with functional group of 100 mass parts.

[3] ionomer of [1] or [2], the metal ingredient in the wherein above-mentioned metal compound particles contains at least a metal that is selected from sodium, magnesium, calcium, zirconium, zinc and aluminium.

[4] ionomer of [1] or [2], wherein above-mentioned metal compound particles contains zinc oxide.

[5] each ionomer in [1]～[4], wherein above-mentioned polymkeric substance with functional group are that ethene, carbonatoms are 3～10 alpha-olefin, have an ethylene series random copolymers that the unsaturated monomer of functional group and non-conjugated diene copolymerization as required obtain.

[6] ionomer of [5], this functional group in the wherein above-mentioned unsaturated monomer with functional group is carboxyl, hydroxyl, epoxy group(ing) or sulfonic group.

[7] ionomer of [5], wherein above-mentioned unsaturated monomer with functional group is the functionality ring compound shown in the following general formula (1):

[changing 1]

(in the general formula (1), R ¹Expression hydrogen atom or carbonatoms are 1～10 alkyl, Y ¹, Y ²And Y ³Independent respectively expression hydrogen atom, carbonatoms be 1～10 alkyl or-COOH, Y ¹, Y ²And Y ³In at least one be-COOH, in addition, Y ¹, Y ²And Y ³In two or morely be-during COOH, they can be the acid anhydrides (CO-(O)-CO-), o is 0～2 integer, p is 0～5 integer) of interconnection formation.

[8] ionomer of [5], wherein above-mentioned ethylene series random copolymers are that 3～10 alpha-olefin, the functionality ring compound shown in 0.01～5 mole of above-mentioned general formula of % (1) and the copolymerization of 0～10 mole of % non-conjugated diene obtain by 35～94.99 moles of % ethene, 5～50 moles of % carbonatomss.

[9] preparation method of ionomer (preparation method's first scheme of ionomer of the present invention), this method has following operation: in median size is in the presence of 1 μ m or the following metal compound particles, and the polymkeric substance with functional group is heat-treated or dynamically thermal treatment.

[10] moulding product, these moulding product are that the formed material that contains each ionomer in [1]～[8] obtains by the method for forming moulding that is selected from injection moulding, extrusion moulding, vacuum forming, powder slush moulding method, rolling-molding method, transfer molding method, solvent casting method and extrusion forming method.

[11] preparation method of ionomer (preparation method's alternative plan of ionomer of the present invention), this method is that ethylene series random copolymers and metallic compound are implemented dynamic thermal treatment, wherein said ethylene series random copolymers is that to make ethene, carbonatoms be that 3～10 alpha-olefin and the functionality ring compound copolymerization shown in the following general formula (2) obtain

[changing 2]

(in the general formula (2), n is 0 or 1, R ¹, R ², R ³And R ⁴Independent respectively expression hydrogen atom, halogen atom or univalent organic group).

[12] preparation method of the ionomer of [11], in the wherein above-mentioned general formula (2), R ¹, R ²And R ³Respectively independent, for hydrogen atom or carbonatoms 1～20 alkyl.

[13] preparation method of the ionomer of [11] or [12], in the wherein above-mentioned general formula (2), R ¹, R ²And R ³All be ethyl, or R ¹, R ²And R ³In one be that the tertiary butyl, two are methyl.

[14] preparation method of each ionomer in [11]～[13], in the wherein above-mentioned general formula (2), R ⁴Be methyl.

[15] preparation method of each ionomer in [11]～[14], wherein, above-mentioned ethylene series random copolymers is that 3～10 alpha-olefin, the functionality ring compound copolymerization shown in 0.01～5 mole of above-mentioned general formula of % (2) generate by 35～94.99 moles of above-mentioned ethene of %, 5～50 moles of above-mentioned carbonatomss of %, and is under 10～2000/ seconds the condition above-mentioned ethylene series random copolymers of 100 mass parts and the above-mentioned metallic compound of 0.1～20 mass parts to be carried out dynamic thermal treatment in 120～350 ℃ of temperature, shearing rate.

[16] preparation method of each ionomer in [11]～[15], wherein, above-mentioned ethylene series random copolymers also can generate the non-conjugated diene copolymerization except that the functionality ring compound shown in above-mentioned ethene, above-mentioned alpha-olefin and the above-mentioned general formula (2).

[17] preparation method of the ionomer of [16], wherein, above-mentioned ethylene series random copolymers can also be with 10 moles of % or following non-conjugated diene copolymerization and generate except that the functionality ring compound shown in above-mentioned ethene, above-mentioned alpha-olefin and the above-mentioned general formula (2).

[18] preparation method of each ionomer in [11]～[17], wherein, above-mentioned metallic compound is metal oxide or metal hydroxides.

[19] ionomer (alternative plan of ionomer of the present invention), this ionomer is obtained by the preparation method of each ionomer in [11]～[18].

[20] preparation method of ionomer composition, this method is: 120～350 ℃ of temperature, shearing rate is to 100 mass parts ethylene series random copolymerss and 0.1～20 mass parts metallic compound under 10～2000/ seconds the condition, 300 mass parts or the following macromolecular compound that is selected from thermoplastic resin and rubber and/or 100 mass parts or following tenderizer are implemented dynamic thermal treatment, wherein said ethylene series random copolymers is by 35～94.99 moles of % ethene, 5～50 moles of above-mentioned carbonatomss of % are 3～10 alpha-olefin, 0.01 functionality ring compound shown in～5 moles of following general formulas of % (2) and the copolymerization of 0～10 mole of % non-conjugated diene obtain

[changing 3]

(in the general formula (2), n is 0 or 1, R ¹, R ², R ³And R ⁴Independent respectively expression hydrogen atom, halogen atom or univalent organic group).

[21] ionomer composition, said composition is obtained by the preparation method of the ionomer composition of [20].

First scheme of ionomer of the present invention has and the same caoutchouc elasticity of ethylene series thermoplastic elastomer in the past, flexibility and forming process, and mechanical characteristics and abrasion resistance are good, fracture tensile strength particularly, resistance to marring and glossiness excellence, pass through injection moulding easily, extrusion moulding, vacuum forming, powder slush moulding method, rolling-molding method, the transfer molding method, solvent casting method and extrusion forming method etc. are processed, has performance as the excellence of thermoplastic elastomer, can obtain having good caoutchouc elasticity, flexibility and mechanical properties, particularly fracture tensile strength, the moulding product of resistance to marring and glossiness excellence.Moulding product of the present invention can be used as and are connected with common ethylene series vulcanized rubber moulding product, the body formed product of ethylene series thermoplastic elastic or laminated.The preparation method's of ionomer of the present invention first scheme can advantageously be made first scheme of above-mentioned ionomer.

The preparation method's of ionomer of the present invention alternative plan is to being that ethylene series random copolymers and the metallic compound that 3～10 alpha-olefin and specific functionality ring compound copolymerization obtain carries out dynamic thermal treatment by ethene, carbonatoms, therefore can obtain having and in the past same caoutchouc elasticity, flexibility and the forming process of ethylene series thermoplastic elastomer, simultaneously mechanical characteristics and abrasion resistance well, the ionomer of resistance to marring excellence particularly.And above-mentioned specific functionality ring compound uses the functionality ring compound shown in the above-mentioned general formula (2), therefore can easily prepare the ethylene series random copolymers by this functionality ring compound, can make preparation section efficient height.In addition, the alternative plan of ionomer of the present invention is the ionomer that the alternative plan by the preparation method of ionomer of the present invention obtains, therefore, have and in the past same caoutchouc elasticity, flexibility and the forming process of ethylene series thermoplastic elastomer, simultaneously mechanical characteristics and abrasion resistance well, resistance to marring excellence particularly.

The accompanying drawing summary

[Fig. 1] is the figure of the infrared absorption spectrum of the ethylene series random copolymers (F) that obtains among the embodiment of expression.

Embodiment

Below specify and implement preferred plan of the present invention (hereinafter referred to as " embodiment "), but the present invention is not limited to following embodiment, can be understood as without departing from the spirit and scope of the present invention, can be according to the suitable in addition design alteration of those skilled in the art's conventional knowledge, improvement etc.

Below the preparation method's of first scheme of ionomer of the present invention, ionomer of the present invention first scheme and the embodiment of moulding product of the present invention are described.The embodiment of first scheme of ionomer of the present invention is to be that 1 μ m or following metal compound particles (hereinafter referred to as " specific metal compound particles ") obtain with the polymer reaction with functional group by making median size.Polymkeric substance with functional group preferably uses ethylene series random copolymers (hereinafter referred to as " specific contain functional group's multipolymer "), and this multipolymer is that ethene, carbonatoms are that 3～10 alpha-olefin and the compound copolymerization with functional group obtain at least.

[specific contain functional group's multipolymer]

The specific of ionomer that is used for obtaining the present embodiment contains the preferred ethene that uses of functional group's multipolymer as monomer component.The usage ratio of ethene preferably accounts for 35～94.99 moles of % of whole monomer components, more preferably 40～89.99 moles of %, preferred especially 45～84.99 moles of %.When the usage ratio of ethene is lower than 35 moles of %, be difficult to and functionality ring compound described later copolymerization.On the other hand, the usage ratio of ethene surpasses 94.99 moles of %, then is difficult to obtain as the necessary caoutchouc elasticity of thermoplastic elastomer.

Specific contains in functional group's multipolymer, and it is 3～10 alpha-olefin (hereinafter referred to as " specific alpha-olefin ") that monomer component preferably uses carbonatoms.By using carbonatoms is 10 or following alpha-olefin, and this alpha-olefin and other monomeric copolymerization are good.The object lesson of specific alpha-olefin has: propylene, 1-butylene, 1-amylene, 4-methyl-amylene-1,1-hexene, 1-heptene, 1-octene, 1-decene etc.Wherein, preferred propylene, 1-butylene, 1-hexene, 1-octene, further preferred propylene, 1-butylene.These compounds can use independent a kind or with 2 kinds or above being used in combination.

The usage ratio of specific alpha-olefin is preferably 5～50 moles of % of whole monomer components, more preferably 10～45 moles of %, preferred especially 15～40 moles of %.When the usage ratio of specific alpha-olefin is lower than 5 moles of %, be difficult to obtain as the necessary caoutchouc elasticity of thermoplastic elastomer.And the usage ratio of specific alpha-olefin surpasses 50 moles of %, and then the elastomeric weather resistance of gained may reduce.

Specific contains in the functional polymer, and monomer component preferably uses the unsaturated monomer (hereinafter referred to as " containing functional group's unsaturated monomer ") with the functional group that can form ionomer.This contains functional group's unsaturated monomer and preferably has carboxyl, hydroxyl, epoxy group(ing) or sulfonic group as functional group.The described functional group's unsaturated monomer that contains preferably uses the functionality ring compound shown in the above-mentioned general formula (1) (hereinafter referred to as " specific functionality ring compound ").

Represent in the general formula (1) of specific functionality ring compound R ¹For hydrogen atom or carbonatoms are 1～10 alkyl, Y ¹, Y ²And Y ³Respectively independent, for hydrogen atom, carbonatoms be 1～10 alkyl or-COOH, Y ¹, Y ²And Y ³In at least one be-COOH Y ¹, Y ²And Y ³In two or morely be-during COOH, they can be the acid anhydrides (CO-(O)-CO-) of interconnection formation.Here, carbonatoms is that the object lesson of 1～10 alkyl has: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl.Repeat number o is 0～2 integer.This repeat number o is 3 or when above, this ring compound is difficult to and other monomer copolymerization.Repeat number p is 0～5 integer.

Described specific functionality ring compound can make cyclopentadiene and contain functional group's unsaturated compound and carry out condensation and prepare by Diels-Alder reaction.The object lesson of specific functionality ring compound has: 5,6-dimethyl-5,6-dicarboxyl-two ring [2.2.1]-2-heptene, 5,6-diethyl-5,6-dicarboxyl-two ring [2.2.1]-2-heptene, 5,6-dimethyl-5,6-two (carboxyl methyl)-two ring [2.2.1]-2-heptene, 5,6-diethyl-5,6-two (carboxyl methyl)-two ring [2.2.1]-2-heptene, 5-methyl-5-carboxyl-two ring [2.2.1]-2-heptene, 5-ethyl-5-carboxyl-two ring [2.2.1]-2-heptene, 5-carboxyl-5-carboxyl methyl-two ring [2.2.1]-2-heptene, 5-methyl-5-carboxyl methyl-two ring [2.2.1]-2-heptene, 5-ethyl-5-carboxyl methyl-two ring [2.2.1]-2-heptene, 8,9-dimethyl-8,9-dicarboxyl-Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecylene, 8,9-diethyl-8,9-dicarboxyl-Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecylene, 8-methyl-8-carboxyl-Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecylene, 8-ethyl-8-carboxyl-Fourth Ring [4.4.0.1 ^2,5.1 ^7,10]-3-dodecylene etc.

