JP3255697B2 - Transparent olefin synthetic wax and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin-based material which has excellent transparency and low-temperature properties and can be effectively used as a lubricant for synthetic resins, an adhesive for hot melt, a grease for lubrication, a water-resistant surface treatment agent, and the like. The present invention relates to a synthetic wax and an efficient method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Olefin-based synthetic waxes are used as modifiers for synthetic resins, lubricants, dispersants, hot melt adhesives, lubricating greases, additives for lubricating oils, and the like. Although widely used, an olefin-based synthetic wax having a low melting point, a low softening temperature and excellent low-temperature properties has been demanded in these applications. Further, transparency is required for some applications. However, conventional olefin-based synthetic waxes are not satisfactory in terms of transparency because of their insufficient low-temperature properties and crystallinity.

[0003] On the other hand, as an olefin-based synthetic wax having good transparency, one comprising ethylene and a specific cyclic olefin component has been disclosed (JP-A-61-9).
No. 8780). However, the synthetic wax disclosed in this publication has a glass transition temperature of 80 to 220 ° C.
And high-temperature characteristics are emphasized, and the low-temperature characteristics are not sufficient. In addition, the method for producing a synthetic wax disclosed in the publication has a low polymerization activity and is not satisfactory.

On the other hand, Japanese Patent Application Laid-Open No. 62-252406 discloses a cyclic olefin copolymer comprising ethylene and a specific cyclic olefin component. Among them, an intrinsic viscosity [η] of 0.01 is disclosed. A copolymer which can be used as a wax in the range of 0.4 to 0.4 dl / g is suggested, but there is no description about its specific properties, production method and the like.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an olefin-based synthetic wax having excellent transparency and low-temperature properties, and an efficient method for producing the same.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a cyclic olefin copolymer having a specific structure having a specific glass transition temperature (Tg) and intrinsic viscosity [η] is used as a wax. It has been found that when used, the above object is effectively achieved, and the present invention has been accomplished.

That is, the present invention provides the following compound (A)
And a catalyst containing (B) as a main component or the following compound (A),
It is manufactured using a catalyst containing (B) and (C) as main components.
(A) Transition metallation containing a tetravalent transition metal of group IVB
Compound (B) reacts with the transition metal compound (A) to form an ionic complex
Compounds that form (C) and a repeating unit derived from repeating units and cycloolefin derived from an organoaluminum compound of ethylene, a glass transition temperature (Tg) of
Is 70 ° C. or less and the intrinsic viscosity [η] is 0.005 to 0.4 d.
The present invention provides a transparent olefin-based synthetic wax comprising a 1 / g cyclic olefin-based copolymer.

Further, the present invention provides an efficient method for producing the above-mentioned transparent olefin-based synthetic wax, which comprises the following compounds (A) and (B) or (A), (B) and (C) as main components. Provided is a method for copolymerizing an α-olefin and a cyclic olefin using a catalyst. (A) a transition metal compound containing a tetravalent transition metal of Group IVB (B) a compound which reacts with the transition metal compound (A) to form an ionic complex (C) an organoaluminum compound

Hereinafter, the present invention will be described in more detail.
The transparent olefin-based synthetic wax of the present invention comprises a cyclic olefin-based copolymer having a repeating unit derived from ethylene and a repeating unit derived from a cyclic olefin.

[0010]

The cyclic olefin is not particularly limited, but may be, for example, a compound represented by the following general formula [Y]:

Embedded image (In the formula [Y], R ^{b to} R ^m each represent a hydrogen atom and a carbon atom of 1;
Represents a hydrocarbon group or a substituent containing a halogen atom, an oxygen atom or a nitrogen atom, and n represents an integer of 0 or more. R ^j or R ^k and R ^l or R ^m may form a ring with each other. R ^{b to} R ^m may be the same or different from each other. ) Which give a repeating unit represented by

In the repeating unit represented by the general formula [Y], R ^{b to} R ^m each represent a hydrogen atom or a carbon atom
To 20 hydrocarbon groups or substituents containing a halogen atom, an oxygen atom or a nitrogen atom. Here, as the hydrocarbon group having 1 to 20 carbon atoms, specifically, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
Alkyl groups having 1 to 20 carbon atoms such as -butyl group, isobutyl group, t-butyl group, hexyl group, etc .; aryl groups having 6 to 20 carbon atoms such as phenyl group, tolyl group, benzyl group, alkylaryl group or arylalkyl. , A methylidene group, an ethylidene group, a propylidene group, etc.
Carbon number 2 such as alkylidene group, vinyl group, allyl group of 0
And -20 alkenyl groups. However,
R ^b , R ^c , R ^f and R ^g exclude an alkylidene group. Note that R
^{When any of d} , R ^e , and R ^{h to} R ^m is an alkylidene group,
The carbon atom to which it is attached has no other substituents.

