JP2005145855A - Cyclic olefin composition and method for producing cyclic olefin polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cyclic olefin composition which can produce a cyclic olefin polymer with a high polymerization activity and excels in storage stability, and a method for producing a cyclic olefin polymer with a high polymerization activity by using this composition. <P>SOLUTION: The cyclic olefin composition comprises a purified cyclic olefin obtained by bringing a cyclic olefin into contact with an alkali, and then, if necessary, removing a low-boiling content and/or a high-boiling content, and an antioxidant agent or comprises a purified cyclic olefin obtained by bringing a cyclic olefin into contact with an inorganic compound and an antioxidant. The method for producing a cyclic olefin polymer comprises subjecting a monomer composition containing the above cyclic olefin composition to polymerization with the use of a polymerization catalyst. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a cyclic olefin composition and a method for producing a cyclic olefin polymer using the composition.

  Cyclic olefin copolymers such as ethylene, propylene, and ethylidene norbornene copolymers are vulcanizable polymers with excellent weather resistance, heat resistance, ozone resistance, etc., automotive industrial parts, industrial rubber It is used as rubber products such as products, electrical insulation materials, civil engineering and building materials, and rubberized fabrics, and is also widely used as a material for plastic blends with polypropylene and polystyrene. When producing a cyclic olefin polymer such as this cyclic olefin copolymer, the polymerization activity may be low depending on the production conditions of the catalyst and the like, and the appearance of a method for producing a cyclic olefin polymer with high polymerization activity has appeared. It was desired.

  Accordingly, the applicant of the present invention uses a norbornene or a derivative thereof contacted with alumina or a norbornene or a derivative thereof contacted with alkaline water as a raw material monomer when producing a cyclic olefin polymer using a metallocene catalyst. (See Patent Document 1).

As a result of further investigation, the inventors of the present application have confirmed that, in producing a cyclic olefin polymer, the purified cyclic olefin and the antioxidant obtained by removing light and / or high boiling components as necessary after contacting with alkali. A cyclic olefin composition comprising an agent, a cyclic olefin composition comprising a purified cyclic olefin obtained by contacting a cyclic olefin with an inorganic compound and an antioxidant, has excellent polymerization activity and is stable in storage. The inventors have found that the present invention is excellent and have completed the present invention.
JP 2000-204120 A

  An object of the present invention is to provide a cyclic olefin composition that can produce a cyclic olefin polymer with high polymerization activity and that has excellent storage stability, and a cyclic olefin composition obtained by this method. And to provide a method for producing a cyclic olefin polymer with high polymerization activity.

  According to this invention, the manufacturing method of the following cyclic olefin composition and cyclic olefin-type polymer is provided, and the said subject is solved.

  (1) A cyclic olefin composition comprising a purified cyclic olefin obtained by bringing a cyclic olefin into contact with an alkali and an antioxidant.

  (2) A cyclic olefin comprising a purified cyclic olefin obtained by contacting a cyclic olefin with an alkali and then removing light and / or high-boiling components, and an antioxidant. Olefin composition.

  (3) The purified cyclic olefin was obtained by removing 0.05% by weight or more of light boiling or high boiling content based on the weight of the cyclic olefin before distillation after contacting with alkali. The cyclic olefin composition according to the above (2), which is a product.

  (4) The purified cyclic olefin was obtained by removing 0.05% by weight or more of light and high-boiling components, respectively, based on the weight of the cyclic olefin before distillation after contacting with alkali. The cyclic olefin composition according to the above (2), which is a product.

  (5) A cyclic olefin composition comprising a purified cyclic olefin obtained by bringing a cyclic olefin into contact with an adsorbent and an antioxidant.

  (6) The cyclic olefin composition according to any one of (1) to (5), wherein the antioxidant is a phenol-based antioxidant or a phosphorus-based antioxidant.

  (7) The cyclic olefin composition according to any one of (1) to (6), wherein the antioxidant is contained at a ratio of 0.1 to 1000 ppm with respect to the total amount of the cyclic olefin and the antioxidant.

  (8) Production of a cyclic olefin-based polymer, wherein the monomer composition containing the cyclic olefin composition according to any one of (1) to (7) is subjected to polymerization using a polymerization catalyst. Method.

  (9) The monomer contained in the monomer composition is composed of the purified cyclic olefin according to any one of (1) to (5) above and another olefin. The manufacturing method of the cyclic olefin type polymer as described in said (8).

  (10) The method for producing a cyclic olefin polymer according to (8) or (9), wherein the polymerization catalyst is an olefin polymerization catalyst.

  (11) The method for producing a cyclic olefin polymer according to (10), wherein the olefin polymerization catalyst contains an organoaluminum oxy compound or an ionized ionic compound as a catalyst component.

  When the cyclic olefin composition of the present invention is used, a cyclic olefin polymer can be produced with high polymerization activity. Moreover, the cyclic olefin composition according to the present invention is excellent in storage stability and can produce a cyclic olefin polymer with high polymerization activity even after being stored for a long period of time.

  According to the method for producing a cyclic olefin polymer of the present invention, a cyclic olefin polymer can be produced with high polymerization activity.

  Hereinafter, the production method of the cyclic olefin composition and the cyclic olefin polymer according to the present invention will be specifically described.

  The cyclic olefin composition according to the present invention contains the following purified cyclic olefin and antioxidant.

(Purified cyclic olefin)
The purified cyclic olefin used in the present invention is obtained by contacting the cyclic olefin with an alkali and then removing light and / or high boiling points as necessary, or contacting the cyclic olefin with an inorganic compound. It was obtained by purification.

The cyclic olefin used for this purification is a cyclic olefin having one or more unsaturated bonds, such as cyclopentene, dicyclopentadiene, cycloheptene, cyclooctadiene, norbornene, tetracyclododecene, 5-ethylidene-2. -Norbornene, 5-vinyl-2-norbornene, dicyclopentadiene, 2-methyl 1,4,5,
Examples thereof include cyclic olefins having 3 to 20 carbon atoms such as 8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, and derivatives thereof.

  The cyclic olefin used in the method for purifying a cyclic olefin of the present invention is a cyclic olefin containing a small amount of impurities such as a commercially available cyclic olefin, and the impurities are usually 100 ppm or more, for example, 100 to 10,000 ppm. include.

  Examples of impurities contained in commercially available cyclic olefins include oxygen-containing compounds such as peroxides and isomers such as 5-vinyl-2-norbornene in 5-ethylidene-2-norbornene. Of these, oxygen-containing compounds are considered to have an adverse effect on polymerization.

The impurity concentration here is obtained as a peak area ratio of FID-GLC.
The presence of peroxide can be confirmed by measuring the absorbance with a colorimetric method. Usually, the peroxide is contained in an amount of 1.0 ppm or more, for example, 1.0 to 100 ppm (in terms of cumene hydroperoxide).

