KR100230661B1 - Higher alpha-olefin copolymer and process for the preparation of the same - Google Patents

Abstract

The higher α-olefin copolymers of the present invention are copolymers of certain higher α-olefins, certain α, ω-dienes and certain non-conjugated dienes, which have a specific molar ratio of higher α-olefins to α, ω-dienes, and nonconjugated. It has a specific content of diene and a specific intrinsic viscosity, which can be prepared using a catalyst for olefin polymerization formed from a specific solid titanium catalyst component, an organometallic compound catalyst component, and an electron donor catalyst component, and the dustproof rubber of the present invention. The molded article is manufactured from the vulcanized product of the copolymer described above, and the copolymer described above can provide excellent vulcanized products because of excellent weatherability, ozone resistance, thermal aging resistance, low temperature characteristics, dustproof characteristics and dynamic fatigue resistance as well as processability.

Description

Higher α-olefin Copolymers and Methods for Making the Same

The present invention relates to a novel higher α-olefin copolymer, a method for producing the copolymer and a copolymer thereof.

Ethylene / propylene / diene copolymers are widely used for plastic parts for automotive parts, industrial rubber products, electrical insulation, civil engineering and building materials, rubberized fiber, pulley propylene and polystyrene because of their high heat resistance and ozone resistance.

However, because ethylene / propylene / diene copolymers have poor homogeneity fatigue resistance, they cannot be used for special applications such as dustproof rubber, rubber rolls, belts, tires, and coating materials for vibration parts.

Natural rubber has excellent dynamic fatigue resistance but has practical problems because of its low heat resistance and ozone resistance.

Regarding copolymers of higher α-olefins and nonconjugated dienes, U.S. Patent Nos. 3,933,769: 4,064,335, and 4,340,705 disclose higher α-olefins, methyl-1, 4-hexadiene and α, ω-diene copolymers. It is. Methyl-1, 4-hexadiene is a mixture of 4-methyl-1, 4-hexadiene and 5-methyl-1, 4-hexadiene. These monomers have different reaction rates. Therefore, in the case of performing the continuous polymerization, it is difficult to recover the monomers for reuse.

In addition, 4-methyl-1 and 4-hexadiene differ from 5-methyl-1 and 4-hexadiene in copolymerization reactivity with higher α-olefins. Therefore, there is a problem of low monomer conversion and poor polymerization efficiency.

In addition, the use of α, ω-diene creates a gel in the final copolymer which adversely affects the physical properties of the final product obtained.

The method for producing the higher α-olefin copolymer described in the above document uses a titanium trichloride type catalyst or a catalyst formed from titanium detrachloride and organoaluminum, and thus has a disadvantage in that the catalyst activity is not sufficient and the manufacturing cost is high.

Dustproof rubber molded parts are used to prevent or reduce vibration transmission and have been widely used in machinery, electrical appliances, civil and building materials, automobiles and other transportation equipment. Natural rubber and SBR have been used so far for such dustproof rubber molded products.

However, the environment using the anti-vibration rubber molded article has become increasingly strict in recent years, and a characteristic of not only long life but also maintenance is required.

In this regard, it has been studied to use ethylene / propylene / diene type rubber (EPDM) having excellent heat aging resistance for dustproof rubber molded articles. However, dustproof rubber molded articles formed by EPDM have a problem of being easily fatigued and easily broken under extreme vibrations, that is, under dynamic conditions.

Therefore, there has been a strong demand for the appearance of long-life dustproof rubber molded articles having excellent heat aging resistance and dynamic fatigue resistance (flexible fatigue resistance).

The present inventors have worked hard to develop copolymers having excellent processability as well as dynamic fatigue resistance, weather resistance, ozone resistance, heat aging resistance and low temperature characteristics, and to develop long-life dustproof rubber molded articles having excellent heat aging resistance and dynamic fatigue resistance. . As a result, it was found that the higher α-olefin copolymer having excellent various properties described above can be obtained by copolymerizing specific higher α-olefins, specific non-conjugated dienes, and specific α, ω-dienes in the presence of a catalyst for specific olefin polymerization.

An object of the present invention is to provide a method and to provide a high quality α-olefin copolymer having excellent processability as well as dynamic fatigue resistance, weather resistance, ozone resistance, heat aging resistance and low temperature characteristics.

Figure 1 is a flow chart showing the production steps of the catalyst for olefin polymerization that can be used for the preparation of the higher α-olefin copolymer of the present invention

Figure 2 is a graph of the relationship between the composite modulus of elasticity (G ^* ) and temperature of rubber

The higher α-olefin copolymer according to the present invention is a high α-olefin having 6-20 atoms, the high α- of the α, ω-diene represented by the following formula [I] and the nonconjugated diene represented by the following formula [II]: Olefin copolymer,

The higher α-olefin copolymer is

(A) molar ratio of higher α-olefins to α, ω-dienes

[Advanced α-olefin / α, ω-diene] is 95/5 to 50/50,

(B) the content of the nonconjugated diene is 0.01 to 30 mol%,

(C) Intrinsic viscosity [eta] is 1.0-10.0 dl / g when measured in decalin at 135 degreeC.

Wherein n is an integer of 1 to 3, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

Wherein n is an integer of 1 to 5, R ³ is an alkyl group having 1 to 4 carbon atoms, R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, provided that both R ⁴ and R ⁵ Not hydrogen.

The process for producing a higher α-olefin copolymer according to the present invention includes a higher α-olefin having 6 to 20 carbon atoms, the above-mentioned formula [I] α, ω-diene, and the nonconjugated diene represented by the above formula [II].

(a) a solid titanium catalyst component containing magnesium, titanium, halogens and electron donors as essential components;

(b) organoaluminum compound catalyst component

(c) A method of copolymerizing in the presence of a catalyst for olefin polymerization comprising the electron donor catalyst component.

The dustproof rubber molded article according to the present invention is a dustproof rubber molded article made of a vulcanized product of a higher α-olefin copolymer, wherein the copolymer is a higher α-olefin having 6 to 20 carbon atoms, α, represented by the formula [I] ω-diene, a copolymer of the non-conjugated diene represented by the formula [II],

(A) molar ratio of higher α-olefins to α, ω-diene [higher α-olefins / α, ω-diene] is 95/5 to 50/50

(B) the content of the non-conjugated diene is 0.01 to 30 mol%,

(C) Intrinsic viscosity [] is 1.0-10.0 dl / g as measured in decalin at 135 degreeC.

The method for producing a dustproof rubber molded article according to the present invention is a method for molding and vulcanizing the above-described high α-olefin copolymer.

The higher α-olefin copolymer of the present invention, the production method of the copolymer, the dustproof rubber molded article according to the present invention and the production method of the molded article will be described in detail below.

First, the higher α-olefin copolymer of the present invention will be described below.

The higher α-olefin copolymers of the present invention are specific copolymers in which specific higher α-olefins, specific α, ω-dienes, and specific non-conjugated dienes are composed of specific ratios.

Higher α-olefins

The higher α-olefins usable in the present invention are higher α-olefins having 6 to 20 carbon atoms.

Specific examples of the higher α-olefin include hexene-1, heptene-1, octene-1, nonene-1, decene-1, undecene-1, dodecene-1, tridecene-1, detradecene-1, Pentadecene-1, hexadecene-1, heptadecene-1, nonadecene-1, eicosene-1, 9-methyldecene-1, 11-methyldecene-1, 12-ethyltetradecene-1 and the like.

In the present invention, the above-mentioned higher α-olefins may be used alone or in combination of two or more. Of these higher α-olefins, especially hexene-1, octene-1 and decene-1 are preferred.

α, ω-diene

(Alpha), ω-diene which can be used by this invention is represented by following formula [I].

In the formula [I], n is an integer of 1 to 3, and R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

Specific examples of α, ω-diene include 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 3-methyl-1, 4-hexadiene, 3-methyl-1, 5- Hexadiene, 3-methyl-1, 6-heptadiene, 4-methyl-1, 6-heptadiene, 3,3-dimethyl-1, 4-hexadiene, 3,4-dimethyl-1, 5-hexadiene , 4,4-dimethyl-1, 6-heptadiene and 4-methyl-1, 6-heptadiene and the like.

In the higher α-olefin copolymer of the present invention, when R ¹ and R ² are each hydrogen, repeating units derived from α, ω-diene exist in the form represented by the following formulas [III] and / or [IV]. It is estimated.

In the higher α-olefin copolymer of the present invention, the aforementioned repeating units are arranged irregularly to form a substantially linear structure.

The structure of these repeating units can be confirmed by ¹³ C-NMR.

The expression "substantially linear structure" as used herein means to include a branched chain structure but not a crosslinked bond structure. It can be seen that the higher α-olefin copolymer of the present invention has a substantially linear structure due to the fact that the copolymer is completely dissolved in decarin at 135 ° C. and does not contain a gel crosslinking copolymer.

Nonconjugated diene

The nonconjugated diene which can be used by this invention is represented by following formula [II].

In the formula [II], n is an integer of 1 to 5, R ³ is an alkyl group having 1 to 4 carbon atoms, R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, provided , R ⁴ and R ⁵ are not both hydrogen atoms.

For example, the specifics of non-conjugated dienes

4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene,

5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene,

6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 4-methyl-1,4-octadiene,

5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene,

5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene,

6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene,

6-ethyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene,

4-ethyl-1,4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene,

6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene,

6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene,

7-ethyl-1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene,

7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene,

5-methyl-1,5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene,

6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene,

6-ethyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene,

8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-methyl-1,7-decadiene,

8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,7-decadiene,

9-methyl-1,8-undecadiene.

In the present invention, the above-mentioned nonconjugated dienes may be used alone or in combination of two or more.

In addition to the non-conjugated dienes described above, other copolymerizable monomers such as ethylene, propylene, butene-1 and 4-methylpentene-1 may be used within a range not contrary to the object of the present invention.

The molar ratio of the higher α-olefins constituting the higher α-olefin copolymer of the present invention to the structural units derived from α, ω-diene (higher α-olefin / α, ω-diene) is 50/50 to 95/5, Preferably it is 60/40-90/10, More preferably, it is 65/35-90/10. The value of molar ratio is the value measured and calculated | required by ¹³ C-NMR method.

In the present invention, the higher α-olefin is copolymerized with α and ω-diene to improve the processability of the resulting higher α-olefin copolymer.

The content of the non-conjugated diene in the higher α-olefin copolymer of the present invention is preferably 0.01 to 30 mol%, preferably 0.1 to 20 mol%, particularly preferably 0.1 to 10 mol%. The iodine value of the higher α-olefin copolymer is 1 to 50, preferably 2 to 30. This characteristic value is a reference value when vulcanizing the higher α-olefin copolymer of the present invention using sulfur or peroxide.

The higher α-olefin copolymer of the present invention has an intrinsic viscosity [η] of 1.0 to 10.0 dl / g, preferably 1.5 to 7 dl / g, measured in decalin at 135 ° C. This characteristic value is a measure of the molecular weight of the higher α-olefin copolymer of the present invention, and is combined with other characteristic values to obtain a copolymer having excellent properties such as weather resistance, ozone resistance, thermal aging resistance, low temperature characteristics and dynamic fatigue resistance. use.