Specific examples of the substituent containing a halogen atom include halogen substituents such as fluorine, chlorine, bromine and iodine, and halogen substituents having 1 to 20 carbon atoms such as chloromethyl, bromomethyl and chloroethyl. Examples include an alkyl group. Specific examples of the substituent containing an oxygen atom include, for example, an alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a phenoxy group, and a carbon atom having 1 to 20 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group. And the like. Specifically as a substituent containing a nitrogen atom,
Examples thereof include an alkylamino group having 1 to 20 carbon atoms such as a dimethylamino group and a diethylamino group, and a cyano group.

Specific examples of the cyclic olefin giving the repeating unit represented by the general formula [Y] include, for example, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, -Methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5-
Phenylnorbornene, 5-benzylnorbornene, 5
-Ethylidene norbornene, 5-vinyl norbornene,
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-methyl-
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-ethyl-
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4
4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4
4a, 5,8,8a-octahydronaphthalene, 1,5
-Dimethyl-1,4,5,8-dimethano-1,2,3
4,4a, 5,8,8a-octahydronaphthalene, 2
-Cyclohexyl-1,4,5,8-dimetano-1,
2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene, 1,2-dihydrodicyclopentadiene,
5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene,
5,6-dicarboxyl norbornene anhydrate, 5-dimethylamino norbornene, 5-cyano norbornene and the like can be mentioned. Among these, norbornene or a derivative thereof is particularly preferred.

The cyclic olefin copolymer used in the present invention is basically obtained by copolymerizing ethylene and a cyclic olefin as described above, but within a range that does not impair the object of the present invention. In addition to these two essential components, another copolymerizable unsaturated monomer component may be used as necessary. Specific examples of such an optionally copolymerizable unsaturated monomer include propylene and 1-butene.
Α-olefins other than ethylene , among the above-mentioned cyclic olefin components, those not previously used, cyclic dienes such as dicyclopentadiene and norbornadiene, and chain dienes such as butadiene, isoprene and 1,5-hexadiene. And monocyclic olefins such as cyclopentene and cycloheptene.

In the cyclic olefin copolymer used in the present invention, the content of repeating units derived from ethylene
[Ethylene] and content of the repeating unit derived from a cyclic olefin [y] is ethylene, depends on the type and combination of cyclic olefins, but generally defined to can not be necessarily normal [ethylene] is 70 to 99 .9
[Y] is in the range of 30 to 0.1 mol% with respect to mol%, preferably
[Ethylene] is 80 to 99.8 mol% and [y] is 2
0 to 0.2 mol%, particularly preferably [ethylene] is 85%
[Y] is 15 to 2 mol% with respect to ９８98 mol%. D
When the content of ethylene units [ethylene] is less than 70 mol%, the glass transition temperature (Tg) of the copolymer increases,
Low-temperature properties and flexibility of the obtained wax may be insufficient. On the other hand, when the content [y] of the cyclic olefin unit is less than 0.1 mol%, the effect of introducing the cyclic olefin component becomes insufficient, and the crystallinity of the copolymer may increase.

The cyclic olefin copolymer is a copolymer in which repeating units derived from ethylene and repeating units derived from a cyclic olefin are arranged substantially linearly, and does not have a gel-like crosslinked structure. Preferably, it is The absence of a gel-like crosslinked structure can be confirmed by the fact that the copolymer is completely dissolved in decalin at 135 ° C.

The cyclic olefin copolymer must have a glass transition temperature (Tg) of 70 ° C. or less. Use of such a copolymer makes it possible to obtain a wax that can be suitably used at a low temperature. A more preferred glass transition temperature (Tg) is -30 to 50C, particularly -30 to 20C. In this case, the cyclic olefin-based copolymer used in the present invention can control the glass transition temperature (Tg) arbitrarily by changing the type and composition of the monomer, and is used for the intended application and use. The glass transition temperature (Tg) can be arbitrarily changed according to the temperature or the like.

The cyclic olefin-based copolymer is 13
The intrinsic viscosity [η] measured in decalin at 5 ° C. is 0.00
It is necessary to be 5 to 0.4 dl / g. More preferred intrinsic viscosity [η] is 0.05 to 0.3 dl / g.