In the present invention, norbornene and its derivatives (hereinafter sometimes referred to as “norbornenes”) are preferably used as the cyclic olefin.
The norbornenes are compounds having a norbornene (bicyclo [2.2.1] hept-2-ene) skeleton represented by the following general formula (I).

In formula, R < ¹ > -R < ⁸ > may mutually be same or different and is a hydrogen atom, a halogen atom, or a hydrocarbon group.
Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
Specific examples of the hydrocarbon group include alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl and octadecyl; and 3 to 3 carbon atoms such as cyclohexyl. 15 cycloalkyl groups; aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl, naphthyl, anthryl, biphenylyl, benzyl, tolyl, ethylphenyl, isopropylphenyl and the like. These hydrocarbon groups may have a halogen substituent.
The hydrocarbon group represented by R ^{5 to} R ⁸ may be partly bonded to form a single ring with the carbon atoms to which each is bonded, and the single ring has a double bond. Also good. Examples of such monocycles are shown below.

In the above examples, the carbon atom numbered 1 or 2 represents a norbornene ring carbon atom to which R ⁵ (R ⁶ ) or R ⁷ (R ⁸ ) is bonded.
R ⁵ and R ⁶ , or R ⁷ and R ⁸ may form an alkylidene group. Such alkylidene groups include ethylidene, propylidene, isopropylidene and the like.

Specific examples of norbornenes represented by the above general formula (I) include bicyclo [2.2.1] hept-2-ene (norbornene), 5-methylbicyclo [2.2.1] hept-2- Ene, 5,6-dimethylbicyclo [2.2.1] hept-2-ene, 1-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept -2-ene, 5-n-
Such as butylbicyclo [2.2.1] hept-2-ene, 5-isobutylbicyclo [2.2.1] hept-2-ene, 7-methylbicyclo [2.2.1] hept-2-ene, etc. A bicyclo [2.2.1] hept-2-ene derivative having an alkyl group;
5-ethylidenebicyclo [2.2.1] hept-2-ene (5-ethylidene-2-norbornene), 5-ethylidene-6-methylbicyclo [2.2.1] hept-2-ene, 5-ethylidene -6-ethylbicyclo [2.2.1] hept-2-ene, 5-ethylidene-6-isopropylbicyclo [2.2.1] hept-2-ene, 5-ethylidene-6-butylbicyclo [2. 2.1] hept-2-ene, 5-n-propylidenebicyclo [2.2.1] hept-2-ene, 5-n-propylidene-6-methylbicyclo [2.2.1] hept-2 -Ene, 5-n-propylidene-6-ethylbicyclo [2.2.1] hept-2-ene, 5-n-propylidene-6-isopropylbicyclo [2.2.1] hept-2-ene, 5 -N-propylidene-6-butylbicyclo [2.2. ] Hept-2-ene, 5-isopropylidene-bicyclo [2.2.1] hept-2-ene, 5-isopropylidene-6-methyl bicyclo [2.
2.1] hept-2-ene, 5-isopropylidene-6-ethylbicyclo [2.2.1] hept-2-ene, 5-isopropylidene-6-isopropylbicyclo [2.2.1] hept- Bicyclo [2.2.1] hept-2-ene derivatives having an alkylidene group such as 2-ene, 5-isopropylidene-6-butylbicyclo [2.2.1] hept-2-ene;
5-ethenylbicyclo [2.2.1] hept-2-ene (5-vinyl-2-norbornene), 5-propenylbicyclo [2.2.1] hept-2-ene, 5-butenylbicyclo [2.2. 1] bicyclo [2.2.1] hept-2-ene derivative having an alkenyl group such as hept-2-ene;
5-phenyl-, 5-methyl-5-phenyl-, 5-benzyl-, 5-tolyl-, 5- (ethylphenyl)-, 5- (isopropylphenyl)-, 5-biphenylyl-, 5- (β- Naphthyl)-, 5- (α-naphthyl)-, 5-anthryl-, 5,6-diphenyl-
A bicyclo [2.2.1] hept-2-ene derivative having an aromatic hydrocarbon group such as
Tricyclo [4.3.0.1 ^2,5 ] -3-decene, 2-methyltricyclo [4.3.0.1 ^2,5 ] -3-decene, 5-methyltricyclo [4.3. Tricyclo [4.3.0.1 ^2,5 ] -3-decene derivatives such as 0.1 ^2,5 ] -3-decene;
Tricyclo [4.4.0.1 ^2,5 ] -3-undecene, such as 10-methyltricyclo [4.4.0.1 ^2,5 ] -3-undecene, etc. ^2,5 ] -3-undecene derivative;
And dicyclopentadiene.

These norbornenes may be used singly or in combination of two or more.

  Among these, a bicyclo [2.2.1] hept-2-ene derivative (norbornene derivative) having an alkylidene group is preferable, and 5-ethylidenebicyclo [2.2.1] hept-2-ene, 5-ethylidene. -6-methylbicyclo [2.2.1] hept-2-ene, 5-ethylidene-6-ethylbicyclo [2.2.1] hept-2-ene, 5-ethylidene-6-isopropylbicyclo [2. 2.1] 5-ethylidene-2-norbornene such as hept-2-ene and 5-ethylidene-6-butylbicyclo [2.2.1] hept-2-ene or derivatives thereof are more preferable, and 5-ethylidene- 2-norbornene is particularly preferred.

Alkali contact treatment;
In the alkali contact treatment in which the cyclic olefin is brought into contact with the alkali, examples of the alkali used for the contact with the cyclic olefin include NaOH water, KOH water, and ammonia water. The concentration of these alkaline waters is usually 0.001 N or more, preferably 0.05 to 1.0 N.

  When the cyclic olefin and the alkaline water are brought into contact, the alkaline water is generally used in a volume ratio of 0.001 to 100, preferably 0.1 to 10, with respect to the volume 1 of the cyclic olefin. The contact time between the cyclic olefin and the alkaline water is usually 1 to 100 minutes, preferably 5 to 30 minutes, and the contact temperature is not particularly limited, but is usually 0 to 100 ° C., preferably 20 to 80 ° C. . Stirring may be performed at the time of contact between the cyclic olefin and the alkaline water.

  After contacting the cyclic olefin and the alkaline water, the cyclic olefin is separated from the aqueous phase. In the present invention, the operation of bringing the cyclic olefin and alkaline water into contact with each other and separating them may be repeated a plurality of times.