The higher α-olefin copolymer of the present invention can be produced by the following method.

The higher α-olefin copolymer of the present invention can be obtained by copolymerizing higher α-olefin, α, ω-diene represented by the above formula [I] and nonconjugated diene represented by the above formula [II] in the presence of an olefin polymerization catalyst. have.

The catalyst for olefin polymerization which can be used in the present invention is composed of a solid titanium catalyst component [A-1], an organometallic compound catalyst component [B], and an electron donor catalyst component [C].

1 is a flow chart showing the steps of preparing a catalyst for olefin polymerization that can be used when preparing the higher α-olefin copolymer of the present invention.

The solid titanium catalyst component [A-1] used in the present invention is a highly active catalyst component containing magnesium, titanium, halogens, and electron donors as essential components.

The solid titanium catalyst component [A-1] can be produced by, for example, bringing a titanium compound, a magnesium compound, and an electron donor into contact with each other as necessary.

Examples of the titanium compound which can be used in the production of the solid titanium catalyst component [A-1] include tetravalent titanium compounds and trivalent titanium compounds.

As said tetravalent titanium compound, the compound represented by a following formula is mentioned.

Ti (OR) _g X _4-g

Wherein R is a hydrocarbon group, X is a halogen atom, and g is a number satisfying the condition of 0 ≦ g ≦ 4.

Specific examples of the compound are as follows.

Titanium tetrahalides such as TiCl ₄ , TiBr ₄ and TiI ₄ ;

Ti (OCH ₃ ) Cl ₃ ,

Ti (OC ₂ H ₅ ) Cl ₃ ,

Ti (On-C ₄ H ₉ ) Cl ₃ ,

Ti (OC ₂ H ₅ ) Br ₃ ,

Trihalogenated alkoxytitanium such as Ti (O-iso-C ₄ H ₉ ) Br ₃ ;

Ti (OCH ₃ ) ₂ Cl ₂ ,

Ti (OC ₂ H ₅ ) ₂ Cl ₂ ,

Ti (On-C ₄ H ₉ ) ₂ Cl ₂ ,

Ti (OC ₂ H ₅ ) ₂ Br ₂ ,

Dihalogenated dialkoxy titanium, such as these,

Ti (OCH ₃ ) ₃ Cl,

Ti (OC ₂ H ₅ ) ₃ Cl,

Ti (On-C ₄ H ₉ ) ₃ Cl,

Ti (OC ₂ H ₅ ) ₃ Br,

Monohalogenated trialkoxy titanium such as;

Ti (OCH ₃ ) ₄ ,

Ti (OC ₂ H ₄ ) ₄ ,

Ti (On-C ₄ H ₉ ) ₄ ,

Ti (Oiso-C ₄ H ₉ ) ₄ ,

Ti (o-2-ethylhexyl) ₄ ,

Tetraalkoxy titanium, such as these, is mentioned.

Among these, titanium tetrahalide is especially preferable, and titanium tetrachloride is used more preferably.

These titanium compounds may be used alone or in combination of two or more kinds thereof.

In addition, these titanium compounds can be diluted with hydrocarbon compounds or halogenated hydrocarbon compounds.

As the trivalent titanium compound, titanium trichloride is used.

Titanium trichloride obtained by contacting and reducing titanium tetrachloride with hydrogen, a metal (i.e., a magnesium metal, an aluminum metal and a titanium metal) or an organometallic compound (i.e., an organic magnesium compound, an organic aluminum compound and an organic zinc compound) is preferable. Is used.

In this invention, the magnesium compound used for manufacture of a solid titanium catalyst component [A-1] can be mentioned a magnesium compound which has a reducing property or does not have.

Here, there is a compound represented by the following formula, for example, of a magnesium compound having reducibility.

X _n MgR _2-n

In the formula, n is a number satisfying the condition of 0 ≦ n ≦ 2; R is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group; if n is 0, the two R's may be the same or different from each other; X is halogen.

The specific example of the organomagnesium compound which has reducibility is as follows. : Dialkyl magnesium compounds such as dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, octyl butyl magnesium and ethyl butyl magnesium; Halogenated alkyl magnesium such as ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride; Alkyl magnesium alkoxides, such as butyl ethoxy magnesium, ethyl butoxy magnesium, and octyl butoxy magnesium; Butylmagnesium hydride and the like.

Specific examples of magnesium compounds having no reducing agent include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride, magnesium methoxy chloride, magnesium ethoxy chloride, isopropoxy chloride, butoxy chloride, and octoxy Alkoxy magnesium halides, such as magnesium chloride; Aryloxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; Alkoxy magnesium, such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, and 2-ethyl hexamethane magnesium; Aryloxy magnesium, such as phenoxy magnesium and dimethyl phenoxy magnesium; Magnesium carbonates, such as magnesium laurate and magnesium stearate, are mentioned.

Moreover, magnesium metal and magnesium hydride can be used as magnesium which does not have reducibility.

These magnesium compounds having no reducing properties may be compounds derived from the above-described reducing magnesium compounds or compounds derived at the time of producing the catalyst component.

To derive a non-reducing magnesium compound from a reducing magnesium compound, for example, the reducing magnesium compound may be a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, a halogen-containing compound or an OH. It is sufficient to contact with a compound having a group or an activated carbon-oxygen bond.

In addition to the magnesium compound with or without reducing properties, it may be in the form of a mixture of an organometallic compound or another metal compound described below such as a complex compound of the magnesium compound with another metal (for example, aluminum, zinc, boron, beryllium, sodium and potassium). good. In addition, the said magnesium compound can be used individually or in combination of 2 or more types of said compounds.

In addition, the said magnesium compound can be used in a liquid phase or a solid phase. When the magnesium compound used is in the solid phase, it can be converted into the liquid phase using an alcohol, carboxylic acid, aldehyde, amine, metal acid ester, etc. described below as the electron donor.

Various titanium compounds other than those described above may be used to prepare the solid titanium catalyst component [A-1], but those in the form of halogen-containing magnesium compounds are preferred among the finally obtained solid titanium catalyst components [A-1]. .

Therefore, when using a magnesium compound which does not contain a halogen, it is preferable to make the said solid titanium catalyst component by making the compound contact-react with a halogen containing compound halfway.

Of the various magnesium compounds, magnesium compounds having no reducing properties are preferable, and among these, magnesium chloride, magnesium alkoxychloride and aryloxymagnesium chloride are particularly preferable.

In the production of the solid titanium catalyst component [A-1], it is preferable to use an electron donor.

Examples of the electron donor include the following: oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, esters of organic or inorganic acids, ethers, diethers, acid amides, acid anhydrides, and alkoxysilanes; Nitrogen-containing electron donors such as ammonia, amine, nitrile, pyridine, and isocyanate, more specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octa C1-C18 alcohols, such as decyl alcohol, oleyl alcohol, benzyl alcohol, phenyl ethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropyl benzyl alcohol, trichloro ethanol, trichloro ethanol, trichlorohexanol, etc. Halogen-containing alcohols of 18 to 18; Phenols having 6 to 20 carbon atoms which may have lower alkyl groups such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, naphthol, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, C3-C15 ketones, such as benzophenone and benzoquinone, acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, C2-C15 aldehyde, methyl formate, methyl acetate, ethyl acetate, Vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl lactate, ethyl gil acetate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexane carbonate, methyl benzoate, benzoic acid Ethyl, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, tol Ethyl laurate, amyl toluate, ethyl ethyl benzoate, methyl anise, ethyl anise, ethyl ethoxybenzoate, (scan) -butyrolactone, δ-valerolactone, coumarin, phthalide, ethyl carbonate C2-C15 acid halides, such as C2-C18 organic acid ester, acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride, methyl ether, ethyl ether, isopropyl ether, butyl ether, alkyl ether, tetrahydro Ethers having 2 to 20 carbon atoms such as furan, anisole and diphenyl ether; Acid amides such as N, N-dimethylacetamide, N, N-dimethylbenzamide, N, and N-dimethyltoluamide; Amines such as trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine, nitriles such as acetonitrile, benzonitrile and trinitrile, pyridine such as pyridine, methylpyridine, ethylpyridine and dimethylpyridine ; Acid anhydrides, such as acetic anhydride, phthalic anhydride, and benzoic anhydride, are used.

Preferred examples of the organic acid ester include polycarboxylates having a skeleton of the following formula.

In the above formula, R ¹ is a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ , R ⁶ is a hydrogen atom, a substituted or unsubstituted hydrocarbon group, R ³ , R ⁴ is a hydrogen atom, a substituted or unsubstituted hydrocarbon group , At least one of R ³ and R ⁴ is preferably a substituted or unsubstituted hydrocarbon group.

R ³ and R ⁴ may be connected to each other to form a cyclic structure. When the hydrocarbon groups R ¹ to R ⁶ are substituted, the substituted hydrocarbon group contains other atoms such as N, O, and S, and groups such as COC, COOR, COOH, OH, SO ₃ H, -CNC, and NH ₂ Have

The specific example of the said polycarboxylate is as follows.

Aliphatic polycarboxylates, alicyclic polycarboxylates, aromatic polycarboxylates, and heterocyclic polycarboxylates

Preferred examples of the polycarboxylates include n-butyl maleate, diisobutyl methyl maleate, di-n-hexylcyclohexene carboxylate, diethylnaate, diisopropyltetrahydrophthalate, diethylphthalate, di Isobutyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate and dibutyl 3,4-furandidicarboxylate.

In particular, phthalates are preferable.

As said diether compound, the compound represented by a following formula is mentioned. :

In said formula, n is an integer which satisfy | fills the conditions of 2 <= n <= 10; R ¹ to R ²⁶ are substituents having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron, and silicon; Any combination formed from R ¹ to R ^{20 -n} , preferably R ¹ to R ²⁶ may form a ring other than the benzene ring; The main chain may contain atoms other than carbon atoms.

The good example is as follows:

2, 2, -diisobutyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2, 2-dicyclohexyl-1, 3-dimethoxypropane And 2, 2-bis (cyclohexyl methyl) -1, 3-dimethoxypropane,

The electron donor may be used in combination of two or more kinds.

In the preparation of the solid titanium catalyst component [A-1] usable in the present invention, the various compounds can be brought into contact with inorganic or organic compounds containing silicon, phosphorus, aluminum, and the like, and reaction aids, which are commonly used as carrier compounds. .

Useful carrier compounds are Al ₂ O ₃ , SiO ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ , ZnO, SnO ₂ , BaO, ThO, stytene / divinylbenzene copolymers and the like. Of these, Al ₂ O ₃ , SiO _2, and styene / divinyl benzene copolymers are preferred.

The solid titanium catalyst component [A-1] usable in the present invention is produced by contacting the titanium compound and the magnesium compound (preferably with the electron donor) with each other.

There is no particular limitation on the method for producing the solid titanium catalyst component [A-1] using the compounds.

An example of a method using a tetravalent titanium compound is outlined.

(1) A method in which a solution composed of a magnesium compound, an electron donor and a hydrocarbon solvent is contacted with a titanium compound to precipitate a solid or at the same time with an organometallic compound.

