JPH04353518A - Production of cyclic olefin polymer - Google Patents

Abstract

PURPOSE:To produce a cyclic olefin polymer suitable for optical applications by bringing a polymer comprising a specific cyclic olefin random copolymer or a cyclic olefin ring-opened polymer into contact with a specific solvent mixture. CONSTITUTION:(A) A cyclic olefin random copolymer produced by copolymerizing (i) ethylene with (ii) a cyclic olefin of formula I (n, r are 0, 1; m is 0, positive integer; R<1> to R<18>, R<a>, R<b> are H, halogen; hydrocarbon) and/or formula II (p,q are >=0; m, n are 0-2; R<1> to R<19> are H, halogen, aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, alkoxy), or (B) a cyclic olefin ring-opened polymer (hydrogenated product) produced by ring opening- polymerization of the cyclic olefin of the component ii is brought into contact with a solvent mixture comprising a poor solvent and a good solvent for the olefinic polymer in a volume ratio of 95/5 to 80/20 to produce the objective polymer.

Description

[Detailed description of the invention]

The present invention relates to a method for producing a cyclic olefin polymer. More specifically, the present invention provides transparency,
A method for producing a cyclic olefin polymer that has excellent heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and various mechanical properties and is substantially free of oligomers formed from ethylene and/or cyclic olefins. Regarding.

0002

[Technical Background of the Invention] A cyclic olefin-based random copolymer consisting of ethylene and a specific noble cyclic olefin is a synthetic resin with well-balanced optical properties, mechanical properties, and thermal properties, and has an optical memory. It is disclosed in the international application WO 89/01950 or Japanese Patent Application Laid-open No. 1-185307 that it can be used for applications in the field of optical materials such as disks and optical fibers. Furthermore, the cyclic olefin ring-opening polymer obtained by ring-opening (co)polymerizing this noble cyclic olefin is also a well-balanced synthetic resin.

Although such cyclic olefin polymers (namely, the above-mentioned cyclic olefin random copolymers and cyclic olefin ring-opening polymers) have excellent properties as described above, the present invention According to research conducted by researchers, it contains a small amount of oligomers consisting of ethylene and/or cyclic olefins. By thermoforming this cyclic olefin polymer, it is possible to produce a molded article in a desired shape, but this cyclic olefin polymer has a significantly higher softening temperature than ordinary olefin polymers. It has been found that even if this cyclic olefin polymer contains a small amount of oligomer, stains thought to be caused by the oligomer may adhere to the mold during repeated use of the molding machine.

[0004] When cyclic olefin polymers are used for applications in the field of optical materials such as optical memory disks or optical fibers, the properties of the products are significantly degraded by the slightest amount of foreign matter mixed into these optical products. There is a need for an improvement in the method for producing a cyclic olefin polymer that can produce a cyclic olefin polymer substantially free of oligomers composed of ethylene and/or cyclic olefins.

[0005]

[Object of the Invention] The present invention has been made in view of the above points, and includes improvements in transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and various mechanical properties. It is an object of the present invention to provide a method for producing a cyclic olefin polymer which has excellent properties and is substantially free of oligomers formed from ethylene and/or cyclic olefins.

[0006]

Summary of the Invention The method for producing a cyclic olefin random copolymer according to the present invention comprises (a) ethylene and (b) at least one cyclic olefin represented by the following formula [I] and/or [II]. Cyclic olefin random copolymer prepared by copolymerizing or (b
) Consists of a cyclic olefin-based ring-opening polymer prepared by ring-opening polymerization of at least one cyclic olefin represented by the following formula [I] and/or [II] or a hydrogenated product of the ring-opening polymer. A mixed solvent containing a cyclic olefin polymer, (A) a voracious solvent for the cyclic olefin polymer, and (B) a good solvent for the cyclic olefin polymer at a volume ratio within the range of 97/3 to 75/25. It is characterized by making contact with

[0007]

[Chemical formula 3]

... [I] However, in the above formula [I], n is 0 or 1, m is 0 or a positive integer, r is 0 or 1, R1 to R18 and Ra, Rb is each independently,
A hydrogen atom, a halogen atom, or a hydrocarbon group, and R1
5 to R18 may be combined with each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond, or R15 and R16, or R1
7 and R18 may form an alkylidene group.