  A solid alkali having low compatibility with the cyclic olefin and water can also be used as the alkali. Specific examples of the method include a batch method in which a solid alkali and a cyclic olefin / water mixture are allowed to coexist, a method in which a cyclic olefin / water mixture is circulated through a column filled with the solid alkali, and the like. Specific examples of the solid alkali include basic ion exchange resins, hydrotalcite, and ion-supporting silica.

In the present invention, the cyclic olefin that has been brought into contact with the alkali may be further brought into contact with ion-exchanged water and the like to perform separation, thereby washing the cyclic olefin.
When the cyclic olefin brought into contact with the alkali and the ion-exchanged water are brought into contact with each other, the ion-exchanged water is usually used in a volume ratio of 0.001 to 100, preferably 0.1 to 10 with respect to the volume of the cyclic olefin. It is done. The contact time between the cyclic olefin contacted with the alkali and the ion exchange water is usually 1 to 100 minutes, preferably 5 to 30 minutes, and the contact temperature is not particularly limited, but is usually 0 to 100 ° C., preferably 20 to 20 minutes. It is in the range of 80 ° C. Stirring may be performed at the time of contact between the cyclic olefin brought into contact with the alkali and the ion exchange water.

After the cyclic olefin brought into contact with the alkali and the ion exchange water are brought into contact with each other, the cyclic olefin is separated from the aqueous phase.
In the present invention, the operation of bringing the cyclic olefin brought into contact with the alkali and the ion-exchanged water into contact with each other and separating them may be repeated a plurality of times.

distillation;
The purified cyclic olefin used in the present invention may be obtained by subjecting the cyclic olefin to the above alkali contact treatment, and then removing light and / or high boiling content from the obtained cyclic olefin.
Here, in the present invention, the light boiling component is a component distilled from the top of the column before the main distillation in batch distillation, and in the case of continuous distillation, when the main distillation is recovered from the column bottom, In general, in any case, it contains a cyclic olefin which is a target component. The high boiling point component is a component that remains in the tower after distilling from the top of the column in batch distillation, and is extracted from the bottom of the main distillation in the continuous distillation. Usually, in any case, it contains a cyclic olefin which is a target component.
The cyclic olefin obtained by subjecting a commercially available cyclic olefin to the alkali contact treatment usually has a light-boiling point impurity of about 0.1 to 1.0% by weight and a high-boiling point impurity of 0.01 to 0.05% by weight. About% is included.

The removal of light and / or high boiling components is usually carried out by distillation using a conventionally known distillation apparatus.
There are no problems with the type of tower, such as trays, irregular packing, and regular packing.
In the distillation of cyclic olefins, there is a concern of alteration due to the reverse Diels-Alder reaction, etc., so that it is usually handled at 180 ° C. or lower, preferably 120 ° C. or lower, more preferably 100 ° C. or lower. The pressure is usually carried out under reduced pressure in order to achieve the aforementioned temperature. In consideration of the refrigerant capacity of the condenser and the capacity of the vacuum device, conditions such that the top temperature is 40 to 100 ° C. are suitable. The number of stages is preferably 5 to 100, and more preferably 15 to 60. The reflux ratio is preferably from 0.1 to 50, and more preferably from 0.5 to 10.
In the case of removing light and high-boiling components, light and high-boiling components are removed in an arbitrary order.
In the case of removing light or high-boiling components, 0.05% by weight or more, preferably 0.05 to 20% by weight, more preferably 2 to 20%, based on the weight of the target cyclic olefin before distillation. It is preferable to remove by weight,
In the case of removing light and high-boiling components, they are each 0.05% by weight or more, preferably 0.05 to 20% by weight, more preferably 1 to 4%, based on the weight of the target cyclic olefin before distillation. It is more preferable to remove 10% by weight.

  The purified cyclic olefin obtained by subjecting the commercially available cyclic olefin to the above alkali contact treatment and distillation as necessary, when used as a monomer for olefin polymerization, The polymerization activity is superior to that used as it is. This is considered to be because impurities that affect the polymerization activity contained in the commercially available cyclic olefin can be removed.

(Adsorbent contact treatment)
The purified cyclic olefin according to the present invention may be purified by an adsorbent contact treatment in which the cyclic olefin containing a trace amount of impurities and the adsorbent are brought into contact with each other.

In the adsorbent contact treatment, for example, the cyclic olefin is contacted with an adsorbent such as alumina (Al ₂ O ₃ ), silica (which may contain various metals), zeolite, activated clay, titanium oxide, ion exchange resin, or the like. Is done.

The particle size of the adsorbent used here is usually in the range of 1 to 10 mm, preferably 2 to 4 mm, and the specific surface area is usually in the range of 50 to 500 m ² / g, preferably 200 to 500 m ² / g. .

When the cyclic olefin and the adsorbent are contacted in a batch system, the adsorbent is usually used in a ratio of 10 to 2000, preferably 20 to 1000, in weight (g) / volume (liter) ratio with respect to the volume 1 of the cyclic olefin. It is done. The contact time between the cyclic olefin and the adsorbent is usually 0.5.
-3 hours, preferably 0.5-2 hours, and the contact temperature is not particularly limited, but is usually 0-100 ° C, preferably 20-80 ° C. In this case, all or part of the adsorbent may be used repeatedly. In the case of repeated use, the adsorbent may be subjected to a regeneration operation such as heat treatment or washing with a polar solvent. When contacting the cyclic olefin and the inorganic compound, bubbling with nitrogen, stirring, or the like may be performed.
When contacting the cyclic olefin and the adsorbent in a continuous manner, a packed column is usually used. The contact time between the cyclic olefin and the adsorbent is usually 0.5 to 24 hours, preferably 0.5 to 4 hours, and the contact temperature is not particularly limited, but is usually 0 to 100 ° C, preferably 20 to 20 hours. It is in the range of 80 ° C.

  When the cyclic olefin and the adsorbent are brought into contact with each other, a hydrocarbon similar to the hydrocarbon medium used for the polymerization described later may coexist.

  After the cyclic olefin and the adsorbent are brought into contact with each other, the cyclic olefin and the adsorbent can be separated by a method such as filtration, sedimentation of the adsorbent and collection of a supernatant.

  The purified cyclic olefin obtained by subjecting the above-mentioned adsorbent contact treatment to the commercially available cyclic olefin is polymerized when used as a monomer for olefin polymerization rather than using the commercially available cyclic olefin as it is. Excellent activity. This is considered to be because impurities that affect the polymerization activity contained in the commercially available cyclic olefin can be removed.

(Antioxidant)
Examples of the antioxidant used in the present invention include phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants.