Although the molecular weight of the cyclic olefin copolymer used in the present invention is not particularly limited, the weight average molecular weight Mw measured by gel permeation chromatography (GPC) is from 500 to 20,000, especially 1 2,000 to 15,000, number average molecular weight Mn is 200
It is preferable that the molecular weight distribution (Mw / Mn) is 1.3 to 4, particularly 1.4 to 3. When the molecular weight distribution (Mw / Mn) is more than 4, the content of the low molecular weight compound becomes large, handling becomes difficult, and when used as a lubricant, it may cause bleed out.

The cyclic olefin-based copolymer preferably has a crystallinity of 0 to 40% as measured by X-ray diffraction. If the crystallinity exceeds 40%, the transparency may decrease. More preferred crystallinity is 0 to 30%,
In particular, it is 0 to 25%.

The cyclic olefin copolymer used in the present invention may be a copolymer consisting of only those having the physical properties in the above-mentioned range. In this case, the glass transition temperature (Tg) is 70 ° C. or less. It may be a mixture of copolymers having certain different Tg. Further, the copolymer may partially contain a copolymer having physical properties outside the above range. In the latter case, it is sufficient that the entire physical property value is included in the above range.

The transparent olefin-based synthetic wax of the present invention comprises a catalyst containing the following compounds (A) and (B) as main components or a catalyst containing the following compounds (A), (B) and (C) as main components. By performing copolymerization of ethylene and a cyclic olefin by using the compound, the compound can be efficiently produced. (A) a transition metal compound containing a tetravalent transition metal of Group IVB (B) a compound which reacts with the transition metal compound (A) to form an ionic complex (C) an organoaluminum compound

[0024]

As such a transition metal compound (A),
Although various compounds can be mentioned, the following general formulas (I) and (I)
A cyclopentadienyl compound represented by I) or (III) or a derivative thereof, or a compound represented by the following general formula (IV) or a derivative thereof is preferable. ^{_{CpM 1 R 1 a R 2 b}} R 3 c ... (I) Cp 2 M 1 R 1 a R 2 b ... (II) (Cp-A e -Cp) M 1 R 1 a R 2 b ... (III) M ¹ R ¹ _a R ² _b R ³ _c R ⁴ _d ... (IV)

[In the formulas (I) to (IV), M ¹ is Ti, Zr
Or Hf atom, Cp is a cyclopentadienyl group,
It represents a cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group such as a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group. R ¹ , R ² , R ³ and R ⁴ are each σ
Ligands such as binding ligands, chelating ligands, and Lewis bases are shown. Specific examples of the σ binding ligand include a hydrogen atom, an oxygen atom, a halogen atom, and a carbon atom having 1 to 1 carbon atoms. 20 alkyl groups, C1-C20 alkoxy groups, C6-C6
Examples of the aryl group include an aryl group, an alkylaryl group or an arylalkyl group having 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an allyl group, a substituted allyl group, a substituent containing a silicon atom, and the like. Examples include an acetylacetonate group and a substituted acetylacetonate group. A represents a covalent crosslink. a, b, c and d
Is an integer of 0 to 4, and e is an integer of 0 to 6. R
Two or more of ¹ , R ² , R ³ and R ⁴ may combine with each other to form a ring. When Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. In the formulas (II) and (III), the two Cp's may be the same or different from each other. ]

The substituted cyclopentadienyl group in the above formulas (I) to (III) includes, for example, methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethyl Cyclopentadienyl group, tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,
2,3-trimethylcyclopentadienyl group, 1,2,2
4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group and the like. In addition, the above (I) to (I
Specific examples of R ^{1 to} R ^{4 in} the formula V) include, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as a halogen atom; a methyl group, an ethyl group, and an n-propyl group as an alkyl group having 1 to 20 carbon atoms. Group, iso-propyl group,
n-butyl group, octyl group, 2-ethylhexyl group; methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group as C1-C20 alkoxy group; C6-C20 aryl group, alkylaryl group or A phenyl group, a tolyl group, a xylyl group, or a benzyl group as an arylalkyl group; a heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms; a trimethylsilyl group or a (trimethylsilyl) methyl group as a substituent containing a silicon atom: Lewis base As dimethyl ether,
Ethers such as diethyl ether and tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 2, Amines such as 2'-bipyridine and phenanthroline; phosphines such as triethylphosphine and triphenylphosphine; linear unsaturated hydrocarbons such as ethylene, butadiene, 1-pentene, isoprene, pentadiene, 1-hexene and derivatives thereof;
Examples of the cyclic unsaturated hydrocarbon include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene, and derivatives thereof. Examples of the crosslink by a covalent bond of A in the above formula (III) include, for example, a methylene bridge, a dimethylmethylene bridge, an ethylene bridge, 1,1′-
Examples include a cyclohexylene cross-link, a dimethylsilylene cross-link, a dimethylgermylene cross-link, and a dimethylstannylene cross-link.