The usage ratio that contains functional group's unsaturated monomer is preferably 0.01～5 mole of % of whole monomer components, more preferably 0.01～4 mole of %.When the usage ratio that contains functional group's unsaturated monomer was lower than 0.01 mole of %, the cross-linking density of gained ionomer was low, and physical strength and thermotolerance also reduce easily.And the usage ratio that contains functional group's unsaturated monomer is when surpassing 5 moles of %, and the cross-linking density of gained ionomer is too high, hardness is too high, becomes fragile, and is not preferred.

Specific contains in functional group's multipolymer, except that above-mentioned monomer component, can use non-conjugated diene conduct monomer component arbitrarily.The object lesson of this non-conjugated diene has: 1, the 4-hexadiene, 1, the 6-hexadiene, 1, straight chain non-annularity diene such as 5-hexadiene, the 5-methyl isophthalic acid, the 4-hexadiene, 3, the 7-dimethyl-, the 6-octadiene, 5,7-dimethyl-octa-1, the 6-diene, 3,7-dimethyl-1, the 7-octadiene, 7-methyl suffering-1, the 6-diene, the non-annularity diene of side chains such as dihydromyrcene, tetrahydroindene, the methyl tetrahydroindene, dicyclopentadiene, two ring [2.2.1]-heptan-2, the 5-diene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-propenyl-2-norbornylene, 5-isopropylidene-2-norbornylene, 5-cyclohexylidene-2-norbornylene, ester ring type diene such as 5-vinyl-2-norbornylene etc.These compounds can use independent a kind or with 2 kinds or above being used in combination.In the above-mentioned non-conjugated diene there be preferred compound: 1, and 4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene etc.The usage ratio of non-conjugated diene is preferably 0～10 mole of % of whole monomer components.The usage ratio of this non-conjugated diene surpasses 10 moles of %, and then the weather resistance of gained ionomer may reduce.

Specific contain the weight-average molecular weight Mw that functional group's multipolymer measures by gel permeation chromatography (GPC) and be generally 1,000～3 through polystyrene conversion, 000,000, preferred 3,000～1,000,000, further preferred 5,000～700,000.Specific contain the melt flow rate (MFR) (MFR) that functional group's multipolymer measures be preferably 0.01～100g/10 minute, more preferably 0.05～50g/10 minute under the condition of 230 ℃ of temperature, load 10kg.The specific second-order transition temperature that contains functional group's multipolymer is-90～50 ℃, preferred-70～10 ℃ especially.The specific functional group's multipolymer that contains can also be the oil extended polymer that is added with tenderizer when polymerization.

The described specific functional group's multipolymer that contains can be by known suitable polymerization process preparation, and concrete preparation method is not particularly limited, and for example can preferably utilize the method for TOHKEMY 2001-247629 communique.

[specific metal compound particles]

The specific metal compound particles of using among the present invention is its metal ingredient and specific contains functional group in functional group's multipolymer by ionic linkage, at the material of this specific intermolecular formation crosslinking structure that contains functional group's multipolymer.The median size of the metal compound particles that this is specific is 1 μ m or following, preferred 0.8 μ m or following.Here, median size is the mean value of the one-level particle diameter obtained from the photograph image that uses transmission electron microscope to take.When using the excessive metallic compound of median size, physical strength and resistance to marring reduce easily.

Can use metal oxide, metal hydroxides, metal-salt and metal complex etc. as the metallic compound that constitutes specific metal compound particles.The object lesson of the metal ingredient in the described metallic compound has: the metal of lithium, potassium, sodium, aluminium, zirconium, magnesium, calcium, barium, caesium, strontium, rubidium, titanium, zinc, copper, iron, tin, lead and other elements periodictable the I～VIII family.Wherein preferred sodium, magnesium, calcium, zirconium, zinc, aluminium.

The object lesson that constitutes the metal oxide of specific metal compound particles has: CuO, MgO, BaO, ZnO, Al ₂O ₃, Fe ₂O ₃, SnO, CaO, TiO ₂, ZrO ₂Deng.In addition, the object lesson that constitutes the metal hydroxides of specific metal compound particles has: LiOH, NaOH, KOH, Cu (OH) ₂, Cu ₂O (OH) ₂, Mg (OH) ₂, Mg ₂O (OH) ₂, Ba (OH) ₂, Zn (OH) ₂, Sn (OH) ₂, Ca (OH) ₂Deng.These metallic compounds can use independent a kind or with 2 kinds or above being used in combination.In order to improve the specific dispersiveness that contains functional group's multipolymer, the specific metal compound particles that contains these metallic compounds can be the particle of handling through silane coupling agent, higher fatty acid.

The usage ratio of specific metal compound particles the contain functional group multipolymer specific with respect to 100 mass parts is generally 0.01～10 mass parts, preferred 0.05～9 mass parts, preferred especially 0.1～8 mass parts.When this ratio was lower than 0.01 mass parts, the cross-linking density of gained ionomer was low, and physical strength and resistance to marring reduce easily.On the other hand, when this ratio surpassed 10 mass parts, the cross-linking density of gained ionomer was too high, and hardness is too high, becomes fragile, and is not preferred.

In the ionomer of the present embodiment, in order to improve specific metal compound particles and specific Combination that contains functional group's multipolymer and the thermotolerance that improves the gained ionomer, except that specific metal compound particles, the metal-salt that can also add carboxylic acid is as activator.The metal-salt of carboxylic acid preferably uses monocarboxylic metal-salt, and further preferred this carboxylic acid is a carbonatoms 3～23.The object lesson of described carboxylic acid has: propionic acid, vinylformic acid, butyric acid, methacrylic acid, valeric acid, caproic acid, sad, 2 ethyl hexanoic acid, capric acid, palmitinic acid, tetradecanoic acid, lauric acid, stearic acid, oleic acid, mountain Yu acid, naphthenic acid, phenylformic acid etc.Metal ingredient in the metal-salt that uses as activator can suitably be selected use from the example of the metal ingredient the specific metal compound particles, preferably with specific metal compound particles in the metal-salt of the congener metal ingredient of metal ingredient.

Usage ratio the contain functional group multipolymer specific with respect to 100 mass parts of the metal-salt that uses as activator is generally 0.3～20 mass parts, preferred 1～15 mass parts.This ratio is lower than 0.3 mass parts, then can not give full play to and use the effect that activator brought, and this ratio surpasses 20 mass parts, and then the oil-proofness of gained ionomer and physical strength significantly reduce.

[ionomer]

The ionomer of the present embodiment can be in specific metal compound particles and the activator that uses as required in the presence of, by functional group's multipolymer is heat-treated to specific containing or dynamically thermal treatment, preferred dynamic thermal treatment obtain.Here, " dynamically thermal treatment " be meant the processing that applies shearing force and the processing of heat treated two aspects.Normally used melting mixing device carried out when described dynamic thermal treatment for example can be used preparation or processing resin or elastomerics.This melting mixing device can be that intermittent type also can be a continous way.The object lesson of melting mixing device has: intermittent type melting mixing devices such as open mixing roller, non-open type Banbury stirrer, kneader, continous way melting mixing devices such as single shaft forcing machine, rotary-type in the same way continous way biaxial extruder, reverse rotation type continous way biaxial extruder.

The dynamic thermal treatment of carrying out for the ionomer for preparing the present embodiment preferably to containing of preparing in advance the specific activator that contains functional group's multipolymer, specific metal compound particles and use as required mixture carry out, concrete method has the method for following (1) and (2).

(1), the mixture that contains the specific activator that contains functional group's multipolymer, specific metal compound particles and use is as required implemented to shear continuously the dynamic thermal treatment of heating by biaxial extruder.

(2) by the intermittent type kneader mixture that contains the specific activator that contains functional group's multipolymer, specific metal compound particles and use is as required implemented to shear the dynamic thermal treatment of heating.

Dynamic heat treated treatment condition are according to the kind of the employed specific fusing point that contains functional group's multipolymer, specific metal compound particles, the kind of melting mixing device etc. and different, treatment temp is 80～350 ℃, preferred 100～300 ℃, treatment time is 20 seconds～320 minutes, preferred 30 seconds～25 minutes.In addition, the shearing force that mixture is applied is shearing rate 10～2000/ seconds, preferred 100～1000/ seconds.

In the present embodiment, the thermal treatment of implementing in order to obtain ionomer is except that dynamic thermal treatment, can also utilize in appropriate solvent, in the presence of specific metal compound particles and the activator that uses as required, to the specific method that functional group's multipolymer is heat-treated that contains, its concrete grammar is the method for following (3).

(3) under heating, the specific functional group's multipolymer that contains is dissolved in the solution that obtains in the appropriate solvent and specific metal compound particles and the activator that uses as required are dissolved or dispersed in the solution or the dispersion liquid that obtain in the appropriate solvent and mixes, from the gained mixed solution, remove the method for desolvating.

The solvent that uses in the method for above-mentioned (3) is not particularly limited, consider from the angle that contains functional group's multipolymer that easy dissolving is specific, for example preferably use aliphatic hydrocarbon, ester ring type hydro carbons, aromatic hydrocarbons and their halogenide, its object lesson has: butane, pentane, hexane, heptane, 2-butane, 2-methyl-2-butane, pentamethylene, methylcyclopentane, hexanaphthene, octane-iso, benzene,toluene,xylene, chlorobenzene, methylene dichloride, ethylene dichloride etc.When employed specific metal compound particles and activator hang down the solvability of above-mentioned solvent, can be prepared into specific metal compound particles and activator are scattered in dispersion liquid in the solvent with suspended state, also can add other solvent, additive in order to dissolve specific metal compound particles and activator.The specific ratio that contains functional group's multipolymer in the solution is preferably 0.1～60 quality %, more preferably 0.2～50 quality %.Preferably both add up to 0.01～60 quality % for the specific metal compound particles in solution or the dispersion liquid and the ratio of activator, more preferably 0.05～50 quality %.The mixing of solution or dispersion liquid can be undertaken by normally used solution stirring device, the temperature during mixing be preferably 20 ℃ or more than, more preferably 30 ℃ or more than.When mixing solutions or dispersion liquid,, can add suitable catalyzer in order to promote the metal corsslinking reaction.By known methods such as heating, decompression, steam distillations, from the above-mentioned mixed solution that obtains, remove and desolvate, can obtain the ionomer of the present embodiment thus.With this mixed solution curtain coating on suitable matrix, remove then and desolvate, can obtain the ionomer of the present embodiment of form of film thus.

First scheme of the above-mentioned ionomer of the present invention that obtains the melt flow rate (MFR) of measuring under the condition of 230 ℃ of temperature, load 10kg (MFR) for 0.5g/10 minute or more than, preferred 1g/10 minute or more than, tensile-permanent set be 30% or below, preferred 20% or below, therefore have and same caoutchouc elasticity and the forming process of ionomer in the past, simultaneously, by embodiment described later as can be known: have good flexibility, physical strength and abrasion resistance, particularly fracture tensile strength height, resistance to marring and glossiness excellence.

[ionomer composition]

First scheme of ionomer of the present invention is by with mixing such as macromolecular compound, tenderizers, use with the form of ionomer composition, wherein said macromolecular compound is selected from thermoplastic resin and the rubber (hereinafter referred to as " other macromolecular compound ") that contains functional group's multipolymer except that specific.Constitute ionomer composition other macromolecular compound so long as the specific compound that contains beyond functional group's multipolymer get final product, be not particularly limited, can use all cpds, its object lesson has: polyethylene and maleic anhydride graft copolymer thereof, polyisobutene, ethylene vinyl acetate copolymer, ethylene-acrylate, ethylene-acrylic acid copolymer, polypropylene and maleic anhydride graft copolymer thereof, polyisobutene, polychloroprene, 4-methylpentene-1 resin, polystyrene, ABS resin, the AS resin, acrylic resin, methacrylic resin, vinyl chloride resin, permalon, polyamide resin, polycarbonate, ethylene rubber and maleic anhydride graft copolymer thereof, ethylene ' alpha '-olefin non-conjugated diene copolymer rubber, styrene butadiene ribber and hydride thereof, the maleic anhydride graft copolymer of the hydride of styrene butadiene ribber, divinyl rubber and hydride thereof, the maleic anhydride graft copolymer of the hydride of divinyl rubber, synthetic polyisoprene and hydride thereof, the maleic anhydride graft copolymer of the hydride of synthetic polyisoprene, styrene isoprene rubber and hydride thereof, the maleic anhydride graft copolymer of the hydride of styrene isoprene rubber, paracril and hydride thereof, acrylic rubber, organo-silicone rubber, viton, isoprene-isobutylene rubber, natural rubber etc., special preferably polyethylene and polypropylene.These macromolecular compounds can use independent a kind or with 2 kinds or above being used in combination.The usage ratio of other macromolecular compound is 300 mass parts or following with respect to the specific functional group's multipolymer that contains that 100 mass parts constitute ionomer, preferred 1～200 mass parts.