Examples of phenolic antioxidants include 2,6-di-tert-butyl-methylphenol, stearyl (3,3-dimethyl-4-hydroxybenzyl) thioglycolate,
Stearyl-β- (4-hydroxy-3,5-di-tert-butylphenol) propionate, distearyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,4,6-tris (3 ′ , 5'-di-tert-butyl-4'-hydroxybenzylthio) -1,3,5-triazine, distearyl (4-hydroxy-3-methyl-5-tert-butylbenzyl) malonate, 2,2 ' -Methylenebis (4-methyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) p-cresol ], Bis [3,5-bis [4-hydroxy-3-tert-butylphenyl] butyric acid] glycol ester, 4,4'-butyryl Denbis (6-tert-butyl-m-cresol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl- 6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butyl) benzyl isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, tetrakis [methylene-3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate] methane, 1,3,5-tris (3,5-di-)
tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl]
Isocyanurate, 2-octylthio-4,6-di (4-hydroxy-3,5-di-tert-butyl) phenoxy-1,3,5-triazine, 4,4′-thiobis (6-tert-butyl- m-cresol) and the like, and 4,4′-butylidenebis (2-tert-butyl-5-methylphenol) carbonic acid oligoesters (for example, polymerization degree 2 to 10) and the like, and polyhydric phenol carbonic acid oligoesters. It is done.

  Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl-, dimyristyl-, distearyl- and polyhydric alcohols of alkylthiopropionic acids such as butyl-, octyl-, lauryl-, stearyl- (for example, glycerin, And esters of trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) (for example, pentaerythritol tetralaurylthiopropionate).

Examples of phosphorus antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-diphenyl phosphite, and tris (2,4-
Di-tert-butylphenyl) phosphite, triphenyl phosphite, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) -1,1,3- tris (2-methyl -5-tert-butyl-4-hydroxyphenyl) butane diphosphite, tetra (C ₁₂ -C ₁₅ mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, tetra (tridecyl) - 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) diphosphite, tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite, tris (mono-dimixed nonylphenyl) phosphite , Hydrogenated-4,4′-isopropylidenedipheno Polyphosphite, bis (octylphenyl) .bis [4,4′-butylidenebis (3-methyl-6-tert-butylphenol)].
6-hexanediol diphosphite, phenyl 4,4'-isopropylidenediphenol pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6 -Di-tert-butyl-4-
Methylphenyl) pentaerythritol diphosphite, tris [4,4′-isopropylidenebis (2-tert-butylphenol)] phosphite, phenyl diisodecyl phosphite, di (nonylphenyl) pentaerythritol diphosphite), tris ( 1,3-di-stearoyloxyisopropyl) phosphite, 4,4′-isopropylidenebis (2-tert-butylphenol) di (nonylphenyl) phosphite, 9,
10-di-hydro-9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, etc. Is mentioned.

Furthermore, as other antioxidants, 6-hydroxychroman derivatives such as various tocopherols of α, β, γ, δ or mixtures thereof, 2- (4-methyl-pent-3-enyl) -6-hydroxychroman 2, 5-dimethyl substituted, 2,5,8-trimethyl substituted, 2,5,7,8-tetramethyl substituted, 2,2,7-trimethyl-5-tert-butyl-6-hydroxychroman, 2, 2,5-trimethyl-7-tert-butyl-6-hydroxychroman, 2,2,5-trimethyl-6-tert-butyl-6-hydroxychroman, 2,2
-Dimethyl-5-tert-butyl-6-hydroxychroman can also be used. Lactones such as a reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene can also be used.

  These antioxidants can be used alone or in combination of two or more.

  Among these, it is particularly preferable to use a phenol-based antioxidant or a phosphorus-based antioxidant. These antioxidants hardly inhibit the polymerization of the cyclic olefin, and the storage stability of the cyclic olefin composition is particularly excellent.

(Cyclic olefin composition)
The cyclic olefin composition according to the present invention contains the purified cyclic olefin and the antioxidant, and the antioxidant is contained in a proportion of 0.1 to 1000 ppm, preferably 1 to 100 ppm.

  The cyclic olefin composition containing the antioxidant in the above ratio is excellent in storage stability and has little decrease in polymerization activity even after being stored for a long period (for example, 140 days).

  The cyclic olefin composition according to the present invention can be prepared by mixing the purified cyclic olefin and the antioxidant and stirring as necessary. Although the temperature at the time of mixing is not specifically limited, Preferably it is the range of 10-60 degreeC.

  The cyclic olefin composition according to the present invention can also be prepared by adding the antioxidant to the cyclic olefin subjected to the alkali contact treatment and distilling the cyclic olefin composition. If the antioxidant is reduced by distillation, it may be further added.

(Method for producing cyclic olefin polymer)
In the method for producing a cyclic olefin polymer according to the present invention, the monomer composition containing the cyclic olefin composition as described above is subjected to polymerization using a polymerization catalyst.

The monomer composition containing the cyclic olefin composition may contain only the purified cyclic olefin and the antioxidant, the purified cyclic olefin and the antioxidant, the chain olefin, and the branched olefin. Or other olefins such as commercially available cyclic olefins.
Examples of chain olefins and branched olefins include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and 1-hexadecene. , 1-octadecene, 1-eicosene, etc., and an α-olefin having 2 to 20 carbon atoms. Of these, linear or branched α-olefins having 2 to 6 carbon atoms such as ethylene and propylene are preferable. Such olefin can be used individually by 1 type or in combination of 2 or more types.
In the present invention, a copolymerizable monomer other than the purified cyclic olefin and other olefins may be used as necessary within the range not impairing the object of the present invention.

Polymerization catalyst;
Examples of the polymerization catalyst used in the method for producing a cyclic olefin polymer according to the present invention include an olefin polymerization catalyst and a metathesis polymerization catalyst.

Examples of the olefin polymerization catalyst include a catalyst composed of a transition metal compound such as vanadium, zirconium, or titanium, and an organoaluminum compound (including an organoaluminum oxy compound) and / or an ionized ionic compound. Specifically, (i) a titanium-based catalyst composed of a solid titanium catalyst component and an organoaluminum compound, (ii) a vanadium-based catalyst composed of a soluble vanadium compound and an organoaluminum compound, and (iii) from Group 4 of the periodic table Examples thereof include metallocene catalysts composed of a metallocene compound of a transition metal selected, an organoaluminum oxy compound and / or an ionized ionic compound, and among these, a metallocene catalyst is particularly preferable.

Transition metal compounds;
The transition metal compound selected from Group 4 of the periodic table that forms the metallocene catalyst suitably used in the present invention is specifically represented by the following general formula (II).
MLx (II)
In the formula, M represents a transition metal selected from Group 4 of the periodic table, specifically zirconium, titanium or hafnium, and x is a number satisfying the valence of the transition metal.
L is a ligand coordinated to a transition metal, and at least one of these ligands L is a group (ligand) having a cyclopentadienyl skeleton and having this cyclopentadienyl skeleton. The ligand may have a substituent.