Examples of such compounds include the following compounds and compounds obtained by substituting zirconium of these compounds with titanium or hafnium. Compounds of formula (I) (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) tribenzylzirconium, (pentamethylcyclopentadienyl) trichloro Zirconium, (pentamethylcyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadienyl) tribenzylzirconium, (cyclopentadienyl) trichloro Zirconium, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium, (methylcyclopentadienyl) trimethyldi Ruconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) dimethyl (methoxy) zirconium,
(Dimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylsilylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium,

A compound of formula (II) bis (cyclopentadienyl) dimethylzirconium,
Bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) diethyl zirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium , Bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydridozirconium, bis (methylcyclopentadienyl) dimethylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclo Pentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) dimethyl zirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, Scan (pentamethylcyclopentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) chloromethyl zirconium,
Bis (pentamethylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl) (pentamethylcyclopentadienyl) dichlorozirconium,

Compound of Formula (III) Ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) dichloro zirconium, ethylene bis (tetrahydroindenyl) dimethyl zirconium, ethylene bis (tetrahydroindenyl) dichloro zirconium, dimethylsilylene bis (cyclo (Pentadienyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dichlorozirconium , [Phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, diphenylmethylene Tadienyl)
(9-fluorenyl) dimethyl zirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexylidene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium,
Cyclopentylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclobutylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium,
Dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dimethylzirconium, dimethylsilylenebis (indenyl) dichlorozirconium

Examples of compounds other than the cyclopentadienyl compounds represented by the above general formulas (I), (II) and (III) include the compounds of the above formula (IV). Examples include zirconium compounds, hafnium compounds, and titanium compounds having one or more of an alkyl group, an alkoxy group, and a halogen atom, such as a compound in which zirconium is replaced with hafnium or titanium. Tetramethyl zirconium, tetrabenzyl zirconium, tetramethoxy zirconium, tetraethoxy zirconium, tetrabutoxy zirconium, tetrachloro zirconium, tetrabromo zirconium,
Butoxytrichlorozirconium, dibutoxydichlorozirconium, bis (2,5-di-t-butylphenoxy) dimethylzirconium, bis (2,5-di-t-butylphenoxy) dichlorozirconium, zirconium bis (acetylacetonate),

The transition metal compound containing a VB-VIII group transition metal is not particularly limited. Specific examples of the chromium compound include, for example, tetramethylchromium, tetra (t
-Butoxy) chromium, bis (cyclopentadienyl) chromium, hydridetricarbonyl (cyclopentadienyl) chromium, hexacarbonyl (cyclopentadienyl) chromium, bis (benzene) chromium, tricarbonyltris (triphenylphosphonate) Chromium, tris (allyl) chromium, triphenyltris (tetrahydrofuran) chromium, chromium tris (acetylacetonate) and the like can be mentioned.

[0033]

[0034]

[0035]

Next, as the compound (B), any compound can be used as long as it reacts with the transition metal compound (A) to form an ionic complex. A compound comprising a bound anion, particularly a coordination complex compound comprising a cation and an anion having a plurality of groups bound to an element, can be suitably used. As a compound comprising such a cation and an anion in which a plurality of groups are bonded to an element, the following formula (V) or (VI)
The compound shown by can be used suitably. ^{([L 1 -R 7] k} +) p ([M 3 Z 1 Z 2 ... Z n] (nm) -) q ... (V) ([L 2] k +) p ([M 4 Z 1 Z 2 ... ^{Z n] (nm) -)} q ... (VI) ( where, L ² is ^{M 5, R 8 R 9 M} 6, R 10 is ₃ C or R ¹¹ M ⁶⁾

In the formulas (V) and (VI), L ¹ is a Lewis base, M ³ and M ⁴ are VB group, VIB group and V
IIB, VIII, IB, IIB, IIIA, IVA and
Element selected from Group VA, preferably, a Group IIIA, elements selected from Group IVA, and group VA, IIIB group of M ⁵ and M ^6, respectively Periodic Table, IVB group, VB group, VIB group, VIIB group, V
Group III, IA Group, IB, Group IIA, element selected from Group IIB and VIIA group, Z ¹ to Z ⁿ are each a hydrogen atom, a dialkylamino group, an alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms Aryloxy group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group, arylalkyl group, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, acyloxy having 1 to 20 carbon atoms group, an organometalloid group or a halogen atom, Z ¹ to Z ⁿ may form a ring of two or more thereof with each other. R ⁷
Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
20 aryl group, an alkyl group, or an arylalkyl group, each R ⁸ and R ⁹ are a cyclopentadienyl group, substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, R ¹⁰ is 1 to 20 carbon atoms It represents an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group. R ¹¹ is tetraphenylporphyrin,
It shows a macrocyclic ligand such as phthalocyanine. m is M ³ , M
A valence of ⁴ and an integer of 1 to 7, n is an integer of 2 to 8 and k is an integer of 1 to 7 of an ionic valence of [L ¹ -R ⁷ ] and [L ² ];
p is an integer of 1 or more, and q = (p × k) / (nm). ]