The tenderizer that constitutes ionomer composition can be added on the specific monomer solution that contains functional group's multipolymer that is used for obtaining to constitute ionomer, also can add when the preparation ionomer or after the preparation.Constitute ionomer composition tenderizer so long as normally used softener of rubber get final product, be not particularly limited, for example have: the mineral oil of paraffin series, naphthene series, aromatics system is low molecular weight hydrocarbons such as hydrocarbon and polybutene system, polyhutadiene system etc.Wherein, preferred mineral oil is hydrocarbon, also preferably has weight-average molecular weight 300～2,000, preferred especially 500～1,500 molecular weight.The softener of rubber that contains mineral oil and be hydrocarbon normally aromatics is hydrocarbon, naphthene series hydrocarbon and paraffin series hydrocarbon three's a mixture, following classification form is arranged respectively: the carbonatoms of paraffin series hydrocarbon account for total carbon atom number 50% or above be paraffin series oil, the carbonatoms of naphthene series hydrocarbon account for total carbon atom number 30～45% for naphthene series oil, aromatics be the carbonatoms of hydrocarbon account for total carbon atom number 30% or above for aromatics system oily.Among the present invention, preferred paraffin series, preferred especially hydrowax is.Mineral oil is that the kinetic viscosity under preferred 40 ℃ of the hydrocarbon is 20～800cSt, is preferably 50～600cSt especially, and in addition, pour point is preferably-40 ℃～0 ℃, preferred-30 ℃～0 ℃ especially.The usage ratio of tenderizer is 100 mass parts or following with respect to the specific functional group's multipolymer that contains that 100 mass parts constitute ionomer, preferred 1～67 mass parts.

Ionomer composition can be mixed and prepare by add other macromolecular compound and/or above-mentioned tenderizer and heating in above-mentioned ionomer, the method for preferred manufacturing procedure has following (4) and (5).

(4) with specific contain functional group's multipolymer, specific metal compound particles and the activator that uses as required, other macromolecular compound and/or tenderizer mixes, and the gained mixture is implemented dynamic heat-treating methods.

Dynamic heat treated treatment condition in this method are according to the kind of the specific fusing point that contains functional group's multipolymer, specific metal compound particles, the fusing point of other macromolecular compound, the kind of melting mixing device etc. and different, treatment temp is 80～350 ℃, preferred 100～300 ℃, treatment time is 20 seconds～320 minutes, preferred 30 seconds～25 minutes.In addition, the shearing force that mixture is applied is shearing rate 10～2000 seconds ^-1, preferred 100～1000 seconds ^-1

(5) under heating, the specific functional group's multipolymer that contains is dissolved in the solution that obtains in the appropriate solvent, specific metal compound particles and the activator that uses as required are dissolved or dispersed in solution or dispersion liquid and the dissolving that obtains in the appropriate solvent or have disperseed the solution of macromolecular compound and/or tenderizer or dispersion liquid to mix, from the gained mixed solution, remove the method for desolvating.

The solvent that uses in this method is not particularly limited, consider from the angle that contains functional group's multipolymer that easy dissolving is specific, for example preferably use aliphatic hydrocarbon, ester ring type hydro carbons, aromatic hydrocarbons and their halogenide, its object lesson has: butane, pentane, hexane, heptane, 2-butane, 2-methyl-2-butane, pentamethylene, methylcyclopentane, hexanaphthene, octane-iso, benzene,toluene,xylene, chlorobenzene, methylene dichloride, ethylene dichloride etc.When employed specific metal compound particles and activator hang down the solvability of above-mentioned solvent, can be prepared into specific metal compound particles and activator are scattered in dispersion liquid in the solvent with suspended state, in order to dissolve specific metal compound particles and activator, also can add other solvent, additive.When macromolecular compound and tenderizer hang down the solvability of above-mentioned solvent, can be scattered in the solvent with suspended state, in order to dissolve macromolecular compound and tenderizer, also can add other solvent, additive, perhaps also can carry out dynamic thermal treatment to it removing desolvate back interpolation macromolecular compound and tenderizer.The mixing of solution or dispersion liquid can be undertaken by normally used solution stirring device, the temperature during mixing be preferably 20 ℃ or more than, more preferably 30 ℃ or more than.When mixing solutions or dispersion liquid,, can add suitable catalyzer in order to promote the metal corsslinking reaction.By known methods such as heating, decompression, steam distillations, from the above-mentioned mixed solution that obtains, remove and desolvate, can obtain ionomer composition thus.With this mixed solution curtain coating on suitable matrix, remove then and desolvate, can obtain the ionomer composition of form of film thus.

Can be as required, in described ionomer composition, mix and use various additives, lubricant for example, antiaging agent, thermo-stabilizer, weather resisting agent, metal passivator, UV light absorber, photostabilizer, stablizers such as copper evil inhibitor, antibacterial mildew inhibitor, dispersion agent, softening agent, nucleator, fire retardant, tackifier, frothing aid, titanium oxide, tinting materials such as carbon black, metal-powders such as ferrite, glass fibre, inorganic fibres such as steel fiber, carbon fiber, organic fibres such as Kevlar, conjugated fibre, potassium titanate palpus crystalline substances etc. are inorganic must be brilliant, granulated glass sphere, glass sphere, sheet glass, asbestos, mica, lime carbonate, talcum powder, silica, Calucium Silicate powder, hydrotalcite, kaolin, diatomite, graphite, float stone, ebonite powder, velveteen, dust cork, barium sulfate, fluoro-resin, filler or their mixtures such as polymeric beads, polyolefin-wax, cellulose powder, rubber powder, fillers such as wood powder, low-molecular weight polymer etc.

[moulding product]

First scheme of ionomer of the present invention or the ionomer composition that contains it method of forming by injection moulding, extrusion moulding, vacuum forming, powder slush moulding method, rolling-molding method, transfer molding method, solvent casting method and extrusion forming method etc. etc. are easily processed, can obtain having good caoutchouc elasticity, flexibility and mechanical properties, particularly fracture tensile strength, the moulding product (moulding product of the present invention) of resistance to marring and glossiness excellence.Described moulding product of the present invention can be used as and are connected with the moulding product of common ethylene series vulcanized rubber moulding product, ionomer or laminated.Moulding product of the present invention have excellent caoutchouc elasticity; flexibility; forming process; resistance to marring and abrasion resistance; therefore can be suitable as: the snubber of automobile; the outer decoration with hammer; envelope window liner; the door sealing liner; the container tightening flap; roof side rail; sign; inner panel; door internal decoration plate; the surfacing of internal and external ornaments such as Console; draught sealing etc.; the leather seat that needs resistance to marring; sealing material that the aircraft boats and ships are used and internal and external ornament surfacing etc.; the sealing material that civil construction is used; internal and external ornament surfacing or waterproof sheet etc.; the sealing material that the conventional mechanical device is used etc.; the packing ring of light current parts; epidermis or shell etc.; information instrument roller; cleaning balde; the electronic component-use film; sealing material; the protect image film of photo etc.; the material of construction decorating film; the Medical Instruments parts; electric wire; the sundry goods product; general processed goods such as sporting goods, the CMP pad that semiconductor grinding is used; various film (the protective membranes of electronic component-use; absorb ballistic film; light polarizing film; absorb the film of specific wavelength etc.); the protective membrane that uses in the manufacturing process of flat-panel monitor such as semiconductor device and liquid crystal indicator (FPD).

Then, the embodiment to the preparation method's of the alternative plan of ionomer of the present invention and ionomer of the present invention alternative plan describes.The alternative plan of ionomer of the present invention is the ionomer that the alternative plan by the preparation method of ionomer of the present invention shown below obtains.

The preparation method's of ionomer of the present invention alternative plan is that ethylene series random copolymers and metallic compound are implemented dynamic thermal treatment, wherein said ethylene series random copolymers is that to make ethene, carbonatoms be that 3～10 alpha-olefin and the functionality ring compound copolymerization shown in the following general formula (2) obtain

[changing 4]

(in the general formula (2), n is 0 or 1, R ¹, R ², R ³And R ⁴Independent respectively expression hydrogen atom, halogen atom or univalent organic group).

[ethylene series random copolymers]

The ethylene series random copolymers that uses among the preparation method of the ionomer of the present embodiment uses ethene as monomer.The usage ratio of ethene preferably accounts for all monomeric 35～94.99 moles of %, more preferably 40～89.99 moles of %, preferred especially 45～84.99 moles of %.When the usage ratio of ethene is lower than 35 moles of %, be difficult to make functionality ring compound described later copolymerization.On the other hand, the usage ratio of ethene surpasses 94.99 moles of %, and ionomer then of the present invention (alternative plan) is difficult to obtain as the necessary caoutchouc elasticity of ethylene series thermoplastic elastomer.

In the above-mentioned ethylene series random copolymers, monomer use carbonatoms is 3～10 alpha-olefin (hereinafter referred to as " specific alpha-olefin ").By using carbonatoms is 10 or following alpha-olefin, and this alpha-olefin and other monomeric copolymerization are good.The object lesson of specific alpha-olefin has: propylene, 1-butylene, 1-amylene, 4-methyl-amylene-1,1-hexene, 1-heptene, 1-octene, 1-decene etc.Wherein, preferred propylene, 1-butylene, 1-hexene, 1-octene, further preferred propylene, 1-butylene.These compounds can use independent a kind or with 2 kinds or above being used in combination.

The usage ratio of above-mentioned specific alpha-olefin is preferably all monomeric 5～50 moles of %, more preferably 10～45 moles of %, preferred especially 15～40 moles of %.When the usage ratio of specific alpha-olefin was lower than 5 moles of %, gained ionomer of the present invention (alternative plan) was difficult to obtain as the necessary caoutchouc elasticity of ethylene series thermoplastic elastomer.And the usage ratio of specific alpha-olefin surpasses 50 moles of %, and then the weather resistance of gained ionomer may reduce.

Above-mentioned ethylene series random copolymers uses the functionality ring compound shown in the above-mentioned general formula (2) as monomer.In the above-mentioned general formula (2), R ¹～R ³Respectively independent, be hydrogen atom, halogen atom or any monovalent organic radical group, be preferably hydrogen atom or carbonatoms and be 1～20 alkyl.Here, carbonatoms is that the object lesson of 1～20 alkyl has: aliphatic hydrocarbyls such as methyl, ethyl, butyl, ester ring type alkyl such as cyclohexyl, aromatic hydrocarbyls such as benzyl.Wherein, preferred especially R ¹～R ³All be ethyl, perhaps one is that the tertiary butyl, two are methyl.R ⁴With R ¹～R ³Independent, be hydrogen atom, halogen atom or any monovalent organic radical group, be preferably the alkyl of carbonatoms 1～20, more preferably methyl.The value of repeat number n is 0 or 1, preferred 1.