As a ligand having a cyclopentadienyl skeleton, for example,
A cyclopentadienyl group;
Methylcyclopentadienyl group, ethylcyclopentadienyl group, n-, i-propylcyclopentadienyl group, n-, i-, sec-, t-butylcyclopentadienyl group, hexylcyclopentadienyl group Octylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, methylethylcyclopentadienyl group, methylpropylcyclopenta Dienyl group, methylbutylcyclopentadienyl group, methylhexylcyclopentadienyl group, methylbenzylcyclopentadienyl group, ethylbutylcyclopentadienyl group, ethylhexylcyclopentadienyl group, methylcyclohexylcyclopentadienyl group Al Examples include a kill-substituted or cycloalkyl-substituted cyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, a fluorenyl group, and the like.
These ligands having a cyclopentadienyl skeleton may be further substituted with a halogen atom, a trialkylsilyl group or the like. Of these, an alkyl-substituted cyclopentadienyl group is particularly preferable.

  When the compound represented by the general formula (II) has two or more groups having a cyclopentadienyl skeleton as the ligand L, the groups having two cyclopentadienyl skeletons are ethylene, An alkylene group such as propylene; a substituted alkylene group such as isopropylidene and diphenylmethylene; a silylene group; a substituted silylene group such as dimethylsilylene, diphenylsilylene, and methylphenylsilylene may be bonded.

As L other than the ligand having a cyclopentadienyl skeleton, a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a sulfonic acid-containing group (—SO ₃ R ^a , where R ^a is An alkyl group, a halogen-substituted alkyl group, an aryl group, a halogen-substituted aryl group or an alkyl-substituted aryl group), a halogen atom or a hydrogen atom.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and the like.
Alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, octyl, decyl, dodecyl;
A cycloalkyl group such as a cyclopentyl group and a cyclohexyl group;
Aryl groups such as phenyl and tolyl;
Examples include aralkyl groups such as benzyl and neophyll.

  Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, pentoxy, hexoxy, octoxy and the like.

Examples of aryloxy groups include phenoxy,
Examples of the sulfonic acid-containing group (—SO ₃ R ^a ) include methane sulfonate, p-toluene sulfonate, trifluoromethane sulfonate, p-chlorobenzene sulfonate, and the like. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Examples of transition metal compounds including two ligands in which M is zirconium and has a cyclopentadienyl skeleton are shown below.
Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (1-methyl-3-butylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (1, 3-dimethylcyclopentadienyl) zirconium dichloride, ethylene-bis (indenyl) dimethylzirconium, ethylene-bis (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylene-bis (indenyl) zirconium Dichloride, methylphenylsilylene-bis (indenyl) zirconium dichloride, rac-ethylene-bis (2-methyl-1-indenyl) zirconium dichloride Lido, rac-dimethylsilylene-bis (2-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (4,7-dimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4 , 7-trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,6-trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (4-phenyl-1-indenyl) zirconium Dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (α-naphthyl) -1-indenyl) zirconium dichloride, rac-jime Tylsilylene-bis (2-methyl-4- (β-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (1-anthryl) -1-indenyl) zirconium dichloride, and the like.

Moreover, the transition metal compound which replaced the zirconium metal in the above compounds with the titanium metal and the hafnium metal can also be mentioned.
In the present invention, a compound represented by the following general formula (III) can also be used as the transition metal compound.
L ¹ M ¹ X ₂ (III)
In the formula, M ¹ represents a transition metal selected from Group 4 of the periodic table,
L ¹ is a derivative of a delocalized π bond group, and gives a constrained geometry to the metal M ¹ active site;
X is independently hydrogen, halogen, a hydrocarbon group containing 20 or less carbon, a silyl group containing 20 or less silicon, or a germanyl group containing 20 or less germanium.
Among such compounds represented by the general formula (III), a compound represented by the following general formula (IV) is preferable.

In the formula, M ¹ represents titanium, zirconium or hafnium, and X is the same as described above. Cp is a cyclopentadienyl group which has a π bond to M ¹ and may have a substituent.
Z is a ligand containing at least one element selected from oxygen, sulfur, boron, and an element belonging to Group 14 of the periodic table (for example, carbon, silicon, germanium, or tin).
Y is a ligand containing nitrogen, phosphorus, oxygen or sulfur.
Z and Y may form a condensed ring.

Specific examples of the compound represented by the general formula (IV) include [dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane] titanium dichloride, [(t
-Butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl]
Titanium dichloride, [dibenzyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane] titanium dichloride, [dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane] dibenzyl Titanium, [dimethyl (t-butylamide) (
Tetramethyl-η ⁵ -cyclopentadienyl) silane] dimethyl titanium, [(t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl] dibenzyl titanium, [(methylamide) ( Tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl] dineopentyl titanium, [(phenylphosphide) (tetramethyl-η ⁵ -cyclopentadienyl) methylene] diphenyl titanium, [dibenzyl (t -Butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) silane] dibenzyltitanium, [dimethyl (benzylamido) (η ⁵ -cyclopentadienyl) silane] di (trimethylsilyl) titanium, [dimethyl (phenylphosphide) ) (tetramethyl-eta ⁵ - cyclopentadienyl) silane] dibenzyl titanium, [(tetramethyl-eta ⁵ - cyclo Ntajieniru) -1,2-ethanediyl] dibenzyl titanium, [2-η ⁵ - (tetramethyl - cyclopentadienyl) -1-methyl - ethanolate (2-)] dibenzyl titanium, [2-η ⁵ - ( Tetramethyl-cyclopentadienyl) -1-methyl-ethanolate (2-)] dimethyltitanium, [2-((4a, 4b, 8a, 9,
9a-η) -9H-fluoren-9-yl) cyclohexanolate (2-)] dimethyltitanium, [2-((4a, 4b, 8a, 9,9a-η) -9H-fluoren-9-yl) And cyclohexanolate (2-)] dibenzyltitanium.

Moreover, the compound which replaced the titanium metal in the above compounds with the zirconium metal and the hafnium metal can also be mentioned.
These transition metal compounds can be used alone or in combination of two or more.

Organoaluminum oxy compounds;
The organoaluminum oxy compound forming the metallocene catalyst may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound (see JP-A-2-78687, etc.).
The conventionally known aluminoxane is specifically represented by the following general formula (i) or (ii).

(In the above general formula, R is a hydrocarbon group such as methyl, ethyl, propyl, butyl, etc., preferably methyl, ethyl, particularly preferably methyl, and m is an integer of 2 or more, preferably 5-40. .)
Here, the aluminoxane is an alkyloxyaluminum unit represented by the formula (OAl (R ¹¹ )) and an alkyloxyaluminum unit represented by the formula (OAl (R ¹² )) (where R ¹¹ and R ¹² are R And R ¹¹ and R ¹² each represent a different group, and may be formed from a mixed alkyloxyaluminum unit.