[0009]

[C4]

... [II] However, in formula [II], p and q are 0 or 1
or more, m and n are 0, 1, or 2, and R1 to R19 are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and Represents an atom or group selected from the group consisting of alkoxy groups, R9 and R13 or R10 and R11
may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when n=m=0, R15 and R12 or R15 and R19 may be bonded to each other to form a monocyclic or polycyclic ring. It may form an aromatic ring.

As described above, by treating a cyclic olefin polymer with a mixed solvent in which a poor solvent and a good solvent are mixed in a specific ratio, oligomers contained in this polymer can be efficiently removed. This treatment does not substantially reduce the yield of the cyclic olefin polymer. Since the cyclic olefin polymer thus obtained does not substantially contain oligomers, mold staining can be reduced by thermoforming using this polymer.

0012

[Detailed Description of the Invention] Next, the present invention will be described in detail. The cyclic olefin polymers used in the present invention include cyclic olefin random copolymers, cyclic olefin ring-opening polymers, and hydrogenated products thereof.

First, the cyclic olefin random copolymer of the present invention will be explained. The cyclic olefin random copolymer used in the present invention can be produced by copolymerizing ethylene and the cyclic olefins represented by formula [I] and/or formula [II].

[0014]

[C5]

[I] However, in the above formula [I], n is 0 or 1, m is 0 or a positive integer, and r is 0 or 1. Note that when r is 0, the bond defined by r is a single bond, and therefore the ring formed here is a 5-membered ring.

In addition, in the above formula [I], R1 to R1
8, Ra and Rb each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group include, each independently, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 3 to 15 carbon atoms. Specific examples of alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, amyl group,
Specific examples of halogenated alkyl include hexyl, octyl, decyl, dodecyl, and octadecyl groups, and specific examples of halogenated alkyl include the above-mentioned alkyl groups in which at least some of the hydrogen atoms forming the alkyl group are fluorine. Mention may be made of groups substituted with atoms, chlorine atoms, bromine atoms or iodine atoms. Moreover, a cyclohexyl group can be mentioned as a specific example of the cycloalkyl group, and this group may have a lower alkyl group. Furthermore, in the above formula [I], R15 and R16 are R17 and R
18, further R15 and R17, R16 and R18
, R15 and R18, or R16 and R17 may each be combined (jointly with each other) to form a monocyclic or polycyclic group, and A monocyclic or polycyclic group may have a double bond.

[0017] Furthermore, R15 and R16 or R17
and R18 may form an alkylidene group. Such alkylidene groups usually have 2 to 20 carbon atoms.
is an alkylidene group, and specific examples of such alkylidene groups include ethylidene group, propylidene group, and isopropylidene group.

[0018]

[C6]

[II] However, in formula [II], p and q are 0 or an integer of 1 or more, and m and n are 0, 1 or 2.

Furthermore, R1 to R19 each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and an alkoxy group. . Here, R9 and R
13 or R10 and R11 are direct or have a carbon number of 1 to
It may be bonded via the alkylene group of 3. Also,
When n=m=0, R15 and R12 or R15 and R19
may be bonded to each other to form a monocyclic or polycyclic aromatic ring.

Here, the halogen atom has the same meaning as the halogen atom in the above formula [I]. Moreover, the aliphatic hydrocarbon group here is an alkyl group having 1 to 20 carbon atoms or a halogenated alkyl group having 1 to 20 carbon atoms. Specific examples of alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group, and octadecyl group, and specific examples of halogenated alkyl groups include Examples include groups in which at least some of the hydrogen atoms forming the alkyl group as described above are substituted with fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms. Further, specific examples of alicyclic hydrocarbon groups include cyclohexyl groups, and specific examples of aromatic hydrocarbon groups include phenyl groups, naphthyl groups, anthracenyl groups, and phenanthrenyl groups. and these groups may have a lower alkyl group.

Specific examples of such cyclic olefins include the following derivatives.

[0023]

[C7]

[0024]

[Chemical formula 8]

[0025]

[Chemical formula 9]

[0026]

[Chemical formula 10]

[0027]

[Chemical formula 11]

[0028]

[Chemical formula 12]

[0029]

[Chemical formula 13]

[0030]

[Chemical formula 14]

[0031]

[Chemical formula 15]

[0032]

[Chemical formula 16]

[0033]

[Chemical formula 17]

[0034]

[Chemical formula 18]

[0035]

[Chemical formula 19]

[0036]

[C20]

[0037]

[C21]

[0038]

[C22]

[0039]

[C23]

[0040]

[C24]

[0041]

[C25]

[0042]

[C26]

[0043]

[C27]

[0044]

[C28]

[0045]

[C29]

The cyclic olefin represented by the above formula [I] or [II] can be easily produced by subjecting cyclopentadiene and the corresponding olefin to a Diels-Alder reaction.