The object lesson of functionality ring compound has: 2-methyl bicyclic [2.2.1] heptan-5-alkene-2-carboxylic acid trimethyl silyl ester, 2-methyl bicyclic [2.2.1] heptan-5-alkene-2-carboxylic acid triethylsilyl ester, 2-methyl bicyclic [2.2.1] heptan-5-alkene-2-carboxylic acid t-butyldimethylsilyl ester, 2-methyl bicyclic [2.2.1] heptan-5-alkene-2-carboxylic acid three normal-butyl silyl esters, 2-methyl bicyclic [2.2.1] heptan-5-alkene-2-carboxylic acid normal-butyl dimetylsilyl ester, 2-methyl bicyclic [2.2.1] heptan-5-alkene-2-carboxylic acid cyclohexyl dimetylsilyl ester, 2-methyl bicyclic [2.2.1] heptan-5-alkene-2-carboxylic acid tribenzyl silyl ester, two the ring [2.2.1] heptan-5-alkene-2-carboxylic acid trimethyl silyl ester, two the ring [2.2.1] heptan-5-alkene-2-carboxylic acid triethylsilyl ester, two the ring [2.2.1] heptan-5-alkene-2-carboxylic acid t-butyldimethylsilyl ester, two the ring [2.2.1] heptan-5-alkene-2-carboxylic acid three normal-butyl silyl esters, two the ring [2.2.1] heptan-5-alkene-2-carboxylic acid normal-butyl dimetylsilyl ester, two the ring [2.2.1] heptan-5-alkene-2-carboxylic acid cyclohexyl dimetylsilyl ester, two the ring [2.2.1] heptan-5-alkene-2-carboxylic acid tribenzyl silyl ester, 2-ethyl two ring [2.2.1] heptan-5-alkene-2-carboxylic acid trimethyl silyl ester, 2-ethyl two ring [2.2.1] heptan-5-alkene-2-carboxylic acid triethylsilyl ester, 2-ethyl two ring [2.2.1] heptan-5-alkene-2-carboxylic acid t-butyldimethylsilyl ester, 2-ethyl two ring [2.2.1] heptan-5-alkene-2-carboxylic acid three normal-butyl silyl esters, 2-ethyl two ring [2.2.1] heptan-5-alkene-2-carboxylic acid normal-butyl dimetylsilyl ester, 2-ethyl two ring [2.2.1] heptan-5-alkene-2-carboxylic acid cyclohexyl dimetylsilyl ester, 2-ethyl two ring [2.2.1] heptan-5-alkene-2-carboxylic acid tribenzyl silyl ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid trimethyl silyl ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid triethylsilyl ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid t-butyldimethylsilyl ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid normal-butyl dimetylsilyl ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid cyclohexyl dimetylsilyl ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid allyl group dichlorosilane base ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid diallyl chloromethane silylation ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-generating vinyl carboxylate base dimetylsilyl ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid chloromethyl dimetylsilyl ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid trimethylphenylmethane base chloromethane silylation ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid tribenzyl silyl ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid dimetylsilyl ester, Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid trimethyl silyl ester, Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid triethylsilyl ester, Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid t-butyldimethylsilyl ester, Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid normal-butyl dimetylsilyl ester, Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid cyclohexyl dimetylsilyl ester, Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid allyl group dichlorosilane base ester, Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid diallyl chloromethane silylation ester, Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-generating vinyl carboxylate base dimetylsilyl ester, Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid chloromethyl dimetylsilyl ester, Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid trimethylphenylmethane base chloromethane silylation ester, Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid tribenzyl silyl ester, Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid dimetylsilyl ester, 4-ethyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid trimethyl silyl ester, 4-ethyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid t-butyldimethylsilyl ester, 4-chlorotetracyclin [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid trimethyl silyl ester, 4-chlorotetracyclin [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid t-butyldimethylsilyl ester, 4-methoxyl group Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid trimethyl silyl ester, 4-methoxyl group Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid t-butyldimethylsilyl ester etc.These functionality ring compounds can use independent a kind or with 2 kinds or above being used in combination.

Wherein, consider preferred 2-methyl bicyclic [2.2.1] heptan-5-alkene-2-carboxylic acid trimethyl silyl ester from the stable equal angles of the polymerizability of functionality ring compound and gained ionomer, 2-methyl bicyclic [2.2.1] heptan-5-alkene-2-carboxylic acid triethylsilyl ester, 2-methyl bicyclic [2.2.1] heptan-5-alkene-2-carboxylic acid t-butyldimethylsilyl ester, 2-methyl bicyclic [2.2.1] heptan-5-alkene-2-carboxylic acid three normal-butyl silyl esters, 2-methyl bicyclic [2.2.1] heptan-5-alkene-2-carboxylic acid normal-butyl dimetylsilyl ester, 2-methyl bicyclic [2.2.1] heptan-5-alkene-2-carboxylic acid cyclohexyl dimetylsilyl ester, 2-methyl bicyclic [2.2.1] heptan-5-alkene-2-carboxylic acid tribenzyl silyl ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid trimethyl silyl ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid triethylsilyl ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid t-butyldimethylsilyl ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid normal-butyl dimetylsilyl ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid cyclohexyl dimetylsilyl ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid tribenzyl silyl ester,

Particularly preferably be: 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid trimethyl silyl ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid triethylsilyl ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid t-butyldimethylsilyl ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid normal-butyl dimetylsilyl ester, 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid cyclohexyl dimetylsilyl ester.

Above-mentioned functionality ring compound is to have the compound that this carboxyl of the ring compound of carboxyl is obtained by silylanizing, therefore need not to shelter and take off to shelter to prepare and contain functional group's ethylene series random copolymers, need not to carry out functional group's conversion that gained contains functional group's ethylene series random copolymers, can prepare ionomer.

The usage ratio of functionality ring compound is preferably all monomeric 0.01～5 mole of %, further preferred 0.01～4 mole of %.When the usage ratio of functionality ring compound was lower than 0.01 mole of %, the cross-linking density of gained ionomer was low, and physical strength and thermotolerance are also low.And the usage ratio of functionality ring compound is when surpassing 5 moles of %, and the cross-linking density of gained ionomer raises, hardness raises, and becomes fragile.

In the ethylene series random copolymers, except that above-mentioned monomer, can also use non-conjugated diene conduct monomer arbitrarily.The object lesson of this non-conjugated diene has: 1, the 4-hexadiene, 1, the 6-hexadiene, 1, straight chain non-annularity diene such as 5-hexadiene, the 5-methyl isophthalic acid, the 4-hexadiene, 3,7-dimethyl-1, the 6-octadiene, 5,7-dimethyl-octa-1, the 6-diene, 3,7-dimethyl-1, the 7-octadiene, 7-methyl suffering-1, the 6-diene, side chain non-annularity diene such as dihydromyrcene, tetrahydroindene, the methyl tetrahydroindene, dicyclopentadiene, two ring [2.2.1]-heptan-2, the 5-diene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-propenyl-2-norbornylene, 5-isopropylidene-2-norbornylene, 5-cyclohexylidene-2-norbornylene, ester ring type diene such as 5-vinyl-2-norbornylene etc.These compounds can use independent a kind or with 2 kinds or above being used in combination.In the above-mentioned non-conjugated diene there be preferred compound: 1, and 4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene etc.The usage ratio of non-conjugated diene is preferably 0～10 mole of % of whole monomer components.The usage ratio of this non-conjugated diene surpasses 10 moles of %, and then the weather resistance of gained ionomer may reduce.

The ethylene series random copolymers that uses among the preparation method of the ionomer of the present embodiment can be by being that 3～10 alpha-olefin and the functionality ring compound shown in the above-mentioned general formula (2) are implemented addition polymerization and handled and obtain to above-mentioned ethene, carbonatoms.Addition polymerization is handled and preferably supply ethene under inert atmosphere such as nitrogen or argon, in reaction vessel, carbonatoms is 3～10 alpha-olefin, functionality ring compound and the conjugated diolefine of using as required, in the presence of appropriate solvent or thinner, under the condition of 0～150 ℃ of the temperature of reaction system, carry out.Further preferred 10～100 ℃ of the temperature of reaction system.

Be used to carry out the catalyzer that addition polymerization handles and preferably use the ethylene series catalyst for copolymerization, this ethylene series catalyst for copolymerization can obtain the multipolymer more randomly arranged from each monomeric structural unit in the copolyreaction of functionality ring compound, ethene, alpha-olefin, the non-conjugated diene that uses as required.Described ethylene series catalyst for copolymerization can use transistion metal compound, and preferred the use contained the compound of the metal that is selected from periodictable the 4th family and the 5th family and the catalyzer of organo-aluminium compound, and concrete catalyzer can exemplify following material.

(1) can exemplify and contain the vanadium compound that is dissolvable in water hydrocarbon compound and the catalyst system of organo-aluminium compound, wherein contain a chlorine atom at least among one of them of vanadium compound and organo-aluminium compound or both.Here, vanadium compound can use compound, the VCl shown in the following general formula (3-1) ₄, VO (acac) ₂, V (acac) ₃Compound shown in (wherein " acac " expression acetylacetonate), the following general formula (3-2) etc.

General formula (3-1): O=VCl _k(OR ¹¹) _3-k

(in the formula, R ¹¹Alkyl such as expression ethyl, propyl group, butyl, hexyl.K represents 0～3 integer).

General formula (3-2): VCl ₃MZ

(in the formula, Z represents to form the Lewis base of complex compound, and this complex compound is dissolvable in water hydrocarbon compounds such as tetrahydrofuran (THF), 2-methyl-tetrahydrofuran (THF), 2-methoxymethyl-tetrahydrofuran (THF), lutidine.M is 2～3 integer).

Organo-aluminium compound can use the trialkyl aluminium compound shown in the following general formula (3-3), alkyl aluminium hydride shown in following general formula (3-4) or the following general formula (3-5), chlorination aluminum alkyls shown in following general formula (3-6), following general formula (3-7) or the following general formula (3-8), the methyl ア Le モ キ サ Application (MAO) that the reaction of the alkoxyl group shown in following general formula (3-9) or the following general formula (3-10) or phenoxy group replacement organoaluminum, water and above-mentioned trialkyl aluminium compound obtains, ethyl ア Le モ キ サ Application, butyl ア Le モ キ サ Application etc.

General formula (3-3): AlR ¹²,

General formula (3-4): HAlR ¹²,

General formula (3-5): H ₂AlR ¹²,

General formula (3-6): R ¹²AlCl ₂,

General formula (3-7): R ¹² ₃Al ₂Cl ₃,

General formula (3-8): R ¹² ₂AlCl,

General formula (3-9): R ¹² ₂Al (OR ¹³),

General formula (3-10): R ¹²Al (OR ¹³) ₂

(in general formula (3-3)～general formula (3-10), R ¹²Alkyl such as expression methyl, ethyl, propyl group, butyl, hexyl.R ¹³Expression methyl, ethyl, propyl group, butyl, octyl group, phenyl, tolyl xylyl, 2,6-di-tert-butyl-phenyl, 4-methyl-2,6-di-tert-butyl-phenyl or 2,6-3,5-dimethylphenyl, 4-methyl-2,6-3,5-dimethylphenyl).

In this catalyst system, ester, ether, amine, ketone, organoalkoxysilane that can further add organic acid or mineral acid in above-mentioned vanadium compound and the organo-aluminium compound etc. contains oxygen or nitrogenous electron donor.

(2) can exemplify the catalyst system that on the carrier that contains silicon-dioxide or magnesium chloride, supports, contain halogenated titanium or zirconium halide, organo-aluminium compound.Here, halogenated titanium or zirconium halide can use titanium tetrachloride, titanium tetrabromide, zirconium tetrachloride etc.Organo-aluminium compound can use trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, methyl ア Le モ キ サ Application etc.In this catalyst system, can further in above-claimed cpd, add phthalic acid dioctyl ester, tetraalkoxysilane, dimethoxydiphenylsilane etc.

(3) can exemplify the catalyst system that contains transistion metal compound and organo-aluminium compound, wherein said transistion metal compound is to have 1 or 2 cyclopentadienyl or transistion metal compounds indenyl, that be selected from the metal of titanium, zirconium, hafnium as dentate, and wherein said cyclopentadienyl or indenyl have the hydrogen of being selected from, alkyl and allylic substituting group; Described organo-aluminium compound contains at least 50 moles of % methyl ア Le モ キ サ Application.

The object lesson of above-mentioned transistion metal compound has: two (cyclopentadienyl) zirconium dimethyl, two (cyclopentadienyl) diethyl zirconium, monochlor(in)ate two (cyclopentadienyl) methylcyclopentadienyl zirconium, dichloride ethylene (cyclopentadienyl) zirconium, monochlor(in)ate ethylene (cyclopentadienyl) methylcyclopentadienyl zirconium, dichloride methylene radical two (cyclopentadienyl) zirconium, dichloride ethylene (indenyl) zirconium, ethylene (indenyl) zirconium dimethyl, ethylene (indenyl) phenylbenzene zirconium, ethylene (4,5,6,7-tetrahydrochysene-1-indenyl) zirconium dimethyl, dichloride ethylene (4-methyl isophthalic acid-indenyl) zirconium, dichloride ethylene (2,3-dimethyl-1-indenyl) zirconium, dichloride dimetylsilyl two (cyclopentadienyl) zirconium, dichloride dimetylsilyl two (indenyl) zirconium, dichloride dimetylsilyl two (dimethyl cyclopentadienyl) zirconium, dichloride dimethyl methyl (fluorenyl) (cyclopentadienyl) zirconium, dichloride diphenyl methyl (fluorenyl) (cyclopentadienyl) zirconium, dichloride diphenylmethyl silylation two (indenyl) zirconium, dichloride dimetylsilyl two (2-methyl-4-phenyl-indenyl) zirconium, two (cyclopentadienyl) dimethyl titanium, monochlor(in)ate two (cyclopentadienyl) methyltitanium, dichloride ethylene (indenyl) titanium, dichloride ethylene (4,5,6,7-tetrahydrochysene-1-indenyl) titanium, dichloride methylene radical two (cyclopentadienyl) titanium, dichloride η 1: the dimetylsilyl η 5-{[(tertiary butyl-amido)] (2,3,4,5-tetramethyl--1-cyclopentadienyl) titanium etc.