(2) A method of contacting a reaction product with a titanium compound after contacting a complex composed of a magnesium compound with a pre-treatment agent with an organometallic compound.

(3) A method in which a product obtained by contacting an inorganic carrier with an organic magnesium compound is brought into contact with a titanium compound.

In this case, the product may be brought into contact with the halogen-containing compound, the electron donor and / or the organometallic compound in advance.

(4) An inorganic or organic carrier carrying a magnesium compound is obtained from a mixture of an inorganic or organic carrier and a solution containing a magnesium compound and an electron donor (and optionally a hydrocarbon solvent), and the resulting carrier is brought into contact with a titanium compound. How to let.

(5) A solution containing a magnesium compound, a titanium compound and an electron donor (and optionally a hydrocarbon solvent) is brought into contact with an inorganic or organic carrier to provide a solid titanium catalyst component [A-1] containing magnesium and titanium. How to get.

(6) A method of bringing a liquid organic magnesium compound into contact with a halogen-containing titanium compound.

(7) A method of bringing a liquid organic magnesium compound into contact with a halogen-containing compound and bringing the obtained product into contact with a titanium compound.

(8) A method of bringing an alkoxy group-containing magnesium compound into contact with a halogen-containing titanium compound.

(9) A method in which a complex composed of an alkoxy group-containing magnesium compound and an electron donor is brought into contact with a titanium compound.

(10) A method in which a complex composed of an alkoxy group-containing magnesium compound and an electron donor is brought into contact with an organometallic compound, and then the resulting product is brought into contact with a titanium compound.

(11) A method of contacting a magnesium compound, an electron donor and a titanium compound in any order. In this reaction, each component can be pretreated with a reaction aid such as an electron donor and / or an organometallic compound or a halogen-containing silicon compound.

(12) A method of depositing a solid magnesium / titanium complex compound by contacting a liquid magnesium compound having no reducibility with a liquid titanium compound in the presence of an electron donor, if necessary.

(13) A method in which the reaction product obtained in the above method (12) is further contacted with a titanium compound.

(14) A method in which the reaction product obtained in the method (11) or (12) is further contacted with an electron donor and a titanium compound.

(15) A method of grinding a magnesium compound and a titanium compound (and an electron donor, if necessary) to obtain a solid product, and treating the solid product with a halogen, a halogen compound or an aromatic hydrocarbon.

The method may include a step of grinding only a magnesium compound, a step of grinding a complex compound composed of a magnesium compound and an electron donor, or a step of grinding a magnesium compound and a titanium compound. After the pulverization, the solid product may be pretreated with a reaction aid and then treated with halogen or the like. Examples of the reaction aid include organometallic compounds and halogen-containing silicon compounds.

(16) A method of contacting a titanium compound with the titanium compound after milling the magnesium compound. In this case, an electron donor or reaction aid may be used in the grinding step and / or contact step.

(17) A method of treating a compound obtained by any of the methods (11) to (16) with a halogen, a halogen compound or an aromatic hydrocarbon.

(18) A method of bringing a reaction product obtained by contacting a metal oxide, an organomagnesium compound and a halogen-containing compound into contact with a titanium compound and, if necessary, an electron donor.

(19) A method of bringing a magnesium compound, such as a magnesium salt of an organic acid, alkoxymagnesium or aryloxymagnesium, into contact with a titanium compound and / or a halogen-containing hydrocarbon and an electron donor as necessary.

(20) A method in which a hydrocarbon solution containing at least a magnesium compound and an alkoxytitanium is contacted with a titanium compound and / or an electron donor. In this case, halogen compounds, such as a halogen containing silicone compound, can be made to further contact as needed.

(21) A method in which a liquid magnesium compound having no reducing property is contacted with an organometallic compound to precipitate a solid magnesium / metal (aluminum) complex compound, and the solid compound is contacted with a titanium compound and an electron donor as necessary.

The preparation of the solid titanium catalyst component [A-1] is usually carried out at a temperature of -70 to 200 ° C, preferably -50 to 150 ° C.

The solid titanium catalyst component [A-1] obtained above contains titanium, magnesium and halogen, and preferably further contains an electron donor.

In the solid titanium catalyst component [A-1], the ratio (atomic ratio) of halogen / titanium is 2 to 200, preferably 4 to 90, and the magnesium / titanium ratio (atomic ratio) is 1 to 100, preferably Preferably it is 2-50.

The electron donor usually contains an electron donor / titanium ratio (molar ratio) of 0.01 to 100, preferably 0.05 to 50.

In the present invention, examples of using a titanium compound as the solid titanium catalyst component [A-1] are disclosed, but a compound in which titanium is substituted with zirconium, hafnium, vanadium, niobium, tantalum or chromium may also be used.

The method for producing the titanium trichloride catalyst component [A-1] is described in detail in, for example, the following Japanese Patent Publication.

In the present invention, a conventionally known titanium trichloride catalyst component [A-2] can also be used as another example of the solid titanium catalyst component exemplified as the transition metal compound catalyst component [A].

The production method of the titanium trichloride catalyst component [A-2] is described in detail in, for example, the following Japanese Patent Publication.

Next, the organometallic compound catalyst component [B] containing a metal selected from the Group I-III metals of the periodic table used to prepare the α-olefin / polyene copolymer-containing polymer [I] will be described.

As the organometallic compound catalyst component [B], for example, an organoaluminum compound [B-1], an alkyl complex compound composed of group I metal and aluminum in periodic table, and an organometallic compound in group II metal in periodic table can be used.

The organoaluminum compound [B-1] is, for example, an organoaluminum compound represented by the following formula;

R ^a _n AlX _3-n

In formula, R ^<a> is a C1-C12 hydrocarbon, X is halogen or hydrogen, n is 1-3.

In the formula, R ^a is a hydrocarbon group having 1 to 12 carbon atoms such as alkyl, cycloalkyl or aryl, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, Cyclohexyl, phenyl, tolyl and the like.

Specific examples of the organoaluminum compounds are illustrated below.

Trialkyl aluminum, such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, and tri 2-ethylhexyl aluminum; Alkenyl aluminum, such as isoprenyl aluminum; Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride and dimethyl aluminum bromide; Alkyl aluminum seski halides, such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; Alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride and ethyl aluminum dibromide; Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; In addition, the compound represented by the formula R ^a _n AlY _3-n may be used as the organoaluminum compound [B-1]. Wherein R ^a is as defined above, Y is -OR ^b , -OSiR ^c ₃ , -OAIR ^d ₂ , -NR ^e ₂ , -SiR ^f ₃ or -N (R ^g ) AIR ^h ₂ , and n is 1 And R ^b , R ^c , R ^d and R ^h are methyl, ethyl, isopropyl, isobutyl, cyclohexyl, phenyl groups, etc .: R ^e is hydrogen, methyl, ethyl, isopropyl, phenyl, trimethylylsilyl And the like; R ^f and R ^g are each methyl or ethyl.

Specific examples of the organoaluminum compound [B-1] include the following compounds.

(Iii) ^a compound of Ra _n Al (OR ^b ) _3-n ; Dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, etc .;

(Ii) ^a compound of Ra _n Al (OSiR ^c ₃ ) _3-n ; (C ₂ H ₅ ) ₂ A1OSi (CH ₃ ) ₃ , (iso-C ₄ H ₉ ) ₂ AiOSi (CH ₃ ) ₃ , (iso-C ₄ H ₉ ) ₂ AlOSi (C ₂ H ₅ ) _3, and the like;

_{^{(Ⅲ) R a n Al (}} OAlR d 2) _3-n in the compound; (C ₂ H ₅ ) ₂ AiOAl (C ₂ H ₅ ) ₂ , (iso-C ₄ H ₉ ) ₂ AlOAl (iso-C ₄ H ₉ ) _2, and the like;

(Iii) ^a compound of Ra _n Al (NR ^e ₂ ) _3-n ; (CH ₃ ) ₂ AlN (C ₂ H ₅ ) ₂ , (C ₂ H ₅ ) ₂ AlNHCH ₃ , (CH ₃ ) ₂ AlNH (C ₂ H ₅ ), (C ₂ H ₅ ) ₂ AlN (Si (CH ₃ ) ₃ ) ₂ , (iso-C ₄ H ₉ ) ₂ AlN (Si (CH ₃ ) ₃ ) _2, etc .;

(Iii) ^a compound of Ra _n Al (SiR ^f ₃ ) _3-n ; (iso-C ₄ H ₉ ) ₂ AlSi (CH ₃ ) _3, etc.,

_{^{(Ⅵ) R a n Al (}} N (R g) -AlR h 2) of the compound _3-n; (C ₂ H ₅ ) ₂ AlN (CH ₃ ) Al (C ₂ H ₅ ) ₂ , (iso-C ₄ H ₉ ) ₂ AlN (C ₂ H ₅ ) Al (iso-C ₄ H ₉ ) _2, and the like.

The exemplified an organic aluminum compound [B-1], formula R ^a ₃ Al, R ^a _n Al (OR ^b) _3-n or _{^{R a n Al (OAlR d 2}} ) an organic aluminum compound represented by _3-n is desirable.

The alkyl complex compound consisting of the metal of the periodic table group I and aluminum can illustrate the compound represented by a following formula.

M ¹ AlR ^j ₄

In formula, M <^1> is Li, Na or K, R <^j> is a C1-C15 hydrocarbon group.

Specific examples of the alkyl complex compounds include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

The organometallic compound of periodic table II metal can illustrate the compound represented by a following formula.

R ₁ R ₂ M ₂

Each of R ₁ and R ₂ is a hydrocarbon group or halogen having 1 to 15 carbon atoms, R ₁ and R ₂ may be the same as or different from each other, except that both are halogen, and M ₂ is Mg, Zn or Cd.

Specific examples include diethyl zinc, diethyl magnesium, butyl ethyl magnesium, ethyl magnesium chloride, and butyl magnesium chloride.

The said compounds can be used in combination of 2 or more type.

Examples of useful electron donor catalyst component [C] used in the present invention include the above-described electron donor and the organosilicon compound represented by the following formula.

R _n Si (OR ¹ ) _4-n

(Wherein R and R 'are a hydrocarbon group and 0 <n <4.)

As an organosilicon compound as mentioned above, specifically; Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane , Diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-O-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolidimethoxysilane, bis-p -Tolyl diethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyl diethoxysilane, ethyltrimethoxysilane, ethyltriethoxysisilane, vinyltrimeth Methoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, -Chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, Butyl triethoxy silane, n-butyl triethoxy silane, iso-butyl triethoxy silane, phenyl triethoxy silane, -Aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisoethoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2 Norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxy Silane, dimethyltetraethoxysilane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, dicyclopentyldimethoxysilane , Bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane, tricyclopentylethoxysilane, tricyclopentylmethoxysilane, dicyclo Pentylmethylmethoxysil Etc., dicyclopentyl ethyl trimethoxysilane, hexenyl trimethoxysilane, dicyclopentyl methyl silane, dimethyl-cyclopentyl trimethoxysilane, cyclopentyl tildi ethyl trimethoxysilane, cyclopentyl dimethyl ethoxy silane.