In the present invention, the cyclic olefin random copolymer is an addition polymer of a cyclic olefin represented by the above formula [I] or formula [II] and ethylene. In this cyclic olefin random copolymer, the repeating unit derived from ethylene/repeating unit derived from cyclic olefin is usually 10/90 to 95/
5, preferably in a molar ratio within the range of 50/50 to 90/10.

The cyclic olefin-based random copolymer can be produced, for example, by polymerizing ethylene and a cyclic olefin in a hydrocarbon medium in the presence of a catalyst formed from a hydrocarbon-soluble vanadium compound and a halogen-containing organoaluminum compound. It can be manufactured by

Such a polymerization method is already known,
This method has been proposed in Japanese Patent Application Laid-Open No. 60-168708. In such a cyclic olefin random copolymer, for example, at least a part of the cyclic olefin represented by the above formula [I] has a structure represented by the following formula [I-A] and is derived from ethylene. It is thought that they are randomly bonded to repeating units.

[0050]

[C30]

...[IA] However, in the above formula [IA], R1 to R18, R
a and Rb and r, m and n have the same meanings as in formula [I].

[0052] It is also believed that the cyclic olefin represented by formula [II] has a structure equivalent to the structure represented by formula [I-A] above, and is randomly bonded to repeating units derived from ethylene. It will be done.

In the cyclic olefin random copolymer, repeating units derived from ethylene and repeating units derived from cyclic olefin are arranged randomly and substantially linearly. The fact that this cyclic olefin random copolymer is substantially linear and has no gel-like crosslinks means that this copolymer has 135
This can be confirmed by complete dissolution in decalin at °C.

In the cyclic olefin random copolymer used in the present invention, in addition to the cyclic olefin component and the ethylene component, α
- It is also possible to use a polymer obtained by adding and polymerizing an olefin (third monomer) or a cyclic olefin (other cyclic olefin) other than the cyclic olefin represented by the above formula [I] or [II]. .

The α-olefin used here may be a linear α-olefin or a branched α-olefin, and examples of such α-olefins include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-
Dodecene, 1-tetradecene, 1-hexadecene, 1-
Mention may be made of α-olefins having 3 to 20 carbon atoms, such as octadecene and 1-eicosene. Among these, α- having 3 to 15 carbon atoms, especially 3 to 10 carbon atoms;
Preference is given to using olefins.

[0056] "Other cyclic olefins" as used herein has a broad concept including unsaturated polycyclic hydrocarbon compounds other than the cyclic olefins represented by formulas [I] and [II].

More specifically, examples of other cyclic olefins include cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, styrene, α-methylstyrene and 3a,
5,6,7a-tetrahydro-4,7-methano-1H-
Examples include indene. In addition, when other cyclic olefins have two or more double bonds in the molecule, in order to improve weather resistance, the remaining double bonds in the copolymer without being used in addition polymerization are Bonds can also be hydrogenated.

For example, by carrying out addition polymerization as described above and hydrogenation if necessary, the iodine number of the cyclic olefin random copolymer used in the present invention is usually 5 or less, and most of them are 1 or less. It can be done.

In the cyclic olefin random copolymer, the fact that the cyclic olefin used as a raw material has a structure represented by the above formula [I-A] means that the 13C-NMR of the cyclic olefin random copolymer This can be confirmed from the measurement results. Such a cyclic olefin random copolymer has a chemically stable structure and is a polymer with excellent heat aging resistance.

The intrinsic viscosity [η
] is within the range of 0.01 to 5 dl/g. In the present invention, the intrinsic viscosity [η] is particularly 0.05 to 4.
It is preferable to use a cyclic olefin random copolymer having a dl/g range.

[0061] These cyclic olefin random copolymers are generally amorphous or have low crystallinity, and by using particularly amorphous cyclic olefin random copolymers, the molded product obtained can be It has good transparency. When the crystallinity of this cyclic olefin random copolymer is measured using X-rays, specifically,
The degree of crystallinity of these cyclic olefin random copolymers is usually in the range of 0 to 10%, preferably 0 to 7%, particularly preferably 0 to 5%.

The glass transition temperature (Tg) of such a cyclic olefin random copolymer by DSC is usually in the range of -50 to 280°C, and in most cases -40 to 250°C.
Observed within the range of °C.