(4) the salicylic aldehyde imide that contains so that dialkyl group replaces or the N-alkyl replaces is the periodic table of elements the 4th group 4 transition metal complex compound of dentate and the catalyst system of methyl ア Le モ キ サ Application (MAO).

Be used to carry out solvent or thinner that addition polymerization handles and for example can use aliphatic hydrocarbon, ester ring type hydro carbons, aromatic hydrocarbons and their halogenide.Specifically have: butane, pentane, hexane, heptane, 2-butylene, 2-methyl-2-butene, pentamethylene, methylcyclopentane, hexanaphthene, octane-iso, benzene,toluene,xylene, chlorobenzene, methylene dichloride, ethylene dichloride etc.These solvents or thinner are to use under 20ppm or the following state make moisture concentration by distillation processing or adsorption treatment preferably.

During described addition polymerization is handled, the adjusting of the interpolation that the adjusting of the molecular weight of the addition copolymer that gained is specific can be by molecular weight regulator, the amount of polymerizing catalyst, the control of polymerization temperature, the methods such as adjusting of the adding rate of polymkeric substance are carried out.Molecular weight regulator can use hydrogen, zinc ethyl, diisobutylaluminium hydride etc.Being used to carry out the reactor that addition polymerization handles can be the arbitrary form of intermittent type and continous way.Flow reactor can use tubular reactor, tower reactor, groove type reactor etc.

The ethylene series random copolymers can followingly obtain: be blown in by the polymeric solution after above-mentioned addition polymerization is handled water vapor carry out solvent remove processing after, separate solid material from the gained slurry, further use screw squeezing machine, forcing machine, warming mill etc., obtain by dehydration, drying.Perhaps concentrate, carry out drying treatment with forcing machine then and obtain with ventage by heating above-mentioned polymeric solution.Also can be as required, to above-mentioned polymeric solution carry out the residual polymerization catalyzer separation, remove processing.Described separation, the concrete grammar of removing processing can utilize following method: make it cross the method for the adsorption column that is filled with silicon-dioxide, aluminum oxide, diatomite etc.; Heavy addition water, alcohol etc. such as wash at method in polymeric solution.

The above-mentioned ethylene series random copolymers that obtains is by being that the polystyrene conversion weight-average molecular weight of the gel permeation chromatography of solvent is preferably 1,000～3,000,000 with the orthodichlorobenzene, more preferably 3,000～1,000,000, preferred especially 5,000～700,000.In addition, the second-order transition temperature of ethylene series random copolymers is-90 ℃～50 ℃, preferred-70 ℃～10 ℃ especially, can obtain having abundant elastic ionomer thus.Here, second-order transition temperature can be measured by scan-type differential thermal analysis meter (DSC).

Can contain various additives such as antioxidant, UV light absorber in the above-mentioned ethylene series random copolymers.

Antioxidant can use: 2, the 6-di-tert-butyl-4-methy phenol, 4,4 '-thiobis-(the 6-tertiary butyl-3-methylphenol), 1,1 '-bis(4-hydroxyphenyl) cyclohexane, 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 2, the 5-di-tert-butyl hydroquinone, four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, two [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic acid] triethyleneglycol ester, it is two that [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] 1,6-hexylene glycol ester, 2,4-pair-(positive hot sulfenyl)-6-(4-hydroxyl-3,5-di-tert-butyl amido)-1,3, the 5-triazine, four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, it is two that [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] 2,2-sulfo--glycol ether ester, 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl, N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamamide, 3,5-tertiary butyl-4-hydroxy-4-benzyl diethyl phosphoric acid, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) phenol such as benzene system or quinhydrones are antioxidant, tricresyl phosphite (4-methoxyl group-3,5-phenylbenzene) ester, tricresyl phosphite (nonyl phenyl) ester, phosphorous antioxidants such as tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester.By with the independent a kind of interpolation of these antioxidants or with 2 kinds or above combination interpolation, can improve the oxidative stability of ethylene series random copolymers.

UV light absorber can be used: 2,4-dihydroxy benaophenonel, 2-hydroxyl-4-methoxy benzophenone, 2, [4-(1 for 2-methylene radical two, 1,3,3-tetramethyl butyl)-6-[(2H-benzotriazole-2-yl) phenol]], hindered amine is that UV light absorber, benzoic ether are UV light absorber.By with the independent a kind of interpolation of these UV light absorber or with 2 kinds or above combination interpolation, can improve the photostabilization of ethylene series random copolymers.

Other additive can make with lubricator, by adding this lubricant, can improve the processibility of ethylene series random copolymers.

In the preparation method's of the ionomer of the present invention alternative plan, mix and implement dynamic thermal treatment, can obtain the alternative plan of ionomer by the ethylene series random copolymers that will obtain as mentioned above and metallic compound.

[metallic compound]

Above-mentioned metallic compound can use metal oxide, metal hydroxides, metal-salt and metal complex etc.The object lesson of metal oxide has: CuO, MgO, BaO, ZnO, Al ₂O ₃, Fe ₂O ₃, SnO, CaO, TiO ₂Deng.In addition, the object lesson of metal hydroxides has: LiOH, NaOH, KOH, Cu (OH) ₂, Cu ₂O (OH) ₂, Mg (OH) ₂, Mg ₂O (OH) ₂, Ba (OH) ₂, Zn (OH) ₂, Sn (OH) ₂, Ca (OH) ₂Deng.In order to improve the dispersiveness with the ethylene series random copolymers, these metallic compounds can be handled through silane coupling agent, higher fatty acid.These metallic compounds can use independent a kind or with 2 kinds or above being used in combination.

The usage ratio of the metallic compound ethylene series random copolymers specific with respect to 100 mass parts is generally 0.01～10 mass parts, preferred 0.05～9 mass parts, preferred especially 0.1～8 mass parts.When this ratio was lower than 0.01 mass parts, the cross-linking density of gained ionomer was low, and physical strength and resistance to marring reduce.On the other hand, when this ratio surpassed 10 mass parts, the cross-linking density of gained ionomer raise, and the hardness height becomes fragile.

Above-mentioned metallic compound can produce metal ion by mixing with the ethylene series random copolymers and implementing dynamic thermal treatment, makes the ethylene series random copolymers crosslinked.Here, be used to make the crosslinked metal ion of ethylene series random copolymers that the metal ion of lithium, potassium, sodium, aluminium, magnesium, calcium, barium, caesium, strontium, rubidium, titanium, zinc, copper, iron, tin, lead and other elements periodictable the I～VIII family is arranged.The metal ion of wherein preferred potassium, sodium, aluminium, magnesium, barium, zinc, iron, calcium, titanium, lead.Therefore, as long as above-mentioned metallic compound can produce these metal ions, be not limited to above-mentioned object lesson.

For the Combination that improves metallic compound and ethylene series random copolymers and the thermotolerance of gained ionomer, except that metallic compound, the metal-salt that can add carboxylic acid is as activator.The metal-salt of carboxylic acid preferably uses monocarboxylic metal-salt, and further preferred this carboxylic acid is the carboxylic acid of carbonatoms 3～23.The object lesson of described carboxylic acid has: propionic acid, vinylformic acid, butyric acid, methacrylic acid, valeric acid, caproic acid, sad, 2 ethyl hexanoic acid, capric acid, palmitinic acid, tetradecanoic acid, lauric acid, stearic acid, oleic acid, mountain Yu acid, naphthenic acid, phenylformic acid etc.Can make selection use the crosslinked composition that metal ion exemplified of ethylene series random copolymers from above-mentioned conduct as the metal ingredient in the metal-salt of activator use, preferably have the metal-salt of the congener metal ingredient of metal that is had with above-mentioned metallic compound.

The usage ratio of the metal-salt that uses as activator is generally 0.3～20 mass parts, preferred 1～15 mass parts with respect to 100 mass parts ethylene series random copolymerss.This ratio is lower than 0.3 mass parts, then can not give full play to and use the effect that activator brought, and this ratio surpasses 20 mass parts, and then the oil-proofness of gained ionomer and physical strength reduce.

[ionomer]

The method of above-mentioned metallic compound, ethylene series random copolymers and the activator mix used as required can be utilized following the whole bag of tricks: prepare the solution or the dispersion liquid of each composition, with they blended methods; Use the method for normally used melting mixing device etc.From the angle of the ionomer that can obtain having stable properties, preferred heating is blended method, the method for especially preferably following (I) specifically down.

(I) with ethylene series random copolymers, metallic compound and the activator mix used as required, the gained mixture is implemented dynamic heat-treating methods.

In the method for above-mentioned (I), " dynamically thermal treatment " is meant the processing that applies shearing force and the processing of heat treated two aspects.Described dynamic thermal treatment for example can use the melting mixing device to carry out.This melting mixing device can be step also can be continous way.The object lesson of melting mixing device has: intermittent type melting mixing devices such as open mixing roller, non-open type Banbury stirrer, kneader, continous way melting mixing devices such as single shaft forcing machine, rotary-type in the same way continous way biaxial extruder, reverse rotation type continous way biaxial extruder.Concrete method has following (I-1) and method (I-2).

(I-1),, obtain the ionomer of the present embodiment thus to containing ethylene series random copolymers, metallic compound and the mixture enforcement dynamic thermal treatment of shearing heating continuously of the activator of use as required by biaxial extruder.

(I-2) by the intermittent type kneader mixture of the activator that contains ethylene series random copolymers, metallic compound and use is as required implemented to shear the dynamic thermal treatment of heating, obtain the ionomer of the present embodiment thus.

Dynamic heat treated treatment condition are according to the fusing point of ethylene series random copolymers, the kind of metallic compound, the kind of melting mixing device etc. and different, treatment temp is preferably 120～350 ℃, further preferred 150～290 ℃, treatment time is preferably 20 seconds～and 320 minutes, further preferred 30 seconds～25 minutes.In addition, the shearing force that mixture is applied is shearing rate 10～2000/ seconds, preferred 100～1000/ seconds.

Like this, the alternative plan of the ionomer of the present invention that the alternative plan of the preparation method by ionomer of the present invention obtains is 230 ℃ of temperature, the melt flow rate (MFR) of measuring under the condition of load 10kg (MFR) for 0.5g/10 minute or more than, preferred 1g/10 minute or more than, tensile-permanent set be preferably 30% or below, further preferred 20% or below, therefore have and same caoutchouc elasticity and the forming process of ethylene series thermoplastic elastomer in the past, simultaneously, has good flexibility, physical strength and abrasion resistance, particularly resistance to marring excellence.

Except that the method for above-mentioned (I), also can prepare the ionomer of this programme by the method for (II) shown below.

(II) under heating, mix the ethylene series random copolymers being dissolved in the solution that obtains in the appropriate solvent and metallic compound and the activator that uses as required being dissolved or dispersed in the solution or the dispersion liquid that obtain in the appropriate solvent, from the gained mixed solution, remove the method for desolvating.

The solvent that uses in the method for above-mentioned (II) is not particularly limited, from easy dissolved olefin is the angle consideration of random copolymers, for example preferably use aliphatic hydrocarbon, ester ring type hydro carbons, aromatic hydrocarbons and their halogenide, its object lesson has: butane, pentane, hexane, heptane, 2-butane, 2-methyl-2-butane, pentamethylene, methylcyclopentane, hexanaphthene, octane-iso, benzene,toluene,xylene, chlorobenzene, methylene dichloride, ethylene dichloride etc.When employed metallic compound and activator hang down the solvability of above-mentioned solvent, can be prepared into metallic compound and activator are scattered in dispersion liquid in the solvent with suspended state, also can be for dissolution of metals compound and activator and add other solvent, additive.The ratio of the ethylene series random copolymers in the solution is preferably 0.1～60 quality %, more preferably 0.2～50 quality %.Preferably both add up to 0.01～60 quality % for the metallic compound in solution or the dispersion liquid and the ratio of activator, more preferably 0.05～50 quality %.The mixing of solution or dispersion liquid can be undertaken by normally used solution stirring device, the temperature during mixing be preferably 20 ℃ or more than, more preferably 30 ℃ or more than.When mixing solutions or dispersion liquid,, can add suitable catalyzer in order to promote the metal corsslinking reaction.By known methods such as heating, decompression, steam distillations, from the above-mentioned mixed solution that obtains, remove and desolvate, can obtain the ionomer of the present embodiment thus.With this mixed solution curtain coating on suitable matrix, remove then and desolvate, can obtain the ionomer of the present embodiment of form of film thus.