Of these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimeth Methoxysilane, bis-p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimesysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxy Silane, phenyltriethoxysilane, dicyclopentyldimethoxysilane, hexenyltrimethoxysilane, cyclopentyltriethoxysilane, tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane and the like are preferable.

The catalyst for olefin polymerization usable in the present invention is composed of a solid titanium catalyst component [A-1], an organometallic compound catalyst component [B], and an electron donor catalyst component [C]. Is used to copolymerize higher α-olefins with α, ω-dienes and nonconjugated dienes.

It is also possible to prepolymerize α-olefins or higher α-olefins using this catalyst for olefin polymerization and then polymerize α, ω-dienes and nonconjugated dienes with higher α-olefins using this catalyst for olefin polymerization. . In prepolymerization, the α-olefin or higher α-olefin is prepolymerized in an amount of 0.1 to 500 g, preferably 0.3 to 300 g, particularly preferably 1 to 100 g per 1 g of the catalyst for olefin polymerization.

The catalyst concentration in the prepolymerization reaction system may be much larger than that in the polymerization reaction system.

The amount of solid titanium catalyst component [A-1] at the time of prepolymerization is generally about 0.01 to 200 mmol, preferably about 0.1 to 100 mmol, more preferably 1 to 50 mmol in terms of titanium atoms per liter of the inert hydrocarbon medium described below. .

The organometallic compound catalyst component [B] is used in an amount from 0.1 to 500 g, preferably 0.3 to 300 g, per 1 g of the solid titanium catalyst component [A-1].

Specifically, the amount of the organometallic compound catalyst component [B] is about 0.1 to 100 moles, preferably about 0.5 to 50 moles, more preferably 1 to 1 mole of titanium atoms contained in the solid titanium catalyst component [A-1]. 20 moles is good.

The electron donor catalyst component [C] is used in an amount of 0.1 to 50 moles, preferably 0.5 to 30 moles, more preferably 1 to 10 moles per mole of titanium atoms contained in the solid titanium catalyst component [A-1]. .

Prepolymerization is preferably carried out under mild conditions by adding an olefin or higher α-olefin and a catalyst for olefin polymerization to an inert hydrocarbon medium.

Specific examples of the inert hydrocarbon medium used herein include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane, Aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures of these hydrocarbons.

Among these inert hydrocarbon media, aliphatic hydrocarbons are particularly preferably used.

It is also possible to prepolymerize with the olefin or higher α-olefin itself as a solvent or to prepolymerize in the substantially absence of a solvent.

The higher α-olefin used in the prepolymerization may be different from or the same as the higher α-olefin used in the polymerization described later.

The reaction temperature at the time of prepolymerization is about -20 to + 100 ° C, preferably about -20 to + 80 ° C, more preferably 0 to + 40 ° C.

Molecular weight regulators such as hydrogen can be used during the prepolymerization.

The molecular weight modifier is preferably used such that the polymer obtained by prophylactic polymerization has an intrinsic viscosity [η] of about 0.2 dl / g, preferably about 0.5 to 10 dl / g, measured in decalin at 135 ° C.

Prepolymerization can be carried out batchwise or continuously.

Solid titanium catalyst component [A-1] (or solid titanium catalyst component [A-1] obtained by prepolymerization with a catalyst for olefin polymerization as described above) organic aluminum compound catalyst component [B] and electron donor catalyst component [C] In the presence of a catalyst for olefin polymerization, copolymerization (polymerization) of higher α-olefins, α, ω-dienes and nonconjugated dienes and nonconjugated dienes is carried out.

When the copolymerization is carried out after the prepolymerization, a component similar to the organometallic compound catalyst component [B] used to prepare a catalyst for olefin polymerization in addition to the prepolymerization catalyst may be used as the organometallic compound catalyst component. In addition, when performing copolymerization after prepolymerization, a component similar to the electron donor catalyst component [C] used to prepare the catalyst for olefin polymerization may be further used as the electron donor catalyst component.

Electron donor organoaluminum compounds that can be used in the copolymerization of higher α-olefins, α, ω-dienes and nonconjugated dienes are not always the same as those used to prepare the catalyst for olefin polymerization described above.

Copolymerization of the higher α-olefins, α, ω-dienes and nonconjugated dienes is generally carried out in the liquid phase.

As the reaction medium (diluent), the above-mentioned inert hydrocarbon medium may be used or an olefin which is liquid at the reaction temperature may be used.

In the copolymerization of the higher α-olefins, α, ω-dienes and non-conjugated dienes, the solid titanium catalyst component [A-1] is about 0.001 to about 1.0 mmol, preferably about 0.005 to about titanium atoms per liter of polymerization volume. It is used in an amount of 0.5 mmol.

The organometallic compound catalyst component [B] has a metal atom of about 1 to 2000 moles, preferably about 5 to 500 moles, per mole of titanium atoms contained in the solid titanium catalyst component [A-1]. Use amount.

The electron donor catalyst component [C] is used in an amount of about 0.001 to 10 mol, preferably 0.01 to 2 mol, and more preferably 0.05 to 1 mol, per mol of the metal atoms contained in the organometallic compound catalyst component [B]. do.

At the time of this copolymerization, hydrogen may be used to adjust the molecular weight of the resulting copolymer.

In the present invention, the polymerization temperature of the higher α-olefin, α, ω-diene, and non-conjugated diene is usually about 20 to 200 ° C, preferably about 40 to 100 ° C, and the pressure is usually atmospheric pressure to 100kg / cm 2, preferably Atmospheric pressure-50 kg / cm <2>.

Copolymerization of the higher α-olefins, α, ω-dienes and nonconjugated dienes may be carried out batchwise, semi-continuous or continuous. In addition, the copolymerization may be carried out in two or more steps having different reaction conditions from each other.

The higher α-olefin copolymer of the present invention obtained by the polymerization described above is excellent in workability as well as dynamic fatigue resistance, weather resistance, earth resistance, thermal aging resistance and low temperature characteristics. In particular, the copolymer exhibits excellent properties when used in resin modifiers and various rubber products.

The higher α-olefin copolymer of the present invention can be used as a resin modifier, for example, as a modifier for polypropylene, polyethylene, polybutene, polystyrene and ethylene / cycloolefin copolymers.

The addition of the higher α-olefin copolymers of the present invention to these resins can significantly improve the impact resistance and the stress crack resistance of the resins.

Since various rubber products are generally used in a vulcanized type, when the higher α-olefin copolymer of the present invention is used in a vulcanized type, its characteristics appear. In the case of using the higher α-olefin copolymer of the present invention for various rubber products, the vulcanized product of the copolymer is prepared by first preparing a vulcanized rubber composition, and then molding the rubber composition into a predetermined form. It can be prepared by vulcanization.

In order to vulcanize the molded rubber composition, a method of heating the rubber composition using a vulcanizing agent or a method of irradiating the rubber composition with an electron beam may be used.

As the vulcanizing agent used for vulcanization, sulfur-based compounds and organic peroxides can be used.

Specific examples of sulfur compounds include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylchiuram disulfide and selenium dimethyldithiocarbamate.

Of these, sulfur is preferably used.

The sulfur compound is used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the higher α-olefin copolymer of the present invention.

As the organic peroxide, conventional general rubber vulcanization peroxides can be used. Preferred organic peroxides include, for example, dicumyl peroxide, di-t-butylperoxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylhydrofooxide, t-butylcumyl Peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5 -Dimethyl-2,5-mono (t-butylperoxy) hexane, α, α-bis (t-butylperoxy-m-isopropyl) benzene and the like. Of these, dicumyl peroxide, di-t-butyl peroxide and di-t-butylperoxy-3,3,5-trimethylcyclohexane are preferably used.

These organic peroxides are used alone or in combination of two or more.

The organic peroxide is used in an amount of 0.0003 to 0.05 mole, preferably 0.001 to 0.03 mole per 100 g of the higher α-olefin copolymer, and the optimum amount is determined according to the required physical property value.

When using a sulfur type compound as a vulcanizing agent, it is good to use combining a vulcanization accelerator.

Specific examples of the vulcanization accelerator are as follows. N-cyclohexyl-2-benzothiazolsulfenamide, N-oxydiethylene-2-benzothiazolsulfenamide, N, N-diisopropyl-2-benzothiazolsulfenamide, 2-merhaptobenzothiazole And thiazole type compounds such as 2- (2,4-dinitrophenyl) merufatobenzobenzoazole, 2 (2,6-diethyl-4-morpholinothio) benzothiazole and dibenzochiazil disulfide; Guanidine compounds, such as phenylguanidine, triphenylguanidine, diolnitriniguanidine, olonitrilebiguanide, and diphenylguanidine phthalate, acetaldehyde / aniline reaction products, butylaldehyde / aniline condensation products, hexamethylenetetramine and acetaldehyde Aldehyde / ammonia type compounds, such as ammonia, and imidazoline type compounds, such as 2-meractomidazoline, and thiocarbanilide, diethyl thiourea, dibutyl thiourea, trimethyl thiourea, and diol sotolyl thiourea, etc. Chiourea type Compounds, tetramethylchiuram monosulfide and tetramethylchiuram disulfide; Chiuram-type compounds, such as tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, and pentamethylene thiuram tetrasulfide, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarba Dithioate type compounds, such as a mate, zinc ethylphenyl dithio carbamate, zinc butylphenyl dithio carbamate, sodium dimethyl dithio carbamate, selenium dimethyl dithio carbamate, and tellurium dimethyl dithio carbamate, and zinc Xanthate type compounds, such as dibutyl xanthate, and other compounds, such as zincation.

The vulcanization accelerator is used in an amount of 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, per 100 parts by weight of the higher α-olefin copolymer.

When using an organic peroxide as a vulcanizing agent, it is good to use combining a vulcanizing adjuvant.

Specific examples of the vulcanization aid include sulfur, quinone dioxime compounds such as P-quinone dioxime, methacrylate compounds such as polyethylene glycol dimethacrylate, allyl such as diallyl phthalate and triallyl cyanurate Type compounds, maleimide compounds, divinylbenzene, and the like.

The vulcanizing aid is used in an amount of 0.5 to 2 mol, preferably about 1 mol, per mol of the organic peroxide.

When vulcanization is carried out using an electron beam without using a vulcanizing agent, an electron beam having an energy of 0.1 to 10 MeV (megaelectron volts), preferably 0.3 to 2 MeV, is used in an unvulcanized rubber composition described later. Irradiation is made to 0.5 to 35 Mrad, preferably 0.5 to 10 Mrad.

In this case, the vulcanizing aid is used in combination with an organic peroxide which is a reddening agent, wherein the amount of the organic peroxide used is in the range of 0.0001 to 0.1 mol, preferably 0.001 to 0.03 mol per 100 g of the higher α-olefin copolymer.

Unvulcanized rubber composition is prepared by the following method.

That is, the higher α-olefin copolymer, filler and softener are kneaded with a mixing apparatus such as a Banbury mixer at a temperature of 80 to 170 ° C. for 3 to 10 minutes, and then a vulcanizing agent and a vulcanizing accelerator or vulcanizing aid are added if necessary. The mixture is then kneaded at a temperature of 40-80 ° C. for 5-30 minutes using a roll such as an open milling roll.