[0063] The thermal decomposition temperature is usually 350 to 420
°C, mostly within the range of 370 to 400 °C. The density is
Usually 0.86-1.10g/cm3, most of which are 0.
．． It is in the range of 88 to 1.08 g/cm3. The refractive index (ASTM D542) is usually 1.47 to 1.5.
8. Many of them are within the range of 1.48 to 1.56, and since they are substantially amorphous, the haze (Haze: ASTM D100)
3) is usually 20% or less, often 10% or less.

As for electrical properties, the dielectric constant (1KHz) measured by ASTM D150 is usually 1.5 to 3.0.
, mostly 1.9 to 2.6, and the dielectric loss tangent is usually 9×1
0-4 to 8×10-5, mostly 3×10-4 to 9×10
It is within the range of -5.

[0065] Next, the cyclic olefin ring-opening polymer treated as a cyclic olefin polymer in the present invention and its hydrogenated product will be explained. The cyclic olefin ring-opening polymer used in the present invention has the above formula [I] and/or [I
A ring-opened ring formed from a cyclic olefin represented by I] (
It is a co)polymer and/or a hydrogenated ring-opened (co)polymer formed by hydrogenating it.

The ring-opening polymer used in the present invention can be prepared by ring-opening polymerization of the above-mentioned cyclic olefins alone or in combination. That is, a ring-opening polymer is prepared by carrying out ring-opening polymerization of a cyclic olefin represented by the above formula [I] and/or [II] in the presence of a ring-opening polymerization catalyst. Examples of ring-opening polymerization catalysts used here include halides of metals such as ruthenium, rhodium, osmium, indium, platinum, molybdenum, and tungsten, nitrates of these metals, acetylacetone compounds of these metals, and alcohols. Alternatively, catalysts comprising a reducing agent such as a tin compound, halogen compounds of metals such as titanium, vanadium, zirconium, tungsten and molybdenum, acetylacetone of these metals, and metal aluminum compounds can be mentioned.

[0067] In preparing the above ring-opening polymer, in addition to the cyclic olefin represented by the above formula [I] or formula [II], additional additives may be added within a range that does not impair the properties of the cyclic olefin resin. Other cyclic olefins can be used.

Examples of other cyclic olefins that can be used here include cyclobutene, cyclopentene,
Cyclooctene, cyclononene, methylcyclopentene, methylcycloheptene, methylcyclooctene, methylcyclononene, methylcyclodecene, ethylcyclopentene, ethylcycloheptene, ethylcyclooctene, ethylcyclononene, dimethylcycloheptene, dimethylcyclooctene, Mention may be made of mononuclear olefins having 4 or more carbon atoms, such as dimethylcyclononene, dimethylcyclodecene, cyclooctadiene and cyclodecadiene. Moreover, as a molecular weight regulator, alkenes such as propylene, 1-butene, 1-pentene, and 1-hexene can be used as a copolymerization component.

In such a ring-opened polymer, at least a portion of the cyclic olefin represented by the above formula [I] is considered to have a structure represented by the following formula [I-B].

[0070]

[Chemical formula 31]

... [I-B] However, in the above formula [I-B], R1 to R18, R
a and Rb and r, m and n have the same meanings as in formula [I].

[0072] The cyclic olefin represented by formula [II] is also considered to have a structure equivalent to the structure represented by formula [IB] above. In the present invention, the intrinsic viscosity [η] measured in decalin at 130°C is 0.
．． 05-10dl/g, preferably 0.08-5dl/
Ring-opened polymers within the range of g are used.

Further, the glass transition temperature (Tg) of this ring-opened polymer as measured by DSC is usually in the range of -50 to 280°C, and in most cases -40 to 250°C. Furthermore, the crystallinity of this ring-opened polymer measured by X-ray diffraction is usually 0 to 10%, preferably 0 to 7%, particularly preferably 0 to 7%.
It is within the range of 5%.

The hydrogenated ring-opening polymer used in the present invention can be obtained by hydrogenating the cyclic olefin ring-opening polymer prepared as described above. For hydrogenation of the ring-opened polymer, a conventional hydrogenation method performed in the presence of a hydrogenation catalyst can be employed.