[ionomer composition]

Embodiment to the preparation method of ionomer composition of the present invention describes below.The alternative plan of the ionomer of the invention described above and the macromolecular compound (below can be described as " specific macromolecular compound ") that is selected from thermoplastic resin and rubber are mixed, can obtain the ionomer composition of the present embodiment.Thermoplastic resin and rubber as specific macromolecular compound use, so long as the compound except that above-mentioned ethylene series random copolymers gets final product, be not particularly limited, can use all cpds, its object lesson has: polyethylene and maleic anhydride graft copolymer thereof, polyisobutene, ethylene vinyl acetate copolymer, ethylene-acrylate, ethylene-acrylic acid copolymer, polypropylene and maleic anhydride graft copolymer thereof, polyisobutene, polychloroprene, 4-methylpentene-1 resin, polystyrene, ABS resin, the AS resin, acrylic resin, methacrylic resin, vinyl chloride resin, permalon, polyamide resin, polycarbonate, ethylene rubber and maleic anhydride graft copolymer thereof, ethylene ' alpha '-olefin non-conjugated diene copolymer rubber, styrene butadiene ribber and hydride thereof, the maleic anhydride graft copolymer of the hydride of styrene butadiene ribber, divinyl rubber and hydride thereof, the maleic anhydride graft copolymer of the hydride of divinyl rubber, synthetic polyisoprene and hydride thereof, the maleic anhydride graft copolymer of the hydride of synthetic polyisoprene, styrene isoprene rubber and hydride thereof, the maleic anhydride graft copolymer of the hydride of styrene isoprene rubber, paracril and hydride thereof, acrylic rubber, organo-silicone rubber, viton, isoprene-isobutylene rubber, natural rubber etc., special preferably polyethylene and polypropylene.These macromolecular compounds can use independent a kind or with 2 kinds or above being used in combination.The usage ratio of specific macromolecular compound is 300 mass parts or following with respect to the ethylene series random copolymers that 100 mass parts constitute ionomer, preferred 1～200 mass parts.

Can in the alternative plan of ionomer of the present invention, add specific tenderizer, make ionomer composition.Above-mentioned specific tenderizer can be added on the monomer solution that is used for obtaining constituting the ethylene series random copolymers of ionomer, also can be when the preparation ionomer or the preparation back add.Above-mentioned specific tenderizer is not particularly limited so long as normally used softener of rubber gets final product, and for example has: the mineral oil of paraffin series, naphthene series, aromatics system is low molecular weight hydrocarbons such as hydrocarbon and polybutene system, polyhutadiene system etc.Wherein, preferred mineral oil is hydrocarbon, also preferably has weight-average molecular weight 300～2,000, preferred especially 500～1,500 molecular weight.The softener of rubber that contains mineral oil and be hydrocarbon is atomatic olefins, naphthene series hydrocarbon and paraffin series hydrocarbon three's mixture normally, following classification form is arranged respectively: the carbonatoms of paraffin series hydrocarbon account for total carbon atom number 50% or above be paraffin series oil, the carbonatoms of naphthene series hydrocarbon account for total carbon atom number 30～45% for naphthene series oil, aromatics be the carbonatoms of hydrocarbon account for total carbon atom number 30% or above for aromatics system oily.Among the present invention, preferred paraffin series, preferred especially hydrowax is.Mineral oil is that the kinetic viscosity under preferred 40 ℃ of the hydrocarbon is 20～800cSt, is preferably 50～600cSt especially, and in addition, pour point is preferably-40 ℃～0 ℃, preferred-30 ℃～0 ℃ especially.The usage ratio of above-mentioned specific tenderizer is 100 mass parts or following with respect to the ethylene series random copolymers that 100 mass parts constitute ionomer, preferred 1～67 mass parts.

Ionomer composition of the present invention can be mixed and prepares by add specific macromolecular compound and/or specific tenderizer and heating in the alternative plan of above-mentioned ionomer, and the preferred especially method by following (III) prepares.

(III) olefin copolymer, metallic compound and the activator that uses as required, specific macromolecular compound and/or specific tenderizer are mixed, the gained mixture is implemented dynamic heat-treating methods.

Dynamic heat treated treatment condition in the method that should (III) are according to the fusing point of the kind of the fusing point of ethylene series random copolymers, metallic compound, specific macromolecular compound, the kind of melting mixing device etc. and different, treatment temp is preferably 120～350 ℃, further preferred 150～290 ℃, treatment time is preferably 20 seconds～and 320 minutes, further preferred 30 seconds～25 minutes.In addition, the shearing force that mixture is applied is preferred 10～2000/ seconds of shearing rate, further preferred 100～1000/ seconds.

Like this, the ionomer composition of the present invention that obtains by the preparation method of ionomer composition of the present invention the melt flow rate (MFR) of measuring under the condition of 230 ℃ of temperature, load 10kg (MFR) be preferably 0.5g/10 minute or more than, further preferred 1g/10 minute or more than, tensile-permanent set be preferably 30% or below, further preferred 20% or below, the hardness preferred 96 that duroscope A measures or below, further preferred 90 or below.Therefore the ionomer composition of the present invention that is obtained by the preparation method of ionomer composition of the present invention has and in the past same caoutchouc elasticity, flexibility and the forming process of ethylene series composition for thermoplastic elastomer, simultaneously, have excellent mechanical intensity and abrasion resistance, particularly the resistance to marring excellence.

Except that the method for above-mentioned (III), also can prepare ionomer composition by the method for (IV) shown below.

(IV) under heating, the ethylene series random copolymers being dissolved in the solution that obtains in the appropriate solvent, metallic compound and the activator that uses as required are dissolved or dispersed in solution or dispersion liquid and the dissolving that obtains in the appropriate solvent or have disperseed specific macromolecular compound and/or the solution or the dispersion liquid of specific tenderizer mixing, from the gained mixed solution, remove the method for desolvating.

Being somebody's turn to do the solvent that uses in the method for (IV) is not particularly limited, from easy dissolved olefin is the angle consideration of random copolymers, for example preferably use aliphatic hydrocarbon, ester ring type hydro carbons, aromatic hydrocarbons and their halogenide, its object lesson has: butane, pentane, hexane, heptane, 2-butane, 2-methyl-2-butane, pentamethylene, methylcyclopentane, hexanaphthene, octane-iso, benzene,toluene,xylene, chlorobenzene, methylene dichloride, ethylene dichloride etc.When employed metallic compound and activator hang down the solvability of above-mentioned solvent, can be prepared into metallic compound and activator are scattered in dispersion liquid in the solvent with suspended state, also can be for dissolution of metals compound and activator and add other solvent, additive.When specific macromolecular compound and specific tenderizer hang down the solvability of above-mentioned solvent, can be scattered in the solvent with suspended state, also can be to add other solvent, additive in order to dissolve specific macromolecular compound and specific tenderizer, perhaps also can carry out dynamic thermal treatment to it removing specific macromolecular compound of the back interpolation of desolvating and specific tenderizer.The mixing of solution or dispersion liquid can be undertaken by normally used solution stirring device, the temperature during mixing be preferably 20 ℃ or more than, more preferably 30 ℃ or more than.When mixing solutions or dispersion liquid,, can add suitable catalyzer in order to promote the metal corsslinking reaction.By known methods such as heating, decompression, steam distillations, from the above-mentioned mixed solution that obtains, remove and desolvate, can obtain ionomer composition thus.With this mixed solution curtain coating on suitable matrix, remove then and desolvate, can obtain the ionomer composition of form of film thus.

Can be as required, in described ionomer composition, mix and use various additives, lubricant for example, antiaging agent, thermo-stabilizer, weather resisting agent, metal passivator, UV light absorber, photostabilizer, stablizers such as copper evil inhibitor, antibacterial mildew inhibitor, dispersion agent, softening agent, nucleator, fire retardant, tackifier, frothing aid, titanium oxide, tinting materials such as carbon black, metal-powders such as ferrite, glass fibre, inorganic fibres such as steel fiber, carbon fiber, organic fibres such as Kevlar, conjugated fibre, potassium titanate palpus crystalline substances etc. are inorganic must be brilliant, granulated glass sphere, glass sphere, sheet glass, asbestos, mica, lime carbonate, talcum powder, silica, Calucium Silicate powder, hydrotalcite, kaolin, diatomite, graphite, float stone, ebonite powder, velveteen, dust cork, barium sulfate, fluoro-resin, filler or their mixtures such as polymeric beads, polyolefin-wax, cellulose powder, rubber powder, fillers such as wood powder, low-molecular weight polymer etc.

In the alternative plan and composition thereof of ionomer of the present invention, the ethylene series random copolymers passes through metal ion crosslinked, therefore dissolve the method for forming etc. by injection molding, extrusion moulding, slush molding, compressed moulding, vacuum forming, laminated into type, calendering formation etc. easily and process, can obtain the ionomer moulding product of caoutchouc elasticity, flexibility and mechanical properties excellence.The moulding product that contain the alternative plan of ionomer of the present invention and composition thereof can be used as and are connected with common ethylene series vulcanized rubber moulding product or the body formed product of ethylene series thermoplastic elastic or make multiple stratification.The alternative plan of ionomer of the present invention and composition thereof have excellent caoutchouc elasticity; flexibility; forming process; resistance to marring; therefore can be widely used in the snubber of the automobile that in the past uses the ethylene series thermoplastic elastomer; the outer decoration with hammer; envelope window liner; the door sealing liner; the container tightening flap; roof side rail; sign; inner panel; door internal decoration plate; the surfacing of internal and external ornaments such as Console; draught sealing etc.; the leather seat that needs resistance to marring; sealing material that the aircraft boats and ships are used and internal and external ornament surfacing etc.; the sealing material that civil construction is used; internal and external ornament surfacing or waterproof sheet etc.; the sealing material that the conventional mechanical device is used etc.; the packing ring of light current parts; epidermis or shell etc.; information instrument roller; cleaning balde; the electronic component-use film; sealing material; the protect image film of photo etc.; the material of construction decorating film; the Medical Instruments parts; electric wire; the sundry goods product, conventional processed goods such as sporting goods.

Embodiment

Below, specific embodiment of the present invention is described, but the present invention is not limited by these.

[embodiment of first scheme of ionomer of the present invention]

The various compositions that use in following embodiment and the comparative example are as follows.

(ethylene series random copolymers)

(1) the specific functional group's multipolymer (A-1) that contains

Specific contain functional group's multipolymer be content from the structural unit of ethene be 73.7 moles of %, from the content of the structural unit of propylene be 24.6 moles of %, from the content of the structural unit of 5-ethylidene-2-norbornene be 1.4 moles of %, from 8-methyl-8-carboxyl-Fourth Ring [4.4.0.1 ^2,5.1 ^7,10The content of the structural unit of]-3-dodecylene is 0.3 mole of %, and weight-average molecular weight (Mw) is 15.6 * 10 ⁴

(2) the specific functional group's multipolymer (A-2) that contains:

Specific contain functional group's multipolymer be content from the structural unit of ethene be 73.5 moles of %, from the content of the structural unit of propylene be 24.9 moles of %, from the content of the structural unit of 5-ethylidene-2-norbornene be 1.4 moles of %, from 8-methyl-8-carboxyl-Fourth Ring [4.4.0.1 ^2,5.1 ^7,10The content of the structural unit of]-3-dodecylene is 0.2 mole of %, and weight-average molecular weight (Mw) is 17.2 * 10 ⁴

(3) the specific functional group's multipolymer (A-3) that contains:

Specific contain functional group's multipolymer be content from the structural unit of ethene be 73.3 moles of %, from the content of the structural unit of propylene be 25.2 moles of %, from the content of the structural unit of 5-ethylidene-2-norbornene be 1.4 moles of %, from 8-methyl-8-carboxyl-Fourth Ring [4.4.0.1 ^2,5.1 ^7,10The content of the structural unit of]-3-dodecylene is 0.1 mole of %, and weight-average molecular weight (Mw) is 17.4 * 10 ⁴

(specific metal compound particles)

(1) metal compound particles (B-1) [being used for the present invention]

Magnesium hydroxide particle (consonance chemical company makes the name of an article " キ ス マ 5N ") through higher fatty acid surface-treated, median size 0.7 μ m.

(2) metal compound particles (B-2) [being used for the present invention]

Median size is the Zinc oxide particles (Sakai chemical industrial company makes, the name of an article " a kind in zinc oxide ") of 0.7 μ m.