Ionized ionic compounds;
The ionized ionic compound that forms the metallocene catalyst reacts with the transition metal compound to form an ionic compound, or reacts with the reaction product of the transition metal compound and the following organoaluminum compound to form an ionic compound. Specifically, Lewis acids, ionic compounds and the like can be mentioned.

Examples of the Lewis acid include a compound represented by BR ¹³ ₃ (R ¹³ is a phenyl group or fluorine which may have a substituent such as fluorine, methyl, trifluoromethyl, etc.), for example, trifluoro Boron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) Examples include boron, tris (o-tolyl) boron, and tris (3,5-dimethylphenyl) boron.

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.
Specifically, examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p- Tolyl) boron, trimethylammonium tetra (o-tolyl) boron, tributylammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (m, m-dimethylphenyl) boron , Tributylammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron and the like.

  Examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N, 2,4,6-pentamethyl. Anilinium tetra (phenyl) boron etc. are mentioned.

  Examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Further examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate and the like.

Organoaluminum compounds;
The metallocene catalyst may contain an organoaluminum compound together with the organoaluminum oxy compound and / or the ionized ionic compound.
Such an organoaluminum compound is represented, for example, by the following general formula (V).
R ¹⁴ _n AlX ¹ _3-n (V)
In the formula, R ¹⁴ is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X ¹ is a halogen atom or a hydrogen atom, and n is 1 to 3.
Examples of the hydrocarbon group having 1 to 15 carbon atoms include an alkyl group, a cycloalkyl group, and an aryl group. Specifically, methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, Examples include octyl group, cyclopentyl, cyclohexyl, phenyl, tolyl and the like.

Specific examples of the organoaluminum compound include the following compounds.
Trialkylaluminiums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum;
Formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x.) Isoprenylaluminum represented by like Alkenylaluminum of
Trialkenyl aluminum such as triisopropenyl aluminum;
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide;
Alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide;
Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Alkyl aluminum dihydrides such as ethyl aluminum dihydride and propyl aluminum dihydride.

Polymerization conditions;
In the method for producing a cyclic olefin polymer according to the present invention, the monomer composition containing the purified cyclic olefin obtained by the above-described refinement method is subjected to polymerization using a polymerization catalyst. The amount of cyclic olefin used varies greatly between polyolefin polymerization and metathesis polymerization, but the larger the proportion of the purified cyclic olefin of the cyclic olefin used, the better. In addition, unreacted cyclic olefins used in the polymerization may be purified in the same manner and used again in the polymerization, or may be used in the polymerization again after omitting part or all of the purification. good.

As the polymerization method when the monomer composition is subjected to polymerization, a liquid phase polymerization method such as a suspension polymerization method or a solution polymerization method is usually employed.
Specific examples of the hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and hexadecane; cyclopentane, cyclohexane, methylcyclopentane, Cycloaliphatic hydrocarbons such as cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane; petroleum fractions such as gasoline, kerosene and light oil or mixtures thereof Etc. can be used. Furthermore, the olefin used for the polymerization can also be used as a hydrocarbon medium. Of these, aromatic hydrocarbons are preferred.

In carrying out the polymerization, the transition metal compound is usually 10 ⁻⁸ to 10 ⁻³ gram atom / liter (medium), preferably 10 ⁻⁷ to 10 ⁻⁴ gram atom / liter, as the concentration of the transition metal atom in the polymerization reaction system. Used in the amount of (medium).
In the organoaluminum oxy compound, the atomic ratio (Al / M) of aluminum (Al) in the organoaluminum oxy compound to the transition metal (M) in the transition metal compound is usually 10 to 10,000, preferably 20 to 5000. Is used in such an amount as to be in the range.

The ionized ionic compound is such that the molar ratio of the transition metal compound to the ionized ionic compound (transition metal compound / ionized ionic compound) is usually in the range of 0.01 to 10, preferably 0.1 to 5. Used in quantity.
Moreover, the organoaluminum compound used as needed includes an aluminum atom (Al ¹ ) in the organoaluminum compound and an aluminum atom (
Al ²⁾ and the atomic ratio of (Al ¹ / Al ²⁾ is usually 0.02 to 20, preferably from 0.2 to 10
Is used in such an amount as to be in the range.

  As a polymerization catalyst, a combination of a transition metal compound and an ionized ionic compound is particularly effective and is one of preferred embodiments.

  The temperature during the polymerization reaction is usually in the range of −50 to 230 ° C., preferably −30 to 200 ° C., and the polymerization pressure is usually normal pressure to 10 MPa, preferably normal pressure to 5 MPa. The polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods, and the polymerization can be carried out in two or more stages having different reaction conditions. The molecular weight of the resulting copolymer can be adjusted by hydrogen and / or polymerization temperature.

  In the present invention, the cyclic olefin polymer is obtained by treating the polymerization reaction mixture after the completion of the polymerization reaction by a conventional method. When producing a cyclic olefin polymer in the presence of a metallocene catalyst as described above, a cyclic olefin polymer can be produced with high polymerization activity by using a monomer composition containing a purified cyclic olefin. . This is considered to be because impurities that adversely affect the polymerization contained in the cyclic olefin can be removed by subjecting the cyclic olefin to alkali contact treatment and distillation, or inorganic compound contact treatment.

In the obtained cyclic olefin polymer, the repeating unit derived from the cyclic olefin is usually 0.1% by weight or more, preferably 1 to 90% by weight, more preferably 1 to 70% by weight. Further, the repeating unit derived from a monomer other than the cyclic olefin, such as a chain or branched α-olefin, is usually 99.9% by weight or less, preferably 10 to 99% by weight, more preferably 30 to 99% by weight. It is in.
The intrinsic viscosity [η] of the cyclic olefin polymer measured in decalin at 135 ° C. is usually in the range of 0.005 to 20 dl / g, preferably 0.01 to 10 dl / g.

Metathesis catalyst;
The (a) transition metal compound catalyst component used in the metathesis polymerization is a compound of a transition metal of Group 4, 5, 6, 7, 8, 9 or 10 of the periodic table, and halides and oxyhalides of these transition metals. , Alkoxy halides, alkoxides, carboxylates, (oxy) acetylacetonates, carbonyl complexes, acetonitrile complexes, hydride complexes, derivatives thereof, complexing agents such as P (C ₅ H ₆ ) _{5 of} these or these derivatives And complexed products.