The mixture is then rolled to produce a rubber composition in the form of a ribbon or sheet. As described above, the rubber composition using the higher α-olefin copolymer of the present invention, that is, the vulcanizable rubber composition is mixed with each component by a mixing apparatus conventionally used in ordinary rubber industries such as Banbury mixers and kneaders. Manufacture.

Reinforcing agents (e.g. carbon black and silica), fillers (e.g. calcium carbonate and talc), crosslinking aids (e.g. triallyl isocyanurate, trimethylolpropane triacrylate and m-phenylenebismaleimide), Various additives commonly used in the rubber industry such as plasticizers, stabilizers, processing aids and coloring agents may be mixed as appropriate.

The rubber composition prepared as described above is then molded into a predetermined shape using an extruder, calender roll or press. The vulcanization of the rubber composition is carried out simultaneously with or after the molding described above. That is, the rubber composition or its molded product is placed in a vulcanization container and then vulcanized by heating at a temperature of 150 to 270 ° C. for 1 to 30 minutes or by irradiating an electron beam in the manner described above. The vulcanization method may be performed using a mold or may be performed without using a mold.

When the mold is not used, molding and vulcanization are generally performed continuously. In the vulcanization vessel, the vessel is heated using hot air, a ura bead fluidized bed, UHF (Ultra High Frequency Electromagnetic Wave), steam, or the like.

Of course, when vulcanizing by irradiation with an electron beam, a rubber composition containing no vulcanizing agent is used.

The vulcanized rubber products manufactured as described above can be used as automotive industrial parts such as dustproof materials, wiper blades, tire and vibration coating materials, electrical insulation, industrial rubber products such as rubber rolls and belts, civil and building materials, rubberized fibers, etc. Can be.

When foaming is carried out by adding a blowing agent to the above-mentioned unvulcanized rubber, a foaming material is obtained, and the foaming material can be used as a heat insulating material, a cushioning material, a sealing material and the like.

Next, the dustproof rubber molded article of the present invention will be described.

The dustproof rubber molded article of the present invention is formed from the above-mentioned vulcanized product of a higher α-olefin copolymer, but further contains a vulcanization aid, for example, a metal activator, a compound having an oxymethylene structure, and a scorch retarder. You may. In addition, by adding additives such as rubber reinforcing agent, filler, softener, anti-aging agent and processing aid to the anti-vibration rubber molded article of the present invention can improve the performance of the anti-vibration rubber molded article. Therefore, the above-mentioned additives are preferably used in the present invention.

The dustproof rubber molded article of the present invention can be produced, for example, by the following method.

That is, the dustproof rubber molded article of the present invention can be obtained by vulcanizing the copolymer by adding a vulcanizing agent to the higher α-olefin copolymer described above.

As described above, the vulcanization is performed by adding a vulcanizing agent to the higher α-olefin copolymer, and the vulcanizing agent is preferably added before molding. Effective methods for vulcanizing higher α-olefin copolymers are sulfur vulcanization and organic peroxide vulcanization.

Sulfur-based compounds used for sulfur vulcanization and organic peroxides Specific examples of organic peroxides used for vulcanization and the amounts thereof are the same as those described above.

The vulcanizing agent is preferably used in combination with the vulcanizing accelerator, and the vulcanizing accelerator and the amount thereof are as described above.

In the production of the anti-vibration rubber-like article of the present invention, it is preferable to use a vulcanizing aid such as a metal activator, a compound having an oxymethylene structure or an anti-scorch agent in combination with the vulcanizing agent and the vulcanizing accelerator.

Specific examples of the metal activator include magnesium oxide, zincation, zinc carbonate, higher fatty acid zinc, minium, lithrage and calcium oxide.

The metal activator is used in an amount of 3 to 15 parts by weight, preferably 5 to 10 parts by weight, per 100 parts by weight of the higher α-olefin copolymer.

In order to cope with various processing steps, it is preferable to add a compound having an oxymethylene structure and an anti-scorching agent.

Specific examples of the compound having an oxymethylene structure that can be used in the present invention include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol and polypropylene glycol.

The compound having an oxymethylene structure is used in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, per 100 parts by weight of the higher α-olefin copolymer.

Usable anti-scoring agents are known anti-scoring agents, and specific examples thereof include maleic anhydride and salicylic acid.

The anti-scoring agent is used in an amount of 0.2 to 5 parts by weight, preferably 0.3 to 3 parts by weight, per 100 parts by weight of the higher α-olefin copolymer.

The performance of dustproof rubber molded articles can be further improved by adding additives such as rubber reinforcements, fillers, softeners, aging inhibitors and processing aids as described above. These additives may be mixed as appropriate with the higher α-olefin copolymer before or after vulcanization.

Specifically, reinforcing agents such as carbon black (eg, SRF, GPF, FEF, HAF, ISAF, SAF, FT and MT) and finely divided silicates, precipitated hard calcium carbonate, heavy calcium carbonate; Fillers such as talc, cray and silica can be used as additives. The type and amount of rubber reinforcing agent or filler to be used may be suitably determined depending on the purpose of the final dustproof rubber molded article, and the amount thereof is at most 300 parts by weight, preferably at most 200 parts by weight per 100 parts by weight of the higher α-olefin copolymer.

As the softener, those generally used for rubber can be used. Examples thereof include petroleum softeners such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt and petrolatum, coal tar softeners such as coal tar and coal tar pitch, castor oil, rinse oil, rapeseed oil and coconut. Aliphatic oil-based softeners, wax oils, waxes, carnauba waxes and lanolin, fats such as ricinolic acid, palmitic acid, barium stearate, calcium stearate and zinc laurate Salts and fatty acids, synthetic polymers such as petroleum resins, atactic polypropylene, and guarone-indene resins.

Of these, petroleum softeners are preferably used, and among them, process oil is preferably used. The amount of softener used may be appropriately selected depending on the purpose of the final vulcanized product, and the amount thereof is 150 parts by weight, preferably 100 parts by weight at most per 100 parts by weight of the higher α-olefin copolymer.

As the anti-aging agent, those generally used for rubber can be used, the amount of which is 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight per 100 parts by weight of the higher α-olefin copolymer.

As the processing aid, those generally used for rubber can be used, and the amount thereof is 10 parts by weight or less, preferably 1 to 5 parts by weight, per 100 parts by weight of the higher α-olefin copolymer.

In addition, other kinds of rubbers such as natural rubbers, diene rubbers (e.g., SBR, IR and BR), and EPDM may be added to the composition for producing the dustproof rubber molded article of the present invention.

The dustproof rubber molded article of the present invention can be obtained, for example, by manufacturing and molding a rubber composition in the following manner. That is, the higher α-olefin copolymer and, if necessary, additives such as reinforcing agents, fillers and softeners are kneaded at a temperature of 80 to 170 ° C. for 3 to 10 minutes in a mixing apparatus such as a Banbury mixer, and then Using the same roll, the vulcanizing agent and, if necessary, the vulcanizing accelerator and the vulcanizing aid are added and then milled for 5 to 30 minutes at a roll temperature of 40 to 80 ° C.

The final mixture is then rolled to produce a ribbon or sheet shaped rubber composition.

The rubber composition thus obtained is then molded and vulcanized using a press molding machine, transfer molding machine, injection molding machine, etc. to obtain a dustproof rubber molded article.

Dust-proof rubber molded parts obtained as described above are often used in combination with iron.

When it is necessary to adhere the dustproof rubber molded article of the present invention to iron, sufficient adhesion between the dustproof rubber molded article and iron can be obtained even with a commercially available adhesive.

Among the many adhesives, Road Far East Co Chemrock 250, 253, etc. are recommended.

The dust-proof rubber molded article manufactured as described above is excellent in thermal fatigue resistance as well as dynamic fatigue resistance (bending fatigue resistance).

Next, a rubber belt molded article, a wiper blade rubber molded article, and a rolled rubber molded article, which are molded articles made of the higher α-olefin copolymer of the present invention, will be described.

These molded articles are preferably produced by the following method, for example.

That is, these products can be obtained by vulcanization by adding a vulcanizing agent to the above-mentioned? -Olefin copolymer.

Various additives and methods that can be used as rubber compositions and vulcanizing agents for these products are the same as those described above for dustproof rubber molded articles.

Specifically, additives such as reinforcing agents, fillers, and softeners, if necessary, are kneaded at 80 to 170 ° C. for about 3 to 10 minutes using a mixing device such as a Banbury mixer, and then vulcanized, if necessary. , By adding a vulcanization accelerator and a vulcanizing aid, using a roll such as an open milling roll for 5-30 minutes at a roll temperature of 40 ~ 80 ℃ and then rolling to prepare a rubber composition in the form of a ribbon or sheet.

In the case of the rubber belt molded article and the wiper blade rubber molded article, the pellet-type rubber composition is directly supplied to the extruder heated to about 80 to 100 ° C., and the high quality α-olefin copolymer and additives are added, and the residence time is about 0.5 to 5 minutes. It can set and manufacture.

Rubber belt molded products are manufactured by molding the rubber composition prepared as described above, using a rolling machine, a carrendering machine, an extruder, etc., and generally forming a molded product in a belt shape, and then molding the molded product at a temperature of 130 to 220 ° C. for 1 to 60 minutes. It can be obtained by vulcanization while heating.

The rubber belt molded article may also be obtained by molding and vulcanizing the above-mentioned rubber composition in a mold by using a press molding machine or an injection molding machine. In this case, the mold temperature is generally 130 to 220 캜 and the period required for vulcanization is 1 to 60 minutes.

The rubber belt molded article thus obtained may be combined with a reinforcing agent such as synthetic fiber, natural fiber steel cord or glass cord to produce a composite rubber belt.

The rubber belt molded article manufactured as described above has excellent heat aging resistance and dynamic fatigue resistance, and has little variation in elastic modulus in a wide temperature range from low temperature to fine.

The wiper blade rubber molded article can be obtained by molding and vulcanizing the rubber composition prepared above using a press molding machine, a transfer molding machine, an injection molding machine and the like.

The wiper blade rubber molded article is manufactured by using the rubber composition alone as described above, but the rubber composition may be laminated with a conventionally used material to obtain a composite wiper blade rubber molded article having a long life. In addition, the wiper blade rubber molded article obtained as described above may be subjected to a surface treatment such as chlorination, bromination, or fluorination, or the surface of the wiper blade rubber is coated with a resin such as polyethylene or by filling short fibers to reduce the coefficient of friction. The performance of the molded article can be much improved.

Rubber molded articles for rolls can be produced by the following method.

After rolling the above-mentioned rubber composition using a rolling machine, a calendering machine, an extruder, etc., the rolled rubber composition is wound around a metal core coated with an adhesive to prepare a roll of the rubber composition.

Then roll the roll tightly with a cloth and finish both ends of the roll with a suitable plate.

In some cases, a wire may be tightly wound on the cloth.

The rolls thus treated are then placed in a vulcanizer and heated to 130-220 ° C. to vulcanize the rolls, after cooling the vulcanized rolls, the cloth and wire rolls are removed from the rolls and the rolls are mechanically polished.

The rubber molded articles for rolls obtained as described above are excellent in both heat aging resistance and dynamic fatigue resistance, and have a small elastic modulus variation in a wide temperature range from low temperature to high temperature.