(3) metal compound particles (B-3) [being used for the present invention]

Median size is the Zinc oxide particles (Sakai chemical industrial company makes, the name of an article " micronized zinc oxide ") of 0.29 μ m.

(4) metal compound particles (B-4) [being used for the present invention]

Median size is the Zinc oxide particles (Sakai chemical industrial company makes, the name of an article " zinc oxide Na ノ Off ア イ Application W-1 ") of 0.01 μ m.

(5) metal compound particles (B-5) [being used for comparison]

Median size is the calcium hydroxide particle (aboveground lime industrial makes, the name of an article " atomic thin calcium hydroxide 50 ") of 6.1 μ m.

(other macromolecular compound)

(1) macromolecular compound (C-1)

MFR (temperature is that 190 ℃, load are 2.16kg) is 20g/10 minute high-density polyethylene resin (Japanese Port リ ケ system company make the name of an article " ノ バ テ Star Network HD HJ490 ").

(2) macromolecular compound (C-2)

MFR (temperature is that 230 ℃, load are 2.16kg) is 5g/10 minute acrylic resin (Japanese Port リ ケ system company make the name of an article " ノ バ テ Star Network MA 4 ").

(3) macromolecular compound (C-3)

Hydrogenated diene multipolymer (JSR company makes, the name of an article " ダ イ Na ロ Application 6200P ").

(other additive)

Activator (D-1): Magnesium Stearate.

Activator (D-2): Zinic stearas.

Activator (D-3): calcium stearate.

Antiaging agent (E-1): vinylformic acid 2-[1-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) ethyl]-4,6-di-tert-pentyl-phenyl ester (Sumitomo Chemical Co. Ltd. makes, the name of an article " Sumilizer GS ").

(embodiment 1)

Contain functional group's multipolymer (A-1), 1 mass parts metal compound particles (B-1), 4.5 mass parts activators (D-1) and 0.2 mass parts antiaging agent that 100 mass parts are specific join the double-arm pressure kneader of the 10L that is heated to 230 ℃ (manufacturing of モ リ ヤ マ company) respectively, with mixing 20 minutes (shearing rate 200s of 40rpm ^-1).By being set in 180 ℃, Off イ one ダ one Le one ダ one (manufacturing of モ リ ヤ マ company) of 40rpm, the block mixing thing of gained molten state is made pellet then, obtain the ionomer pellet.By electric heating pressurization pressure forming machine (manufacturing of Northwest ロ one Le company), pellet to the gained ionomer under 180 ℃ of die temperatures, 10 minutes pressurized, heated time, the pressurization condition of 5 minutes cooling times carries out extrusion forming, obtains the matrix band of 12cm * 12cm * 0.2cm.

The Fourier transform infrared spectrophotometer " FT-720 " that uses the hole field to make the manufacturing of company of institute carries out infrared spectroscopic analysis to gained ionomer and the specific functional group's multipolymer (A-1) that contains, as seen: in the gained ionomer, detect 1700cm in functional group's multipolymer (A-1) in specific containing ^-1Under-the COOH peak disappears 1500～1600cm ^-1The peak of middle appearance-COOMg.

(evaluation of ionomer)

Under the condition of 230 ℃ of temperature, load 10kg to ionomer measure melt flow rate (MFR) (MFR), with this index as flowability.The result is as shown in table 1 below.

Use the matrix band of gained ionomer, measure duroscope A hardness by the following method and extend as physical strength and glossiness, abrasion resistance and proportion as caoutchouc elasticity index, fracture tensile strength and tension fracture, carry out following resistance to marring test 1 and resistance to marring test 2 simultaneously as flexibility index, tensile-permanent set.The result is as shown in table 1.

(1) hardness (duroscope A hardness): measure according to JIS-K6253.

(2) tensile-permanent set: measure according to JIS-K6262.

(3) fracture tensile strength and tension fracture elongation: measure according to JIS-K6251.

(4) glossiness: use the glossmeter " GM-26 " that the color institute system is made in the village, under the condition of input angle 60 degree, measure glossiness.

(5) abrasion resistance:, measure wear volume and wearing and tearing opposing index according to the wearing test that JIS-K6264 carries out DIN.

(6) proportion: measure according to JIS-K7112.

(7) the resistance to marring test 1: use the smart mechanism of Japan to make the テ one バ one cut tester of manufacturing, the metal claw that is applied with 10g load is slidably reciprocated on the surface of matrix band.Load is increased 10g successively on one side,, on the surface of matrix band, produce cut, the value of load when writing down this matrix band surface generation cut Yi Bian repeat this operation.In this test, the load value of record is big more, then the resistance to marring excellence.

(8) resistance to marring test 2: with the surface of thumbnail scraping matrix band, the surface of this matrix band of visual observation, what do not have cut is evaluated as zero, have being evaluated as of cut *.

(comparative example 1)

With 100 mass parts specific contain functional group's multipolymer (A-1) and 0.2 mass parts antiaging agent joins the double-arm pressure kneader of the 10L that is heated to 230 ℃ (manufacturing of モ リ ヤ マ company) respectively, with mixing 20 minutes (shearing rate 200s of 40rpm ^-1).By being set in 180 ℃, Off イ one ダ one Le one ダ one (manufacturing of モ リ ヤ マ company) of 40rpm, the block mixing thing of gained molten state is made pellet then.Similarly to Example 1,, the mixing thing of pelletization is made matrix band, estimate by extrusion forming.The result is as shown in table 1.

(embodiment 2～7 and comparative example 2)

According to the blending ratio shown in the following table 1, each composition is joined the double-arm pressure kneader of the 10L that is heated to 230 ℃ (manufacturing of モ リ ヤ マ company), mixing 20 minutes with 40rpm.By being set in 180 ℃, Off イ one ダ one Le one ダ one (manufacturing of モ リ ヤ マ company) of 40rpm, the block mixing thing of gained molten state is made pellet then, obtain ionomer or ionomer composition pellet.Similarly to Example 1,, the particle of gained granulating ionomer or ionomer composition is made matrix band, estimate by extrusion forming.The result is as shown in table 1.

[table 1]

			Embodiment							Comparative example
												1	2	3	4	5	6	7	1	2
			The mixed proportion ︵ mass parts ︶ of composition	Specific contain functional group's multipolymer (A-1) specific contain functional group's multipolymer (A-2) specific contain functional group's multipolymer (A-3)		100 - -	100 - -	100 - -	100 - -	- 100 -	- - 100										100 - -	100 - -	100 - -
Metal compound particles (B-1) metal compound particles (B-2) metal compound particles (B-3) metal compound particles (B-4) metal compound particles (B-5)		1.0 - - - -										- 1.4 - -	- - 1.4 - -	- - - 1.4 -	- - - 1.4 -	- - - 1.4 -	- - - 3.5 -	- - - - -	- - - - 1.2
				Macromolecular compound (C-1) macromolecular compound (C-2) macromolecular compound (C-3)		- - -	- - -	- - -	- - -	- - -	- - -									25 25 100	- - -	- - -
Activator (D-1) activator (D-2) activator (D-3) antiaging agent (E-1)		4.5 - - 0.2										- 4.8 - 0.2	- 4.8 - 0.2	- 4.8 - 0.2	- 4.8 - 0.2	- 4.8 - 0.2	- 10 - 0.2	- - - 0.2	- - 4.7 0.2
				Evaluation result	MFR (230 ℃, 10kg) [g/10 minute]		11	17	19	13	18									15	35	57	2
Duroscope A hardness		58	65									65	61	58	57	75	55	65
					Tensile-permanent set [%]		12	10	9	9	10								11	12	9	12
Fracture tensile strength [MPa]		12	22									27	31	20	15	18	1.2	12
					Tension fracture elongation [%]		910	680	650	700	840								950	810	1470	860
Glossiness		40	72									75	78	73	75	74	24	44
					Abrasion resistance	Wear volume [cm 3]	0.048	0.0347	0.033	0.037	0.048								0.054	0.86	0.406	0.113
Wearing and tearing opposing index [%]	67	29	28									52	67	75	119	343	95
						Proportion		0.9	0.9	0.9	0.9							0.9	0.9	0.9	0.9	0.9
Resistance to marring test 1[g]		330	270		360							440	220	180	210	30	50
						Resistance to marring test 2		○	○	○	○							○	○	○	×	×

As shown in Table 1: the ionomer of embodiment 1～7 or the physical strength of its composition, resistance to marring, glossiness, caoutchouc elasticity and abrasion resistance are all excellent.And comparative example 1 is the multipolymer by metal ion crosslinked not, so physical strength, caoutchouc elasticity, resistance to marring and abrasion resistance are low.In the comparative example 2, the median size of employed metal compound particles is 6.1 μ m, so resistance to marring is low.

[embodiment of the alternative plan of ionomer of the present invention]

The various compositions that use in following embodiment and the comparative example are as follows.

(ethylene series random copolymers (F))

In having carried out nitrogen metathetical 300mL three-necked flask fully, add 32.8g (150mmol) 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid, 200mL dry tetrahydrofuran and 13.1g (165mmol) dry pyridine, under 0 ℃ of temperature, in this reaction system, slowly drip 24.9g (165mmol) chlorotriethyl silane, drip finish after, at room temperature stirred 5 hours.Then filter this solution, behind the concentrated filtrate, after adding 100mL normal hexane stirred 1 hour, filter this solution.Concentrated filtrate then, underpressure distillation under 143-147 ℃, the condition of 1.5mmHg obtains 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid triethylsilyl ester.

In the separable flask of nitrogen metathetical 2L, add 1000mL hexane, 3.5mL 4-methyl Fourth Ring [6.2.1.1 as solvent ^3,6.0 ^2,7] 1.0mol/L hexane solution, the 2ml 5-ethylidene-2-norbornene of 12 carbon-9-alkene-4-carboxylic acid triethylsilyl ester, ethene without interruption (supply: 5.0L/ minute) under 20 ℃/propylene (supply: 4.5L/ minute)/hydrogen (supply: 0.6L/ minute) mixed gas, after 5 minutes, in detachable flask, add 3.66mL VOCl ₃The 0.32mol/L hexane solution, after 5 minutes, in the detachable flask of 2L, add 20.7mLAl ₂(C ₂H ₅) ₃Cl ₃The 0.41mol/L hexane solution, the addition polymerization of trigger monomer is handled.Handle 25 ℃ of addition polymerizations of carrying out 10 minutes, in reaction system, add 4.8mL acetate then, stop polyreaction.

With the 500mL water washing of gained polymeric solution, by being injected in a large amount of methyl alcohol multipolymer is separated out then, with its vacuum-drying, obtain the ethylene series random copolymers (F) of 21.1g white.

This ethylene series random copolymers is analyzed, wherein proportional from containing of the structural unit of ethene be 73.18 moles of %, from containing of the structural unit of propylene proportional be 25.50 moles of %, proportional from containing of the structural unit of 5-ethylidene-2-norbornene be 0.94 mole of %, from 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid triethylsilyl ester structural unit to contain proportional be 0.38 mole of %.By being that the polystyrene conversion weight-average molecular weight (Mw) of the gel permeation chromatography of solvent is 25.5 * 10 with the orthodichlorobenzene ⁴The infrared absorption spectrum of gained ethylene series random copolymers as shown in Figure 1.

(ethylene series random copolymers (G))

With 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid triethylsilyl ester replaces with 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid t-butyldimethylsilyl ester, in addition same with above-mentioned ethylene series random copolymers (F), obtain the ethylene series random copolymers (G) of 17.7g white.