Specific examples of the above Lewis base include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as trimethylamine, triethylamine, tri-n-butylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p- bromo- N, N-dimethylaniline, p-nitro-N, N-dimethylaniline; Phosphines such as fin, triphenylphosphine and diphenylphosphine;
Dimethyl ether, diethyl ether, tetrahydrofuran, and dioxane, diethyl thioether, thioethers such as tetrahydrothiophene, ethyl
Esters such as rubenzoate . Specific examples of M ³ and M ⁴ include B, Al, Si, P, As, S
b, etc., preferably B or P, as completely as examples of M ⁵ L
i, Na, Ag, Cu, Br, I, I 3 , etc., specific examples of ^{M 6 Mn, Fe, Co,} Ni, Zn and the like.

Specific examples of Z ^{1 to} Z ⁿ include, for example, a dimethylamino group and a diethylamino group as a dialkylamino group; a methoxy group, an ethoxy group and an n-butoxy group as an alkoxy group having 1 to 20 carbon atoms; A phenoxy group, a 2,6-dimethylphenoxy group, a naphthyloxy group as an aryloxy group having from 20 to 20; a methyl group, an ethyl group, an n-propyl group as an alkyl group having from 1 to 20 carbon atoms;
iso-propyl group, n-butyl group, n-octyl group,
2-ethylhexyl group; an aryl group having 6 to 20 carbon atoms,
A phenyl group, p-tolyl group, benzyl group, 4-tert-butylphenyl group, 2,6-dimethylphenyl group,
3,5-dimethylphenyl group, 2,4-dimethylphenyl group, 2,3-dimethylphenyl group; p-fluorophenyl group, 3,5-difluorophenyl group as a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, Pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5- bis (trifluoromethyl) phenyl group; F, Cl, Br,
I; Examples of the organic metalloid group include a pentamethylantimony group, a trimethylsilyl group, a trimethylgermyl group, a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group. Specific examples of R ⁷ and R ¹⁰ include:
The same ones as mentioned above can be mentioned. R ⁸ and R
Specific examples of the substituted cyclopentadienyl group ⁹ include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Here, the alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups can be selected as an integer of 1 to 5. (V), (V
Among the compounds of the formula (I), those in which M ³ and M ⁴ are boron are preferred.

Among the compounds of the formulas (V) and (VI), the following compounds can be particularly preferably used. Compound of formula (V): triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyltri (n-butyl) ammonium tetraphenylborate, benzyltributyltetraphenylborate (N-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyltetraphenylborate (2-cyanopyridinium ), Trimethylsulfonium tetraphenylborate, benzyldimethylsulfonium tetraphenylborate ,

Triethylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate
Tetrabutylammonium borate, tetrakis (pentafluorophenyl) borate (tetraethylammonium),
Tetrakis (pentafluorophenyl) borate (methyltri (n-butyl) ammonium), tetrakis (pentafluorophenyl) borate (benzyltri (n-butyl))
Ammonium), methyldiphenylammonium tetrakis (pentafluorophenyl) borate, methyltriphenylammonium tetrakis (pentafluorophenyl) borate, dimethyldiphenylammonium tetrakis (pentafluorophenyl) borate, anilinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluoro) Phenyl) methylanilinium borate,
Dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, dimethyltetrakis (pentafluorophenyl) borate (m-nitroanilinium), dimethyltetrakis (pentafluorophenyl) borate (p-bromo) Anilinium),

Pyridinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (p-cyanopyridinium), tetrakis (pentafluorophenyl) borate (N-methylpyridinium), tetrakis (pentafluorophenyl) borate (N
-Benzylpyridinium), tetrakis (pentafluorophenyl) borate (O-cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate (p
-Cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate (p-cyano-N-benzylpyridinium), trimethylsulfonium tetrakis (pentafluorophenyl) borate, benzyldimethylsulfonium tetrakis (pentafluorophenyl) borate, tetrakis ( Tetraphenylphosphonium (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tetrakis
[3,5-bis (trifluoromethyl) phenyl] dimethylanilinium borate, triethylammonium hexafluoroarsenate,