Specifically, TiCl ₄ , TiBr ₄ , VOBr ₃ , WBr ₄ , WBr ₆ , WCl ₂ , WCl
₄ , WCl ₅ , WCl ₆ , WF ₄ , WI ₂ , WOCl ₄ , MoBr ₂ , MoBr ₃ , MoBr ₄ ,
MoCl ₄ , MoCl ₄ , MoF ₄ , MoOCl ₄ , WO ₂ , H ₂ WO ₄ , NaWO ₄ , K ₂ WO ₄ , (HN ₄ ) ₂ WO ₄ , CaWO ₄ , CuWO ₄ , MgWO ₄ , (CO) ₅ WC (OC ₂ H ₅ ) (
CH ₃ ), (CO) ₅ WC (OC ₂ H ₅ ) (C ₄ H ₅ ), tridecyl ammonium molybdate, tridecyl ammonium tungstate and the like are exemplified. In practical terms, W, Mo, Ti or V compounds are preferred from the standpoint of polymerization activity and the like, and these halides, oxyhalides or alkoxyhalides are particularly preferred.

  (B) The metal compound promoter component used in the metathesis polymerization catalyst is a compound of a metal of Group 1, 2, 12, 13 or 14 of the periodic table and has at least one metal element-carbon bond or metal element-hydrogen bond Examples thereof include organic compounds such as Al, Sn, Li, Na, Mg, Zn, Cd, and B.

Specifically, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, triisobutylaluminum, triphenylaluminum, diethylaluminum monochloride, di-n-propylaluminum monochloride, diethylaluminum monobromide, diethyl Organoaluminum compounds such as aluminum monoiodide, diethylaluminum monohydride, di-n-propylaluminum monohydride, diisobutylaluminum monohydride, methylaluminum sesquichloride, ethylaluminum dichloride, isobutylaluminum dichloride;
Organotin compounds such as tetramethyltin, diethyldimethyltin, tetraethyltin, dibutyldiethyltin, tetrabutyltin;
organolithium compounds such as n-butyllithium;
organic sodium compounds such as n-pentyl sodium;
Organomagnesium compounds such as methylmagnesium iodide, ethylmagnesium bromide, t-butylmagnesium chloride, allylmagnesium chloride;
Organozinc compounds such as diethylzinc;
Organic cadmium compounds such as diethyl cadmium;
Organoboron compounds such as trimethylboron;

  A metathesis polymerization activity can be enhanced by adding a third component in addition to the component (a) and the component (b). Such tertiary components include aliphatic tertiary amines, aromatic tertiary amines, molecular oxygen, alcohols, ethers, peroxides, carboxylic acids, acid anhydrides, acid chlorides, esters, ketones, Examples thereof include nitrogen compounds, sulfur-containing compounds, halogen-containing compounds, molecular iodine, and other Lewis acids. Among them, aliphatic or aromatic tertiary amines are preferable, and specific examples thereof include triethylamine, dimethylaniline, tri-n-butylamine, pyridine, α-picoline and the like.

  In addition, a compound containing an OH group, such as an alcohol, functions as an inactivating agent that inhibits metathesis polymerization activity when added in excess of the stoichiometric amount, so it is necessary to add less than the stoichiometric amount. . Here, the stoichiometric amount is the product of the number of moles of the component (a) and the oxidation number of the transition metal contained in the component (a) per molecule of the chemical containing the OH group. It refers to the number of moles represented by a numerical value divided by the number of OH groups.

The quantitative relationship of these components is 1 mol or more, preferably 2 mol or more, 100 mol or less, preferably 50 mol or less, and usually (1 mol) of the metal element (b) with respect to 1 mol of the metal element (a). a) The third component is used in an amount of 0.005 mol or more, preferably 0.05 mol or more and 10 mol or less, preferably 3 mol or less with respect to 1 mol of the component. If the amount of the component (b) is too small relative to the component (a), sufficient activity cannot be obtained with respect to the amount of the component (a). If the amount is too large, it becomes difficult to remove the excessive component (b) It becomes high. When the amount of the third component is too small relative to the component (a), the effect of adding the third component is small, and when the amount is too large, it is difficult to remove the excessive third component or the cost is increased.

  Metathesis polymerization is usually carried out in an inert organic solvent. The solvent to be used is not particularly limited as long as it is a polymerization-inert organic solvent, and examples thereof include hydrocarbons used for polymerization using the metallocene catalyst.

  The purified monomer composition containing a cyclic olefin is 3 parts by weight or more, preferably 5 parts by weight or more, more preferably 10 parts by weight or more and 50 parts by weight or less, preferably 40 parts by weight with respect to 100 parts by weight of the solvent. In the following, more preferably in the range of 35 parts by weight or less, the metathesis polymerization catalyst is 0.001 mol or more, preferably 0.005 with respect to 100 mol of the monomer composition containing the purified cyclic olefin as component (a). It is added in a range of not less than mol, more preferably not less than 0.01 mol and not more than 10 mol, preferably not more than 5 mol, more preferably not more than 2 mol.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

(Alkaline contact treatment)
150 ml of 5-ethylidene-2-norbornene (manufactured by San Petrochemical; Lot
3B02, hereinafter abbreviated as “ENB”. ) And 50 ml of 0.1N NaOH water,
The operation of stirring for a minute and then separating was repeated three times. Next, the operation of mixing ENB brought into contact with NaOH water and 50 ml of ion-exchanged water, stirring for 5 minutes and separating the mixture was repeated three times to obtain 140 ml of ENB (1) subjected to alkali contact treatment.

(Input of antioxidant)
Immediately thereafter, 50 g of ENB (1) was purged with nitrogen in advance and charged into a 100 ml branch flask containing 5.0 mg of 2,6-di-tert-butyl-methylphenol and a rotor. Immediately after the addition, the mixture was stirred with a stirrer for 30 minutes to obtain an ENB composition (2).

(Polymerization 1)
In a 2 liter stainless steel autoclave at 23 ° C. sufficiently purged with nitrogen, 884 ml of heptane from which impurities have been removed and 16 ml of the above-mentioned ENB composition (2), which has passed one day after the addition of 2,6-di-tert-butyl-methylphenol Was charged. Next, 17 N-liter of propylene was charged into this autoclave, heated to 80 ° C., and when it reached 80 ° C., it was pressurized with ethylene so that the total pressure became 0.8 MPa. Next, 0.2 mmol of triisobutylaluminum was first injected, followed by 0.01 mmol / ml of [dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane] titanium dichloride in hexane. 0.1 ml (0.001 mmol) and 1.0 ml (0.002 mol / ml) of a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (Asahi Glass Co., Ltd.) were individually injected. After press-fitting triphenylcarbenium tetrakis (pentafluorophenyl) borate, copolymerization was carried out for 20 minutes. During the polymerization, the pressure was maintained immediately after injection by ethylene pressurization, and the temperature was maintained at 80 ° C. After 20 minutes, 3 ml of methanol was pressed into the autoclave with nitrogen to stop the polymerization. As a result, 47 g of an ethylene / propylene / ENB copolymer having an ethylene content of 62 mol%, an iodine value of 25 g / 100 g, and an intrinsic viscosity of 3.0 dl / g was obtained.