The present invention will be described with reference to the following examples. However, the present invention is not limited to these examples.

Example 1

[Preparation of solid titanium catalyst component [A-1]]

95.2 g of magnesium chloride anhydride, 442 ml of decane, and 390.6 g of 2-ethylhexyl alcohol were mixed with each other while heating at 130 ° C. for 2 hours to obtain a homogeneous solution. Then, 21.3 g of phthalic anhydride was added to the solution. After mixing for 1 hour at 130 ° C. to dissolve phthalic anhydride, the siliceous solution was cooled to room temperature and 75 ml of the solution was added dropwise to 200 ml of titanium tetrachloride maintained at −20 ° C. for 1 hour. The temperature was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.22 g of diisobutyl phthalate was added to the mixed solution.

Then, the mixed liquid was stirred at the same temperature for 2 hours. After completion of the reaction for 2 hours, the solid was collected by heating filtration, suspended in 275 ml of titanium tetrachloride, and then the suspension was heated to 110 ° C. for 2 hours to carry out the reaction.

After completion of the reaction, the suspension was again filtered by heating to collect solids. The solid part was washed sufficiently with decane and hexane at 110 ° C. until no titanium compound was detected in the washing solution. The titanium catalyst component [A-1] prepared through the above process was dried partly for inspection of the catalyst composition, but the others were stored as decans slurry. The solid titanium catalyst component [A-1] obtained as above was composed of 2.5 wt% titanium, 65 wt% chlorine, 19 wt% magnesium, and 13.5 wt% diisobutyl phthalate as essential components.

[polymerization]

Copolymerization of octene-1, 1,5-hexadiene and 7-methyl-1, 6-octadiene was carried out continuously using a 4 liter glass polymerizer with a stirring vane.

That is, the concentration of octene-1 in the polymerizer is 200 g / l, the concentration of 1,5-hexadiene is 39 g / l, and the concentration of 7-methyl-1, 6-octadiene is 10 g / l. Hexane solution of 1,5-hexadiene, 7-methyl-1, 6-octadiene at a feed rate of 2.1 L / hr, and a solid titanium catalyst component so that the concentration of titanium in the polymerization reactor was 0.045 mmol / L with a catalyst [ The concentration of silane in the polymerizer was increased at a feed rate of 0.4 L / hr for the hexane solution of A-1] and at a rate of 1 L / hr for the hexane solution of triisobutyl aluminum at a feed rate of 8 mmol / L for the aluminum concentration in the polymerization reactor. The hexane solution of trimethylmethoxysilane was continuously supplied at the top at a feed rate of 0.5 L / hr to 2.6 mmol / L, and at the same time, the polymerization was carried out from the bottom of the polymerizer such that the amount of the polymerization solution in the polymerizer was always 2 liters. The solution was drawn off continuously.

In addition, hydrogen was continuously supplied to the polymerization reactor at a feed rate of 1 L / hr and nitrogen was supplied at a feed rate of 50 L / hr, and hot water was circulated in a jacket provided outside of the polymerization reactor to carry out copolymerization at 50 ° C.

Next, a small amount of methanol was added to the polymerization solution extracted from the bottom of the polymerization reactor to terminate the copolymerization reaction, and the polymerization solution was introduced into a large amount of methanol to precipitate a copolymer.

The copolymer was washed well with methanol and then dried at 140 ° C. under reduced pressure for 24 hours to obtain an octene-1 / 1.5-hexadiene / 7-methyl-1, 6-octadiene copolymer at a rate of 90 g / hr.

The copolymer thus obtained had a molar ratio of octene-1 to 1,5-hexadiene (octene-1 / 1,5-hexadiene) of 68/32, an iodine value of 7.7, and an intrinsic measurement in decalin at 135 ° C. The viscosity [η] was 4.8 dl / g.

EXAMPLES 2-6

The procedure of Example 1 was repeated. However, the copolymer shown in Table 1 was prepared by changing the higher α-olefin and polymerization conditions to those shown in Table 1.

^From the results obtained by ¹³ C-NMR analysis, it was found that the repeating unit derived from the 1,5-hexadiene component forms a cyclic structure represented by the following formula. In addition, the peak of the peak by the double coupling was found, and from the strength of the peak it was confirmed that more than 99% of the repeating unit forms the annular structure.

The peaks in the ¹³ C-NMR spectrum of the hexene-1 / 1,5-hexadiene / 7-methyl-1, 6-octadiene copolymer based on deuterated benzene (128.0 ppm) are as follows.

No. Chemical shift [ppm]

1.30.9-32.9

2. 33.6 -34.1

3. 38.4

4.39.8-39.9

5. 40.1-41.0

6. 42.5-42.7

7. 44.3-44.4

8. 40.5-44.4

9.40.5-43.0

10.33.7-35.1

11.36.3

12.37.0-37.1

13. 38.4

14.35.3

15.29.3-29.4

16.23.5-23.6

17.14

18.27.1-27.3

19. 135.2

20. 124.0-124.5

21.14

22. 17.9

23. 140

24. 115

In the following formulae, C represents cis and T represents trans.

TABLE 1

|

TMMS: trimethylmethoxysilane, TMES: trimethylethoxysilane, HexD: 1,5-hexadiene, HepD: 1,6-heptadiene, MOD: 7-methyl-1, 6-octadiene

Example 7

The octene-1 / 1,5-hexadiene / 7-methyl-1,6-octadiene copolymer prepared in Example 1 was milled with the additives shown in Table 2 using an 8 inch open milling roll to unvulcanized A rubber composition was obtained.

The workability of the unvulcanized rubber composition was evaluated and shown in Table 3.

TABLE 2

1) Product Name: Asahi 80 (manufactured by Asahi Kabon Co., Ltd.)

2) Product Name: Sensell M (manufactured by Sanshin)

3) Product Name: Senser TT (manufactured by Sanshin Corporation)

In addition, the above-mentioned rubber composition was heated for 20 minutes by the press heated to 160 degreeC, and the vulcanization sheet was manufactured.

The following test was done with a vulcanization sheet.

[Test Items] are as follows.

[[Test Items]]

Tensile test, hardness test, ozone resistance test, aging test, bending test, low temperature property test.

[[Test Methods]]

Tensile test, hardness test, ozone resistance test, aging test and bending test were carried out in accordance with JIS K 6301.

That is, tensile strength (T _B ) and elongation (E _B ) were measured in the tensile test, and JIS A hardness (H _S ) was measured in the hardness test.

The ozone resistance test was carried out in an ozone test vessel (static test, ozone concentration: 50pphm, elongation rate: 20%, temperature: 40 ° C, time: 200 hours) to test the surface degradation (cracking occurrence) of the vulcanized sheet.

The aging test was carried out by heating the vulcanized sheet with heated air at 120 ° C. for 70 hours. In this test, maintenance of physical properties of the vulcanized sheet before aging,

That is, the retention of tensile strength A _R (T _B ) and the retention of elongation A _R (E _B ) were measured.

In the bending test, the resistance of crack growth was tested by the Dematia group. That is, the vulcanized sheet was repeatedly bent until the crack length became 15 mm, and the number of bending was measured.

Low temperature characteristics were tested by a brittle test in accordance with JIS K 6301, and the temperature at which the chips were broken was measured in this test. The results are shown in Table 3.

Example 8

The procedure of Example 7 was repeated. However, instead of the octene-1 / 1,5-hexadiene / 7-methyl-1,6-octadiene copolymer prepared in Example 1, the octene-1 / 1,5-hexadiene / 7 prepared in Example 2 -Methyl-1,6-octadiene copolymer was used. The results are shown in Table 3.

Example 9

The procedure of Example 7 was repeated. However, instead of octene-1 / 1,5-hexadiene / 7-methyl-1 and 6-octadiene copolymer prepared in Example 1, hexene-1 / 1,5-hexadiene / 7 prepared in Example 3 -Methyl-1, 6-octadiene copolymer was used. The results are shown in Table 3.

Example 10

The procedure of Example 7 was repeated. However, instead of octene-1 / 1,5-hexadiene / 7-methyl-1 and 6-octadiene copolymer prepared in Example 1, hexene-1 / 1,5-hexadiene / 7 prepared in Example 4 -Methyl-1, 6-octadiene copolymer was used. The results are shown in Table 3.

Example 11

The procedure of Example 7 was repeated. However, instead of octene-1 / 1,5-hexadiene / 7-methyl-1 and 6-octadiene copolymer prepared in Example 1, hexene-1 / 1,5-hexadiene / 7 prepared in Example 5 -Methyl-1, 6-octadiene copolymer was used. The results are shown in Table 3.

Example 12

The procedure of Example 7 was repeated. However, instead of octene-1 / 1,5-hexadiene / 7-methyl-1,6-octadiene copolymer prepared in Example 1, decene-1 / 1,5-heptadiene / 7 prepared in Example 6 -Methyl-1, 6-octadiene copolymer was used. The results are shown in Table 3.

Comparative Example 1

The procedure of Example 7 was repeated. However, copolymerization was carried out under the polymerization conditions shown in Table 1 without using 1,5-hexadiene to prepare an octene-1 / 7-methyl-1, 6-octadiene copolymer.

The procedure of Example 7 was then repeated.

However, instead of the octene-1 / 1,5-hexadiene / 7-methyl-1,6-octadiene copolymer prepared in Example 1, the octene-1 / 7-methyl-1, 6-octadiene prepared above. Copolymers were used. The results are shown in Table 3.

TABLE 3

(1) Machinability evaluation (five-step evaluation):

1 2 3 4 5

Bad ← → Good

5: It is easy to cut, tail and round the vulcanized sheet in roll milling process.

4: It is difficult to cut the vulcanized sheet in roll milling process, but it is easy to tailing and rounding.

3: It is difficult to cut and tail the vulcanized sheet in roll milling process, but it is easy to round.

2: It is difficult to cut and tail the vulcanized sheet in the rolling ring process, but it is rounded.

1: Difficulty cutting, tailing and rounding of the vulcanized sheet in the rolling milling process.

Example 13

80 parts by weight of polypropylene (J700 manufactured by Mitsui Corporation), 20 parts by weight of the octene-1 / 7-methyl-1, 6-octadiene copolymer prepared in Example 1, and 2,6-di-t-butyl 0.1 parts by weight of -4-methylphenol was kneaded at 190 DEG C for 30 minutes using a Banbury mixer, and then the mixture was rolled into a sheet using an open milling roll, and the sheet thus obtained was angular pelitetizer. ) To pelletized.

Then, the obtained pellets were injection molded and molded into sheets (150 mm x 120 mm x 2 mm). Injection molding conditions are as follows.

Injection molding condition

Injection primary pressure: 1,000kg / ㎠, 5 second cycle

Injection secondary pressure: 800kg / ㎠, 5 second cycle

Injection speed: 40 mm / sec

Resin Temperature: 230 ℃

The sheet obtained above was measured for stress at yield point (Y _S ) and elongation at break (E _L ) according to the method according to JIS K 6758, and the Izod impact strength was measured in an atmosphere of 23 ° C. according to ASTM D 256.

The results are shown in Table 4.