Compound of Formula (VI) Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, manganese tetraphenylborate (ferromanganese tetraphenylporphyrin), ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (1,1'-
Dimethylferrocenium), decamethylferrocenium tetrakis (pentafluorophenyl) borate, acetylferrocenium tetrakis (pentafluorophenyl) borate, formylferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate Cyanoferrocenium, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (tetra Phenylporphyrin manganese), tetrakis (pentafluorophenyl) borate (tetraphenylporphyrin iron chloride), tetrakis (pentafluoro) Phenyl) borate (tetraphenylporphyrin zinc), silver tetrafluoroborate, hexafluoroarsenate, silver hexafluoroantimonate, silver

Compounds other than formulas (V) and (VI), for example, tris (pentafluorophenyl) boron, tris
[3,5-bis (trifluoromethyl) phenyl] boron, triphenylboron and the like can also be used.

Examples of the organoaluminum compound as the component (C) include compounds represented by the following general formulas (VII), (VIII) and (IX). R ¹² _r AlQ _3-r (VII) (R ¹² is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to ¹² carbon atoms such as an alkyl group, an alkenyl group, an aryl group and an arylalkyl group; Q is a hydrogen atom; Represents an alkoxy group or a halogen atom having 1 to 20 carbon atoms, and r is in the range of 1 ≦ r ≦ 3.) As the compound of the formula (VII), specifically, trimethylaluminum, triethylaluminum, triisopropyl Examples include aluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, and ethylaluminum sesquichloride.

[0046]

Embedded image (R ¹² is the same as in formula (VII). S indicates the degree of polymerization, and is usually 3 to 50, preferably 7 to 40.)

[0047]

Embedded image (R ¹² is the same as in formula (VII). S represents the degree of polymerization, and the preferred number of repeating units is 3 to 50, and preferably 7 to 40.) Aluminoxane. Among the compounds of the formulas (VII) to (IX), preferred are an alkyl group having 3 or more carbon atoms, especially an alkyl group-containing aluminum compound having at least one or more branched alkyl group or an aluminoxane. Particularly preferred is triisobutylaluminum or an aluminoxane having a degree of polymerization of 7 or more. When this triisobutylaluminum, aluminoxane having a polymerization degree of 7 or more, or a mixture thereof, high activity can be obtained.

Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the method is not particularly limited, and the reaction may be carried out according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, a method in which an organoaluminum compound is added at the beginning of polymerization and water is added later, a crystal water contained in a metal salt or the like, A method of reacting water adsorbed on inorganic or organic substances with an organoaluminum compound, a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane, and further reacting water.

The catalyst used in the production of the olefinic synthetic wax of the present invention comprises the above components (A) and (B) or components (A), (B) and (C) as main components. In this case, the use conditions of the component (A) and the component (B) are not limited, but the ratio (molar ratio) of the component (A) to the component (B) is 1: 0.01 to 1: 100, particularly 1: 1: 0.5 ~
1:10, particularly preferably 1: 1 to 1: 5. The working temperature is preferably in the range of -100 to 250 ° C, and the pressure and time can be set arbitrarily.

The amount of component (C) used is generally 0 to 2,000 mol, preferably 5 to 2000 mol per mol of component (A).
It is 1,000 mol, particularly preferably 10 to 500 mol. When the component (C) is used, the polymerization activity can be improved. However, when the content is too large, a large amount of the organic aluminum compound remains in the polymer, which is not preferable.

There are no particular restrictions on the manner of use of the catalyst component. For example, the component (A) and the component (B) may be brought into contact with each other in advance, or the contact product may be separated and washed before use. It may be used in contact. Further, the component (C) may be used in contact with the component (A), the component (B) or a contact product of the component (A) and the component (B) in advance.
The contact may be made in advance, or may be brought into contact in the polymerization system. Further, the catalyst component can be added in advance to the monomer and the polymerization solvent, or can be added to the polymerization system. The catalyst component can be used by supporting it on an inorganic or organic carrier, if necessary.

The usage ratio of the catalyst to the reaction raw material is such that the raw material monomer / component (A) (molar ratio) or the raw material monomer / component (B) (molar ratio) is 1 to 10 ⁹ , especially 1
It is preferable to be a 00-10 ^7.

The polymerization methods include bulk polymerization, solution polymerization,
Any method such as suspension polymerization and gas phase polymerization may be used.
Further, a batch method or a continuous method may be used. When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane;
Aliphatic hydrocarbons such as pentane, hexane, heptane and octane, and halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Further, a monomer such as an α-olefin may be used as the solvent.