This ethylene series random copolymers is analyzed, wherein proportional from containing of the structural unit of ethene be 74.36 moles of %, from containing of the structural unit of propylene proportional be 22.95 moles of %, proportional from containing of the structural unit of 5-ethylidene-2-norbornene be 2.30 moles of %, from 4-methyl Fourth Ring [6.2.1.1 ^3,6.0 ^2,7] 12 carbon-9-alkene-4-carboxylic acid t-butyldimethylsilyl ester structural unit to contain proportional be 0.39 mole of %.By being that the polystyrene conversion weight-average molecular weight (Mw) of the gel permeation chromatography of solvent is 22.2 * 10 with the orthodichlorobenzene ⁴

(metallic compound)

Metallic compound: zinc oxide (Sakai chemical industrial company makes, trade(brand)name " Na ノ Off ア イ Application W-1 ", median size 0.01 μ m)

(additive)

Activator: Zinic stearas (Sakai chemical industrial company makes, trade(brand)name " SZ-2000 ")

Antiaging agent: vinylformic acid 2-[1-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) ethyl]-4,6-di-tert-pentyl-phenyl ester (Sumitomo Chemical Co. Ltd. makes, trade(brand)name " Sumilizer GS ")

Weather resisting agent: hindered amine is weather resisting agent (Asahi Electro-Chemical Co. Ltd makes, trade(brand)name " ア デ カ ス Block LA-502 ")

Pigment: contain the polyethylene-based masterbatch of 40 quality % sooty (big Japanese ink chemical industrial company makes trade(brand)name " ペ オ ニ one Block Star Network F-30940MM ")

(embodiment 8)

100 mass parts polyolefin random copolymerss (F) (polymkeric substance (F)), 1.4 mass parts metallic compounds, 4.8 mass parts activators, 0.2 mass parts antiaging agent, 0.3 mass parts weather resisting agent and 1.25 mass parts pigment are joined the double-arm pressure kneader of the 10L that is heated to 230 ℃ (manufacturing of モ リ ヤ マ company) respectively, with mixing 20 minutes (shearing rate 200s of 40rpm ^-1).By being set in 180 ℃, Off イ one ダ one Le one ダ one (manufacturing of モ リ ヤ マ company) of 40rpm, the block mixing thing of gained molten state is made pellet then, obtain the ionomer pellet.By electric heating pressurization extrusion forming machine (manufacturing of Northwest ロ one Le company), pellet to the gained ionomer under 180 ℃ of die temperatures, 10 minutes pressurized, heated time, the pressurization condition of 5 minutes cooling times carries out extrusion forming, obtains the matrix band of 12cm * 12cm * 0.2cm.

(evaluation of ionomer)

According to JIS K7201, under the condition of 230 ℃ of temperature, load 10kg, the gained ionomer is measured melt flow rate (MFR) (MFR), with this index as flowability.The result is as shown in table 2 below.Use the matrix band of gained ionomer, measure duroscope A hardness by the following method and extend as physical strength and abrasion resistance and proportion as caoutchouc elasticity index, fracture tensile strength and tension fracture, carry out following resistance to marring test 1 and resistance to marring test 2 simultaneously as flexibility index, tensile-permanent set.The result is as shown in table 2.

(1) hardness (duroscope A hardness): measure according to JIS-K6253.

(2) tensile-permanent set: measure according to JIS-K6262.

(3) fracture tensile strength and tension fracture elongation: measure according to JIS-K6251.

(4) abrasion resistance: carry out the DIN wearing test according to JIS-K6264, measure wear volume and wearing and tearing opposing index.

(5) proportion: measure according to JIS-K7112.

(6) the resistance to marring test 1: use the smart mechanism of Japan to make the テ one バ one cut tester of manufacturing, the metal claw that is applied with 10g load is slidably reciprocated on the surface of matrix band.Load is increased 10g successively on one side,, on the surface of matrix band, produce cut, the value of load when writing down this matrix band surface generation cut Yi Bian repeat this operation.In this test, the load value of record is big more, then the resistance to marring excellence.

(7) the resistance to marring test 2: with the surface of thumbnail scraping matrix band, according to its scuffing degree of the visual judgement of following benchmark (1 and 2 is qualified level).

1: do not have cut, 2 fully: simple cut is arranged but recovery immediately, cut disappearance, 3: simple cut, 4 is arranged: dark cut is arranged.

(embodiment 9)

Use ethylene series random copolymers (G) (polymkeric substance (G)) to replace ethylene series random copolymers (F), in addition same with the situation of embodiment 8, preparation ionomer pellet, the matrix band of preparation ionomer.Gained ionomer and matrix band thereof are carried out the evaluation of above-mentioned ionomer.The result is as shown in table 2.

(comparative example 3)

Do not use metallic compound and activator, in addition same with the situation of embodiment 8, preparation ethylene series thermoplastic elastomer pellet, the matrix band of preparation ethylene series thermoplastic elastomer.Gained ethylene series thermoplastic elastomer and matrix band thereof are carried out the evaluation of above-mentioned ionomer.The result is as shown in table 2.

[table 2]

	Embodiment 8	Embodiment 9	Comparative example 3
				Polymkeric substance (F)	100	-	-
Polymkeric substance (G)	-	100	100
				Metallic compound	1.4	1.4	0
Activator	4.8	4.8	0
				Antiaging agent	0.2	0.2	0.2
Weather resisting agent	0.3	0.3	0.3
				Pigment	1.25	1.25	1.25
MFR (230 ℃, 10kg) [g/10 minute]	21	14	30
				Hardness (duroscope A hardness)	61	64	61
Fracture tensile strength [MPa]	9.6	10.4	4.5
				Tension fracture elongation [%]	780	650	1130
Tensile-permanent set [%]	10	9	15
				Wear volume [cm 3]	0.048	0.03	0.186
Wearing and tearing opposing index [%]	40	25	154
				Resistance to marring test 1	500g or more than	50g or more than	60g
Resistance to marring test 2	1	1	4
				Proportion	0.9	0.9	0.9

As shown in Table 2: the ionomer caoutchouc elasticity of embodiment 8,9, flexibility, forming process (flowability), resistance to marring and abrasion resistance are all excellent.And the ethylene series thermoplastic elastomer of comparative example 3 does not add metallic compound and activator, therefore has fracture tensile strength low especially, the problem of abrasion resistance and resistance to marring difference.

Industrial applicability

Ionomer of the present invention contains the ionomer of caoutchouc elasticity, flexibility, forming process, resistance to marring and the abrasion resistance of tool excellence, therefore, in various moulding product fields such as trolley part, can be used as the equivalent material of metal parts, the equivalent material of RIM polyurethane part, the equivalent material of vulcanized rubber, the equivalent material of soft PVC etc.Specifically; can be widely used in the snubber of automobile; the outer decoration with hammer; envelope window liner; the door sealing liner; the container tightening flap; roof side rail; sign; inner panel; door internal decoration plate; the surfacing of internal and external ornaments such as Console; draught sealing etc.; the leather seat that needs resistance to marring; sealing material that the aircraft boats and ships are used and internal and external ornament surfacing etc.; the sealing material that civil construction is used; internal and external ornament surfacing or waterproof sheet etc.; the sealing material that the conventional mechanical device is used etc.; the packing ring of light current parts; epidermis or shell etc.; information instrument roller; cleaning balde; the electronic component-use film; sealing material; the protect image film of photo etc.; the material of construction decorating film; the Medical Instruments parts; electric wire; the sundry goods product; general processed goods such as sporting goods, the CMP pad that semiconductor grinding is used; various film (the protective membranes of electronic component-use; absorb ballistic film; light polarizing film; absorb the film of specific wavelength etc.); the protective membrane that uses in the manufacturing process of flat-panel monitor such as semiconductor device and liquid crystal indicator (FPD).The preparation method of ionomer of the present invention can prepare the ionomer of the invention described above effectively.

Claims (21)

1. ionomer, this ionomer is that 1 μ m or following metal compound particles obtain with the polymer reaction with functional group by making median size.

2. the ionomer of claim 1, wherein the ratio of above-mentioned metal compound particles is 0.01～10 mass parts with respect to the above-mentioned polymkeric substance with functional group of 100 mass parts.

3. claim 1 or 2 ionomer, the metal ingredient in the wherein above-mentioned metal compound particles contains at least a metal that is selected from sodium, magnesium, calcium, zirconium, zinc and aluminium.

4. claim 1 or 2 ionomer, wherein above-mentioned metal compound particles contains zinc oxide.

5. each ionomer in the claim 1～4, wherein above-mentioned polymkeric substance with functional group are that ethene, carbonatoms are 3～10 alpha-olefin, have an ethylene series random copolymers that the unsaturated monomer of functional group and non-conjugated diene copolymerization as required obtain.

6. the ionomer of claim 5, this functional group in the wherein above-mentioned unsaturated monomer with functional group is carboxyl, hydroxyl, epoxy group(ing) or sulfonic group.

7. the ionomer of claim 5, wherein above-mentioned unsaturated monomer with functional group is the functionality ring compound shown in the following general formula (1),

[changing 1]

(in the general formula (1), R ¹Expression hydrogen atom or carbonatoms are 1～10 alkyl, Y ¹, Y ²And Y ³Independent respectively expression hydrogen atom, carbonatoms be 1～10 alkyl or-COOH, Y ¹, Y ²And Y ³In at least one be-COOH Y in addition ¹, Y ²And Y ³In two or morely at least be-during COOH, they can be the acid anhydrides (CO-(O)-CO-), o is 0～2 integer, p is 0～5 integer) of interconnection formation.

8. the ionomer of claim 5, wherein above-mentioned ethylene series random copolymers are that 3～10 alpha-olefin, the functionality ring compound shown in 0.01～5 mole of above-mentioned general formula of % (1) and the copolymerization of 0～10 mole of % non-conjugated diene obtain by 35～94.99 moles of % ethene, 5～50 moles of % carbonatomss.

9. the preparation method of ionomer, this method has following operation: in median size is in the presence of 1 μ m or the following metal compound particles, and the polymkeric substance with functional group is heat-treated or dynamically thermal treatment.

10. moulding product, these moulding product are that the formed material that will contain each ionomer in the claim 1～8 obtains by the method for forming moulding that is selected from injection moulding, extrusion moulding, vacuum forming, powder slush moulding method, rolling-molding method, transfer molding method, solvent casting method and extrusion forming method.

11. the preparation method of ionomer, this method is that ethylene series random copolymers and metallic compound are carried out dynamic thermal treatment, wherein said ethylene series random copolymers is that to make ethene, carbonatoms be that 3～10 alpha-olefin and the functionality ring compound copolymerization shown in the following general formula (2) obtain

[changing 2]

(in the general formula (2), n is 0 or 1, R ¹, R ², R ³And R ⁴Independent respectively expression hydrogen atom, halogen atom or univalent organic group).

12. the preparation method of the ionomer of claim 11, in the wherein above-mentioned general formula (2), R ¹, R ²And R ³Respectively independent, for hydrogen atom or carbonatoms 1～20 alkyl.

13. the preparation method of the ionomer of claim 11 or 12, in the wherein above-mentioned general formula (2), R ¹, R ²And R ³All be ethyl or R ¹, R ²And R ³In one be the tertiary butyl, two is methyl.

14. the preparation method of each ionomer in the claim 11～13, in the wherein above-mentioned general formula (2), R ⁴Be methyl.

15. the preparation method of each ionomer in the claim 11～14, wherein,

Above-mentioned ethylene series random copolymers is that 3～10 alpha-olefin and the functionality ring compound copolymerization shown in 0.01～5 mole of above-mentioned general formula of % (2) generate by 35～94.99 moles of above-mentioned ethene of %, 5～50 moles of above-mentioned carbonatomss of %,

And be under 10～2000/ seconds the condition above-mentioned ethylene series random copolymers of 100 mass parts and the above-mentioned metallic compound of 0.1～20 mass parts to be carried out dynamic thermal treatment in 120～350 ℃ of temperature, shearing rate.

16. the preparation method of each ionomer in the claim 11～15, wherein, above-mentioned ethylene series random copolymers also can make the non-conjugated diene copolymerization generate except that the functionality ring compound shown in above-mentioned ethene, above-mentioned alpha-olefin and the above-mentioned general formula (2).

17. the preparation method of the ionomer of claim 16, wherein, above-mentioned ethylene series random copolymers can also make 10 moles of % non-conjugated diene copolymerization generate except that the functionality ring compound shown in above-mentioned ethene, above-mentioned alpha-olefin and the above-mentioned general formula (2).

18. the preparation method of each ionomer in the claim 11～17, wherein, above-mentioned metallic compound is metal oxide or metal hydroxides.

19. ionomer, this ionomer is obtained by the preparation method of each ionomer in the claim 11～18.

20. the preparation method of ionomer composition, this method is: 120～350 ℃ of temperature, shearing rate is to 100 mass parts ethylene series random copolymerss under 10～2000/ seconds the condition, 0.1～20 mass parts metallic compounds, carry out dynamic thermal treatment with 300 mass parts or the following macromolecular compound that is selected from thermoplastic resin and rubber and/or 100 mass parts or following tenderizer, wherein said ethylene series random copolymers is by 35～94.99 moles of % ethene, 5～50 moles of above-mentioned carbonatomss of % are 3～10 alpha-olefin, 0.01 functionality ring compound shown in～5 moles of following general formulas of % (2) and the copolymerization of 0～10 mole of % non-conjugated diene obtain

[changing 3]

(in the general formula (2), n is 0 or 1, R ¹, R ², R ³And R ⁴Independent respectively expression hydrogen atom, halogen atom or univalent organic group).

21. ionomer composition, said composition is obtained by the preparation method of the ionomer composition of claim 20.

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