Comparative Example 2

The procedure of Example 13 was repeated.

However, polypropylene itself was injection molded without the use of the higher α-olefin copolymer.

The results are shown in Table 4.

TABLE 4

[Example of dustproof rubber molded article]

Example 14

Vulcanization Rubber Manufacturing

To the octene-1 / 1,5-hexadiene / 7-methyl-1,6-octadiene copolymer (advanced α-olefin copolymer) obtained in Example 1, an additive shown in Table 5 was added to prepare an unvulcanized rubber composition. Got it.

The copolymer, zincification, stearic acid, and FEF carbon described above in the above step were kneaded with each other for 6 minutes using a 4.3 liter Banbury mixer (manufactured by Kobe Seiko Co., Ltd.), and the kneaded material was left for 1 day.

A vulcanization accelerator and sulfur were added to the kneaded product thus obtained and milled with an open milling roll (front roll / rear roll: 50/60 ° C., 16/18 rpm) to obtain a rubber composition.

TABLE 5

1) Brand Name: Tokai Carbon Co., Ltd., SHEST SO

2) Trade name: Ouchi Shin-Kagaku Co., Nok Seller M

3) Trade name: Ouchi Shingo Chemical Co., Ltd., Nok Cell TT

The rubber composition obtained above was heated for 20 minutes using a press heated to 160 ° C. to prepare a vulcanized sheet, and the prepared sheet was subjected to the following test. [Test Items] are as follows.

[Test Items]

Flexural test and adhesion test

In the flexural test, the resistance to crack growth was tested by the Dematia group according to JIS K 6301. That is, the number of bending was measured by repeatedly bending the vulcanized sheet until the crack length became 15 mm. The number of bends was used as an indicator of dynamic fatigue resistance. Moreover, the bending test was carried out similarly to the aged test piece heated by 120 degreeC heating air for 70 hours.

In the adhesion test, the adhesion between the vulcanized sheet and the metal was tested according to Method A of ASTM D 429.

Chemlock 253 (manufactured by Roadfist) was used as the adhesive.

The results are shown in Table 6.

Example 15

The procedure of Example 14 was repeated. However, instead of the copolymer prepared in Example 1, hexene-1 / 1,5-hexadiene / 7-methyl-1, 6-octadiene prepared in Example 5 was used. The results are shown in Table 6.

Example 16

The procedure of Example 14 was repeated. However, instead of the copolymer prepared in Example 1, decene-1 / 1,6-heptadiene / 7-methyl-1, 6-octadiene prepared in Example 6 was used. The results are shown in Table 6.

Comparative Example 3

After roughly milling a natural rubber (RSS No. 3) having a Mooney viscosity (ML _{1 + 4} (100 ° C)) of 60 with a 14-inch open milling roll, the milled natural rubber was added with the additives shown in Table 7 and open milled. Milling using a roll yielded an unvulcanized rubber composition.

Then, the rubber composition was heated for 60 minutes using a press heated to 140 ° C. to prepare a vulcanized sheet, and the prepared sheet was subjected to the same test as described in Example 14.

The results are shown in Table 6.

[Comparative Example 4]

The procedure of Example 14 was repeated. However, instead of the copolymer prepared in Example 1, it had a molar ratio of ethylene to propylene of 75/25 (ethylene / propylene), a urine value of 10, and a Mooney viscosity of 70 (ML _{1 + 4} (100 ° C.)]]. The ethylene / propylene / 5-ethylidene-2-norbornene copolymer was used and changed to the amounts of the ingredients shown in Table 8.

The results are shown in Table 6.

TABLE 6

(Note 1) R-100: Rubber part breakdown = 100%

(Note 2) R-25: Breakage of rubber part = 25%

RC-75: Interface Peeling Between Rubber and Adhesives = 75%

TABLE 7

1) Trade name: Tokai Carbon Co., Ltd.

2) Trade Name: Idemitsu Kosan Co., Ltd., Diana Process Oil AH-16

3) Trade name: Ouchi Shin-Kagaku Co., Ltd., Knock Rock DP

4) Trade name: Ouchi Shin-Kagaku Co., Nokseller DM

TABLE 8

1) Trade name: Tokai Carbon Co., Ltd.

2) Trade name: Idemitsu Kosan Co., Ltd., Diana Process Oil PW-380

3) Trade name: Ouchi Shin-Kagaku Co., Nocrack TS

4) Trade name: Ouchi Shin-Kagaku Co., Nok Seller M

[Example of Rubber Belt Molded Article]

Example 17

The additive shown in Table 9 was added to the octene-1 / 1,5-hexadiene / 7-methyl-1,6-octadiene copolymer obtained in Example 1 to obtain an unvulcanized rubber composition.

TABLE 9

1) Trade name: Asai Carbon, Asai # 80

2) Trade name: Ouchi Shin-Kagaku Co., Nok Seller M

3) Trade name: Ouchi Shin-Kagaku Co., Nokseller TT

In the process, a copolymer as described above; Zinc, stearic acid, and ISAF carbon were kneaded for 5 minutes using a 4.3 liter Banbury mixer (manufactured by Kobe Seiko Co., Ltd.), and allowed to stand at room temperature for one day. Milling yielded a rubber composition.

In this milling process, the surface temperatures of the front and rear rolls were 50 ° C and 60 ° C, respectively, and the rotation speeds of the front and rear rolls were 16 rpm and 18 rpm, respectively.

The rubber composition obtained above was filled into a belt-forming mold and a bending test sample-forming mold, and the rubber composition was vulcanized for 20 minutes using a press heated to 160 ° C in each mold, and then the obtained vulcanized product was tested as follows. The test items are as follows.

[Test Items]

Tensile test, hardness test, aging test, bending test, modulus of elasticity

[Test Methods]

Tensile tests, hardness tests, aging tests, and bending tests were conducted in accordance with JIS K 6301.

That is, tensile strength (T _B ) and elongation (E _B ) were measured in the tensile test, and JIS A hardness (H _S ) was measured in the hardness test.

The aging test was carried out by heating the vulcanized product with heating air at 135 ° C. for 70 hours. In this test, maintenance of physical properties of the vulcanized product before aging test,

That is, the maintenance of tensile strength A _R (T _B ), the maintenance of elongation A _R (E _B ), and the variation ratio (ΔH _S ) of hardness were measured.

In the flexural test, crack growth resistance was tested with Dematia group. That is, the test piece was repeatedly bent until the crack length became 15 mm, and the number of bends was measured.

The composite modulus of elasticity (G) was measured at 10 Hz using a dynamic spectrometer (manufactured by Leometric) as a variation of the modulus of elasticity with temperature.

The results are shown in Table 11 and FIG.

Example 18

The process of Example 17 was repeated. However, instead of the copolymer obtained in Example 1, the hexene-1 / 1,5-hexadiene / 7-methyl-1, 6-octadiene copolymer obtained in Example 5 was used, and the results are shown in Table 11 and FIG. 2. Indicates.

Example 19

The process of Example 17 was repeated. However, instead of the copolymer obtained in Example 1, decene-1 / 1,6-heptadiene / 7-methyl-1, 6-octadiene copolymer obtained in Example 6 was used, and the results are shown in Table 11 and FIG. 2. Indicates.

[Comparative Example 5]

The process of Example 17 was repeated. However, chloroprene rubber (trade name: Neoprene WRT manufactured by DuPont) was used and its composition and amount were changed to those shown in Table 10.

TABLE 10

1) Trade name: Tokai Kabon Co., Ltd., Kyowa Mug # 150

2) Trade name: Tokai Carbon Co., Ltd., SHEST SO

3) Trade name: Hiroshima Wakosa Co., DOP

4) Trade name: manufactured by Saga Chemical Co., Ltd. One

5) Trade name: Kawaguchi Kagaku High School, Accel 22

TABLE 11

[Example of wiper blade rubber molded article]

Example 20

The additive shown in Table 12 was added to the octene-1 / 1,5-hexadiene / 7-methyl-1,6-octadiene copolymer obtained in Example 1 to obtain an unvulcanized rubber composition.

TABLE 12

1) Trade Name: Asahi Carbon Co., Ltd., Asahi # 80

2) Brand Name: Ouchi Shingoku, Tutoring, Nokselling M

3) Trade name: Ouchi Shingoku, Takugo Teacher, Nokseller TT

In the above process, the copolymer, zincation, stearic acid and ISAF carbon as described above were kneaded for 5 minutes using a 4.3 liter Banbury mixer (manufactured by Kobe Seiko Co., Ltd.) and left at room temperature for 1 day.

The kneaded product thus obtained was added with a vulcanization accelerator and sulfur and milled by an open milling roll to obtain a rubber composition.

In this milling process, the surface temperatures of the front and rear rolls were 50 ° C. and 60 ° C., respectively, and the rotation speeds of the front and rear rolls were 16 rpm and 18 rpm, respectively.

The rubber composition obtained above was heated for 30 minutes by the press heated to 160 degreeC, the vulcanization sheet was manufactured, and the following test was done.

The test items are as follows.

[Test Items]

Tensile test, hardness test, aging test, bending test, ozone resistance test and weather test

[Test Methods]

Tensile tests, hardness tests, aging tests, bending tests, and ozone resistance tests were conducted in accordance with JIS K 6301.

That is, tensile strength (T _B ), elongation (E _B ) and tear strength (T _R ) were measured in the tensile test, and JIS A hardness (H _S ) was measured in the hardness test.

The vulcanization sheet was heated with 100 ° C. heated air for 70 hours and subjected to aging test. In this test, the retention of physical properties of the vulcanized product, that is, the retention of tensile strength A _R (T _B ) and the retention of elongation A _R (E _B ) were measured before the aging test.

Ozone resistance test is carried out in an ozone test vessel (static test, ozone concentration: 40 rpm, elongation: 20%, temperature: 40 ° C, time: 200 hours). The time until a crack was generated was measured.

In the flexural test, flexural growth resistance was tested with a Dematia group. That is, the vulcanization sheet was repeatedly bent until the crack length became 15 mm, and the number of bends was measured. Moreover, the bending test was carried out similarly to the test piece heated and heated for 70 hours by 120 degreeC heating air. The weathering test was carried out according to JIS B 7753, and the vulcanization sheet was measured with a sunshine wheatherometer to hold the tensile strength A _R (T _B ) and the retention of elongation A _R (E _B ) after 1000 hours of exposure test. . The results are shown in Table 15.

Example 21

The process of Example 20 was repeated. However, instead of the copolymer obtained in Example 1, the hexene-1 / 1,5-hexadiene / 7-1, 6-octadiene copolymer obtained in Example 5 was used. The results are shown in Table 15.

Example 22

The process of Example 20 was repeated. However, instead of the copolymer obtained in Example 1, decene-1 / 1,5-heptadiene / 7-1, 6-octadiene copolymer obtained in Example 6 was used. The results are shown in Table 15.

Comparative Example 6

The process of Example 20 was repeated. Ethylene / propylene / 5-ethylidene- with a molar ratio of ethylene to propylene of 67/33 instead of the copolymer obtained in Example 1, a Mooney viscosity of 63 [ML _{1 + 4} (100 ° C.)] and an iodine value of 20. 2-norbornene copolymer (hereinafter abbreviated as "EPDM (1)") was used and its composition and amount were changed to those shown in Table 13.