Regarding the polymerization conditions, the polymerization temperature is 50 ° C. or higher,
In particular, the temperature is preferably from 50 to 250 ° C, particularly preferably from 70 to 200 ° C. When the polymerization temperature is lower than 50 ° C., the molecular weight of the copolymer becomes high, so that the copolymer may not be used as a wax. The polymerization time is usually 1 minute to 10 hours, the reaction pressure is normal pressure to 100 kg / cm ² G, preferably normal pressure to 50 Kg.
g / cm ² G.

Further, the partial pressure of ethylene was set to 10 kg / cm ²
It is preferable to carry out the copolymerization at less than 8 kg / cm ² , in particular. When the partial pressure of ethylene is 10 kg / cm ² or more , the molecular weight of the copolymer may be too high.

The molecular weight of the copolymer can be adjusted by selecting the amount of each catalyst component and the polymerization temperature, and furthermore, by a polymerization reaction in the presence of hydrogen, and particularly preferably a polymerization reaction in the presence of hydrogen. . When the copolymerization is carried out in the presence of hydrogen, the hydrogen partial pressure is preferably 0.01 to 20 kg / cm ² G, particularly preferably 0.1 to 10 kg / cm ² G. If the hydrogen partial pressure is less than 0.01 kg / cm ² G, the molecular weight of the copolymer may be too high, and
^If it exceeds ² G, the molecular weight of the copolymer may be too low.

The olefin synthetic wax of the present invention can be used, for example, as a modifier for synthetic resins, a lubricant, a dispersant, an adhesive for hot melt, a grease for lubrication, an additive for lubricating oil, a light oil pour point depressant, and a candle. , Matching Impregnants, Paper Capacitors, Electrical Insulating Agents, Surface Modifiers for Construction Materials, Electrophotographic Toners, Corrugated Waterproofing Agents, Textile Processing Aids, Ceramics and Metal Powder Molding Binders, Pigment Bases, etc. Can be used for applications.

In this case, if necessary, various additives such as an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a dye and a pigment may be added to the olefin-based synthetic wax of the present invention. Can be.

[0059]

EXAMPLES Next, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the following examples. Example 1 (1) Synthesis of dimethylanilinium tetrakis (pentafluorophenyl) borate pentafluorophenyllithium prepared from 152 mmol of bromopentafluorobenzene and 152 mmol of butyllithium was reacted with 45 mmol of boron trichloride in hexane. And tris (pentafluorophenyl) boron as a white solid. 41 mmol of the obtained tris (pentafluorophenyl) boron was reacted with 41 mmol of lithium pentafluorophenyl , and lithium tetrakis (pentafluorophenyl) boron was isolated as a white solid. Then, lithium te
By reacting 16 mmol of trakis (pentafluorophenyl) boron and 16 mmol of dimethylaniline hydrochloride in water, 11.4 mmol of dimethylanilinium tetrakis (pentafluorophenyl) borate was obtained as a white solid. The fact that the product is the desired product is based on ¹ H-
Confirmed by NMR and ¹³ C-NMR.

(2) Copolymerization of ethylene and 2-norbornene In a 1-liter autoclave at room temperature under a nitrogen atmosphere, 400 ml of toluene, 0.6 mmol of triisobutylaluminum (TIBA), and 10 micromol of biscyclopentadienyl zirconium dichloride were added. 20 micromoles of dimethylanilinium tetrakis (pentafluorophenyl) borate prepared in the above (1) was added in this order, 0.15 mol of 2-norbornene was added, the temperature was raised to 90 ° C., and the ethylene partial pressure was increased. Is 0.5kg
/ Cm ² while introducing ethylene continuously.
The reaction was performed for 0 minutes. After completion of the reaction, toluene was distilled off under reduced pressure to obtain a cyclic olefin-based copolymer (olefin-based synthetic wax). Table 1 shows catalyst components, polymerization conditions, polymerization results, and physical properties of the obtained copolymer.

The measurement of each physical property in Table 1 was performed as follows. Norbornene content From the ratio of the sum of a peak based on ethylene and a peak based on methylene at the 5th and 6th positions of norbornene and a peak based on a methylene group at 7th position of the norbornene appearing at around 32.5 ppm, in ^13C -NMR, I asked. Intrinsic viscosity [η] Measured in decalin at 135 ° C. Using a TMA-100 manufactured by Seiko Denshi Co., Ltd. as a softening temperature measuring apparatus, a temperature of 10 ° C./min was applied to the test piece at a rate of 10 ° C./min by applying a load of 5 g to a temperature at which the needle penetrated 0.06 mm.