(Polymerization 2)
Except for using the ENB composition (2) 140 days after the addition of 2,6-di-tert-butyl-methylphenol as the ENB composition, ethylene, propylene and ENB were co-polymerized in the same manner as in the above polymerization 1. Polymerized. As a result, 47 g of an ethylene / propylene / ENB copolymer having an ethylene content of 62 mol%, an iodine value of 25 g / 100 g, and an intrinsic viscosity of 3.0 dl / g was obtained.

(Alkaline contact treatment)
The operation of mixing 150 ml of ENB and 50 ml of 0.1N NaOH aqueous solution, stirring for 5 minutes and then separating was repeated 3 times. Next, ENB (3) subjected to alkali contact treatment was obtained by mixing the ENB in contact with the NaOH water and 50 ml of ion-exchanged water, stirring for 5 minutes and then separating the mixture three times. This operation was performed three times to obtain 430 ml of ENB (3) subjected to alkali contact treatment.

(distillation)
The day after the alkali contact treatment, ENB (3) was distilled using a batch distillation apparatus having 15 stages of Oldersho. 270 g of ENB (3) was put in, and heating was started at a top pressure = 10.6 KPa. First, 27 g of distillate was discarded at rr = 10. Thereafter, rr was set to 3 and distillation was carried out until the residue in the kettle became 54 g to obtain 189 g of ENB (4).

(Input of antioxidant)
Immediately thereafter, 50 g of ENB (4) was purged with nitrogen in advance and charged into a 100 ml branch flask containing 5.0 mg of 2,6-di-tert-butyl-methylphenol and a rotor. Immediately after the addition, the mixture was stirred with a stirrer for 30 minutes to obtain an ENB composition (5).

(Polymerization 1)
In the same manner as in Polymerization 1 of Example 1, except that the ENB composition (5) that had passed 1 day after the addition of 2,6-di-tert-butyl-methylphenol was used instead of the ENB composition (2). Then, ethylene, propylene and ENB were copolymerized. As a result, 57 g of an ethylene / propylene / ENB copolymer having an ethylene content of 64 mol%, an iodine value of 23 g / 100 g, and an intrinsic viscosity of 3.2 dl / g was obtained.

(Polymerization 2)
Instead of the ENB composition (2), the same ENB composition (5) as 140 days after 2,6-di-tert-butyl-methylphenol was added was used, and the same as in Polymerization 1 of Example 1 Then, ethylene, propylene and ENB were copolymerized. As a result, 57 g of an ethylene / propylene / ENB copolymer having an ethylene content of 63 mol%, an iodine value of 23 g / 100 g, and an intrinsic viscosity of 3.2 dl / g was obtained.

[Comparative Example 1]
(Polymerization 1)
Instead of the ENB composition (2), ethylene, propylene, and ENB were copolymerized in the same manner as in the polymerization 1 of Example 1 except that the ENB (1) that had passed one day after the alkali contact treatment was used. As a result, 47 g of an ethylene / propylene / ENB copolymer having an ethylene content of 62 mol%, an iodine value of 25 g / 100 g, and an intrinsic viscosity of 3.0 dl / g was obtained.

(Polymerization 2)
Instead of the ENB composition (2), ethylene, propylene and ENB were copolymerized in the same manner as in the polymerization 1 of Example 1 except that the ENB (1) 140 days after the alkali contact treatment was used. As a result, 28 g of an ethylene / propylene / ENB copolymer having an ethylene content of 57 mol%, an iodine value of 26 g / 100 g, and an intrinsic viscosity of 2.7 dl / g was obtained.

[Comparative Example 2]
(Polymerization 1)
Instead of the ENB composition (2), ethylene, propylene, and ENB were copolymerized in the same manner as in the polymerization 1 of Example 1 except that the ENB (4) that had passed one day after distillation was used. As a result, 57 g of an ethylene / propylene / ENB copolymer having an ethylene content of 64 mol%, an iodine value of 23 g / 100 g, and an intrinsic viscosity of 3.2 dl / g was obtained.

(Polymerization 2)
Instead of the ENB composition (2), ethylene, propylene and ENB were copolymerized in the same manner as in the polymerization 1 of Example 1 except that the ENB (4) 140 days after the alkali contact treatment was used. As a result, 30 g of an ethylene / propylene / ENB copolymer having an ethylene content of 59 mol%, an iodine value of 26 g / 100 g and an intrinsic viscosity of 2.8 dl / g was obtained.

Claims (11)

  A cyclic olefin composition comprising a purified cyclic olefin obtained by bringing a cyclic olefin into contact with an alkali and an antioxidant.   A cyclic olefin composition comprising a purified cyclic olefin obtained by contacting a cyclic olefin with an alkali and then removing light and / or high boiling content, and an antioxidant. .   The purified cyclic olefin is obtained by removing 0.05% by weight or more of light boiling or high boiling content based on the weight of the cyclic olefin before distillation after contacting with alkali. The cyclic olefin composition according to claim 2, wherein the composition is a cyclic olefin composition.   The purified cyclic olefin was obtained by contacting with alkali and removing 0.05% by weight or more of light and high-boiling components based on the weight of the cyclic olefin before distillation. The cyclic olefin composition according to claim 2.   A cyclic olefin composition comprising a purified cyclic olefin obtained by bringing a cyclic olefin into contact with an adsorbent and an antioxidant.   The cyclic olefin composition according to any one of claims 1 to 5, wherein the antioxidant is a phenol-based antioxidant or a phosphorus-based antioxidant.   The cyclic olefin composition according to any one of claims 1 to 6, wherein the antioxidant is contained in a proportion of 0.1 to 1000 ppm with respect to the total amount of the cyclic olefin and the antioxidant. .   A method for producing a cyclic olefin polymer, comprising subjecting the monomer composition containing the cyclic olefin composition according to any one of claims 1 to 7 to polymerization using a polymerization catalyst.   The monomer contained in the monomer composition is composed of the purified cyclic olefin according to any one of claims 1 to 5 and other olefins. The manufacturing method of the cyclic olefin polymer of description.   The method for producing a cyclic olefin polymer according to claim 8 or 9, wherein the polymerization catalyst is an olefin polymerization catalyst.   The said olefin polymerization catalyst contains an organoaluminum oxy compound or an ionized ionic compound as a catalyst component, The manufacturing method of the cyclic olefin type polymer of Claim 10 characterized by the above-mentioned.