The results are shown in Table 15.

TABLE 13

1) Trade name: Asahi Car Corporation, Asahi # 80

2) Trade name: Idemitsu Kosan Co., Ltd., Diana Process Oil PW-90

Comparative Example 7

The process of Example 20 was repeated. However, natural rubber (RSS # 3) and chloroprene rubber (trade name: Neoprene WRT manufactured by DuPont) were used, and the composition and amount thereof were changed to those shown in Table 14.

The results are shown in Table 15.

TABLE 14

1) Trade name: Asahi Car Corporation, Asahi # 80

2) Trade name: Idemitsu Kosan Co., Ltd., Diana Process Oil PW-90

3) Brand Name: Seiko Co., Ltd., High Cross

Example 23

The rubber composition obtained in Example 20 was extruded into a molded article of a wiper blade type, and then vulcanized for 30 minutes in steam under a pressure of 6.5 kg / cm 2 to obtain a wiper blade rubber molded product.

The wiper blade rubber molded article thus obtained was evaluated for friction characteristics and ozone resistance in the following manner.

The results are shown in Table 15.

[Test Methods]

(1) friction characteristics

(a) coefficient of friction

The wiper blade rubber molded article was tested for durability using a flat glass plate under the following conditions and the coefficient of friction was measured in a dry state.

Wiper Blade Length: 100mm

Dark load: 155g

Stroke Length: 150mm

Speed: 45 round trips per minute

Water spray cycle: 1 minute spray / 4 minute stop

(b) Friction coefficient after weathering test

The friction coefficient was measured for the test piece exposed to 1000 hours by the sunshine weatherometer in the same manner as described in the said test (a).

(2) ozone resistance

Ozone resistance was carried out in an ozone test vessel (static test, ozone concentration: 50pphm, elongation: 20%, temperature: 40 ° C, time: 200 hours), and the time period until cracking occurred was measured.

Example 24

The rubber composition obtained in Example 20 and the rubber composition for wiper blades obtained in Comparative Example 7 were extruded in two layers to prepare a wiper blade whose surface was coated with the rubber composition of Example 20, and then vulcanized with steam under a pressure of 6.5 kg / cm 2. The wiper blade rubber molded product was obtained.

The thus obtained wiper blade rubber molded article was evaluated for frictional characteristics and ozone resistance in the same manner as described in Example 23, and the results are shown in Table 15.

Comparative Example 8

The process of Example 24 was repeated. However, instead of the rubber composition obtained in Example 20, the rubber composition obtained in Comparative Example 6 was used and the results are shown in Table 15.

Comparative Example 9

The process of Example 24 was repeated. However, instead of the rubber composition obtained in Example 20, the rubber composition obtained in Comparative Example 7 was used and the results are shown in Table 15.

TABLE 15

Table 15 (continued)

[Example of Rubber Molded Article for Roll]

Example 25

To the octene-1 / 1,5-hexadiene / 7-methyl-1,6-octadiene copolymer obtained in Example 1, the additives shown in Table 16 were added to obtain an unvulcanized rubber composition.

TABLE 16

1) Brand Name: Sankai Co., Ltd., Zincation No. One

2) Trade Name: Asahi Car Corporation, Asahi # 60

3) Trade name: Idemitsu Kosan Co., Ltd., Diana process oil PW-380

4) Trade name: Ouchi Shingo Kagaku Co., Ltd., Bannock R

5) Trade name: Ouchi Shingo Kagaku Co., Ltd., Nok Cell TRA

6) Trade name: Ouchi Shingo Kagaku Co., Ltd., Nokseller TT

In this process, the copolymer, zincated, stearic acid, FEF carbon and process oil as described above are kneaded for 5 minutes using a 4.3 liter Banbury mixer (manufactured by Kobe Seiko Co., Ltd.), and then left at room temperature for 1 day, followed by vulcanization. The rubber composition was obtained by milling with an open milling roll by adding accelerator and sulfur.

The obtained rubber composition was rolled to obtain a rubber sheet having a thickness of about 2 mm.

In the milling process, the surface temperatures of the front and rear rolls were 50 ° C. and 60 ° C., respectively, and the rotation speeds of the front and rear rolls were 16 rpm and 18 rpm, respectively.

The rubber sheet was wound around a hollow pipe-type metal core (SUS 304) having a 60 mm outer diameter, spirally wound a cloth (glass fiber tape) on the rubber sheet, and the rubber sheet was vulcanized at 160 ° C for 30 minutes. After vulcanization was completed, the vulcanized rubber was cooled and separated from the metal core. Then, the vulcanized rubber was punched out to obtain a No. Three types of dumbbell test pieces were obtained. Then, the fracture stress T _B (1) and the elongation at break E _B (1) were measured according to JIS K 6301 under the tensile velocity of 500 mm / min and the temperature conditions of 25 degreeC with the test piece.

In addition, JIS A hardness H _S (1) was measured for the vulcanized rubber obtained above.

Then, No. The dumbbell test piece of 3 was heated with 150 degreeC heating air for 3 days using the test tube aging test machine (made by Toyosei Seisakusho Co., Ltd.). The aged dumbbell test piece was then measured for breakage stress T _B (2), break elongation E _B (2) and JIS A hardness H _S (2) in the same manner as described above.

Fracture energy can be roughly expressed as the tensile product (T _B × E _B ). As a result, the ratio (TE) between the tensile product before the aging test and the tensile product after the aging test and the difference between the JIS A hardness before the aging test and the JIS A hardness after the aging test (ΔH _S ) can be calculated by the following equation. It is taken as the value of aging resistance.

TE (%) = [(T _B after aging test) × (E _B after aging test) × 100] / [(T _B before aging test) × (E _B before aging test)]

ΔH _S = H _S (2)-H _S (1)

The above-mentioned tensile products are described in pages 150-164 of J. Elastomers Plastics, published April 17, 1985 by R. D. Allen.

In addition, a vulcanization test piece having a thickness of 12.7 mm and a diameter of 29.0 mm was prepared from the above-mentioned rubber composition for rolls according to JIS K 6301, and subjected to a permanent compression deformation test.

In addition, a vulcanization test piece was prepared from the rubber composition described above according to ASTM D 2228.

The pico adhesion test was done with this test piece, and the adhesion index of the test piece was measured.

Then, the unvulcanized sheet of the rubber composition having a thickness of 2 mm was punched out, and according to JIS K 6301, No. A dumbbell test piece of type 1 was obtained.

The test piece was subjected to a tensile test under a tensile speed of 100 mm / min and a temperature of 23 ° C. to measure the tensile strength at yield.

The results are shown in Table 18.

Example 26

The process of Example 25 was repeated. However, the hexene-1 / 1,5-hexadiene / 7-methyl-1, 6-octadiene copolymer obtained in Example 5 was used instead of the copolymer obtained in Example 1.

The results are shown in Table 18.

Example 27

The process of Example 25 was repeated. However, instead of the copolymer obtained in Example 1, the decene-1 / 1,6-heptadiene / 7-methyl-1, 6-octadiene copolymer obtained in Example 6 was used.

The results are shown in Table 18.

Comparative Example 10

The process of Example 25 was repeated. However, instead of the copolymer obtained in Example 1, ethylene / propylene / 5-ethylidene having a molar ratio of 80/20 ethylene / propylene, a Mooney viscosity of 120 [ML _{1 + 4} (100 ° C.)] and a urethra value of 10 The 2-norbornene copolymer (hereinafter abbreviated as "EPDM (2)") was used and the composition and amount thereof were changed to those shown in Table 17.

The results are shown in Table 18.

TABLE 17

1) Trade name: Asahi Car Corporation, Asahi # 80

2) Trade name: Idemitsu Kosan Co., Ltd., Diana Process Oil PW-90

3) Trade name: Ouchi Shingo Kagaku Teacher Co., Nocler TS

4) Trade name: Ouchi Shingo Kagaku Teacher Co., Nocseller M

TABLE 18

The higher α-olefin copolymers of the present invention contain specific higher α-olefins, specific α, ω-dienes, and specific non-conjugated dienes in specific ratios and have an intrinsic viscosity [η] of specific values.

Therefore, this higher α-olefin copolymer has excellent workability as well as weather resistance, ozone resistance, heat aging resistance, low temperature characteristics, dustproofness and dynamic fatigue resistance. Further, because of these properties, excellent vulcanized products can be obtained from higher α-olefin copolymers.

According to the method of the present invention for producing the higher α-olefin copolymer, the higher α-olefin copolymer having excellent properties as described above can be efficiently produced in high yield.

Since the anti-vibration rubber molded article of the present invention is formed from a vulcanized product of a copolymer of a specific higher α-olefin, a specific α, ω-diene, and a specific non-conjugated diene, the anti-vibration rubber molded article has both excellent heat aging resistance and dynamic fatigue resistance, Have a long life.

According to the method of the present invention for producing a dustproof rubber molded article, a dustproof rubber molded article having the above excellent characteristics can be obtained.

Since the rubber belt molded article according to the present invention is formed from the vulcanized articles of the above-described higher α-olefin copolymer, both the heat aging resistance and the dynamic fatigue resistance are excellent, and also have a small elastic modulus variation over a wide range from low temperature to high temperature.

Since the wiper blade rubber molded article according to the present invention is formed from the vulcanized article of the above-described high α-olefin copolymer, it is not only environmental aging resistance (heat aging resistance, weather resistance, ozone resistance), but also excellent in fatigue resistance and long life. Have

Since the rubber molded article for roll according to the present invention is formed from the vulcanized article of the above-described high α-olefin copolymer, it has excellent water absorption resistance, heat aging resistance, and permanent compression set characteristics, and also has a low hardness of 37 or less in terms of JIS A hardness. Have

Claims (2)

Higher α-olefin having 6 to 20 carbon atoms, α, ω-diene represented by the following formula [I] and non-conjugated diene represented by the following formula [II], (A) higher α-olefin Molar ratio [higher α-olefin / α, ω-diene] to α, ω-diene is 95/5 to 50/50, (B) the content of nonconjugated diene is 0.01 to 30 mol%, and (C) 135 Higher-alpha-olefin copolymer characterized by the intrinsic viscosity [η] measured in decalin at 캜 of 1.0 to 10.0 dl / g. Wherein n is an integer of 1 to 3, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, Wherein n is an integer of 1 to 5, R ³ is an alkyl group having 1 to 4 carbon atoms, R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, provided that R ⁴ and R ⁵ Are not both hydrogen atoms. Higher α-olefins having 6 to 20 carbon atoms, α, ω-dienes represented by the following formula [I], and non-conjugated dienes represented by the following formula [II]: (a) magnesium, titanium, halogen and electron donor A method for producing a higher α-olefin copolymer characterized by copolymerizing in the presence of a catalyst for olefin polymerization comprising a solid titanium catalyst component, (b) an organometallic compound catalyst component, and (c) an electron donor catalyst component. Wherein n is an integer of 1 to 3, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, Wherein n is an integer of 1 to 5, R ³ is an alkyl group having 1 to 4 carbon atoms, R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁴ and R ⁵ are both Not hydrogen.