As a glass transition temperature (Tg) measuring device, Vibron 11 manufactured by Toyo Bolding Co., Ltd.
-Using EA type, width 4mm, length 40mm, thickness 0.1
mm was measured at a heating rate of 3 ° C./min and a frequency of 3.5 Hz, and was determined from the peak of the loss elastic modulus (E ″) at this time. Melting point (Tm): Perkin Elmer 7 series DSC 10
The temperature was measured in the range of -50 ° C to 150 ° C at a heating rate of ° C / min. Crystallinity Using a test piece prepared by hot pressing, X at room temperature
It was determined by a line diffraction method. Haze Digital Haze Computer (DIGITAL HAZE COMPU
TER) (manufactured by Suga Test Instruments Co., Ltd.)
The measurement was performed according to 7105. The above measuring methods are all the same in the following examples.

Example 2 A cyclic olefin-based copolymer (olefin-based synthetic wax) was produced in the same manner as in Example 1, except that the catalyst components and the polymerization conditions were changed as shown in Table 1. In this example, copolymerization was carried out after hydrogen was introduced at the start of polymerization so that the partial pressure became 3 kg / cm ² . Table 1 shows catalyst components, polymerization conditions, polymerization results, and physical properties of the obtained copolymer.

Examples 3 and 4 A cyclic olefin copolymer (olefin synthetic wax) was produced in the same manner as in Example 1 except that the catalyst components and the polymerization conditions were changed as shown in Table 1. Catalyst components,
Table 1 shows the polymerization conditions, the polymerization results, and the physical properties of the obtained copolymer.

Comparative Example 1 In Example 1 (2), 100 mmol of ethyl aluminum sesquichloride was used in place of triisobutylaluminum (TIBA), and VO (OC ₂ H ₅ ) Cl ₂ was used in place of biscyclopentadienyl zirconium dichloride. Was used, dimethylanilinium tetrakis (pentafluorophenyl) borate was not used, the amount of 2-norbornene used was 0.14 mol, the polymerization temperature was 30 ° C., and the ethylene partial pressure was 1 kg / cm 2. ^2. Example 1 except that the hydrogen partial pressure was 1 kg / cm ^2.
A cyclic olefin copolymer was produced in the same manner as in (2). Table 1 shows catalyst components, polymerization conditions, polymerization results, and physical properties of the obtained copolymer.

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[Table 1]

[0067]

As described above, the transparent olefin synthetic wax of the present invention has water resistance, flexibility, transparency,
It has excellent low-temperature characteristics. In addition, the transparent olefin synthetic wax of the present invention softens from a low temperature, has good workability at room temperature, and has excellent heat aging resistance and excellent dielectric properties. Further, according to the production method of the present invention, such a transparent olefin-based synthetic wax can be efficiently produced.

[Brief description of the drawings]

FIG. 1 is a flowchart showing a method for producing a transparent olefin-based synthetic wax of the present invention.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-221206 (JP, A) JP-A-62-252406 (JP, A) JP-A-61-211315 (JP, A) JP-A-1- 156308 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/60-4/70 C08F 32/00-32/08 C08F 232/00-232/08

Claims (3)

(57) [Claims] 1. A compound comprising the following compounds (A) and (B) as main components:
Or the following compounds (A), (B) and (C)
(A) a transition metal compound containing a tetravalent transition metal of group IVB, (B) a ionic complex which reacts with the transition metal compound (A) and is produced using a catalyst as a component.
Compounds that form (C) and a repeating unit derived from repeating units and cycloolefin derived from an organoaluminum compound of ethylene, a glass transition temperature (Tg) of
Is 70 ° C. or less and the intrinsic viscosity [η] is 0.005 to 0.4 d.
A transparent olefin-based synthetic wax comprising a cyclic olefin-based copolymer of 1 / g. 2. The molar ratio of a repeating unit derived from ethylene to a repeating unit derived from a cyclic olefin is from 70 to 70.
The transparent olefin-based synthetic wax according to claim 1, which has a ratio of 99.9: 30 to 0.1. 3. The process for producing a transparent olefin-based synthetic wax according to claim 1, wherein the compound (A)
And a method for producing an olefin-based synthetic wax, wherein ethylene and a cyclic olefin are copolymerized using a catalyst containing (B) or (A), (B) and (C) as main components. (A) a transition metal compound containing a group IVB tetravalent transition metal (B) a compound which reacts with the transition metal compound (A) to form an ionic complex (C) an organoaluminum compound