[0075] The hydrogenation catalyst used here is:
Hydrogenation catalysts such as heterogeneous catalysts or homogeneous catalysts that are commonly used in the hydrogenation of olefin compounds can be used. Specific examples of heterogeneous catalysts include metals such as nickel, palladium and platinum, and solid catalysts (e.g. , nickel/silica, nickel/diatomaceous earth, palladium/carbon, palladium/silica,
palladium/diatomaceous earth, palladium/alumina, etc.). Further, examples of homogeneous catalysts include catalysts based on metals of group VIII of the periodic table; examples of such catalysts include cobalt naphthenate/triethylaluminum, cobalt octenoate/n-butyllithium, Examples include organometallic compounds formed from nickel compounds such as nickel acetylacetonate/triethylaluminum or cobalt compounds and metals from groups I to III of the periodic table, and Rh compounds can also be used.

The hydrogenation reaction using the hydrogenation catalyst as described above can be carried out in either a heterogeneous system or a homogeneous system depending on the type of catalyst. The reaction conditions in such a system are usually set at a temperature of 0 to 180°C, preferably 20 to 100°C, under hydrogen pressure of 1 to 150 atmospheres. The hydrogenation rate under these conditions can be adjusted by appropriately setting conditions such as hydrogen pressure, reaction temperature, reaction time, and catalyst concentration. Usually, 50% or more, preferably 80% or more, and more preferably 90% or more is hydrogenated.

In such a hydrogenated ring-opening polymer,
For example, at least a portion of the cyclic olefin represented by the above formula [I] is considered to have a structure represented by the following formula [I-C].

[0078]

[C32]

...[I-C] However, in the above formula [I-C], R1 to R18, R
a and Rb and r, m and n have the same meanings as in formula [I].

Further, the cyclic olefin represented by formula [II] is also considered to have a structure equivalent to the structure represented by formula [I-C] above. In the present invention, the intrinsic viscosity [η] measured in decalin at 130°C is 0.
．． 05-10dl/g, preferably 0.08-5dl/
Hydrogenated ring-opened polymers within the range of g are used.

Further, the glass transition temperature (Tg) of this hydrogenated ring-opening polymer by DSC is usually -50 to 280°C,
In most cases, it is within the range of -40 to 250°C. moreover,
The degree of crystallinity of this hydrogenated ring-opening polymer measured by X-ray diffraction is usually in the range of 0 to 10%, preferably 0 to 7%, particularly preferably 0 to 5%.

[0082] In the method of the present invention, the above-mentioned cyclic olefin random copolymers, ring-opening polymers, and hydrogenated ring-opening polymers may be used alone as the cyclic olefin polymer. It is also possible to use mixtures (compositions) of these.

When the cyclic olefin polymer obtained as described above is dissolved or dispersed in the reaction solvent, alcohol or the like is added to the reaction solution containing the cyclic olefin polymer to precipitate the polymer. After that, the catalyst is usually removed (deashed), and if necessary, the catalyst is washed and dried.

The cyclic olefin polymer thus obtained contains an oligomer component in a proportion of about 1% by weight or less in most cases. In the method of the present invention, such a cyclic olefin polymer is brought into contact with a mixed solvent in which (A) a phagocytic solvent for the polymer and (B) a good solvent for the polymer are mixed at a predetermined ratio to be washed. .

The poor solvent (A) used in the present invention is an organic solvent that does not substantially dissolve the cyclic olefin polymer to be treated. Specific examples of such organic solvents include acetone, ketones such as methyl ethyl ketone and methyl isobutyl ketone, alcohols such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, 2-ethylhexyl alcohol and ethylene glycol, dimethyl ether, diethyl Mention may be made of ethers such as ether and di-n-butyl ether, and esters such as methyl acetate and ethyl acetate.

The good solvent (B) used in the present invention is an organic solvent that can dissolve the cyclic olefin polymer to be treated at room temperature or higher. Specific examples of such good solvents include n-pentane, n-
- aliphatic hydrocarbons such as hexane, n-heptane, n-octane, n-decane, cyclopentane, cyclohexane, decalin and methylcyclohexane, benzene,
Mention may be made of aromatic hydrocarbons such as toluene, xylene and cumene, as well as halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride ethylene dichloride.

In the present invention, as mentioned above, the poor solvent is
It is an organic solvent that does not substantially dissolve the cyclic olefin polymer, and a good solvent is an organic solvent that can dissolve the cyclic olefin polymer. Ethylene tetracyclo[4] is a typical example of olefin polymer.
．． 4.0.1 2,5.17,10 ]-3-dodecene random copolymer ([η] = 0.54 dl/g) at 1.
Organic solvents that can dissolve 0g or more are classified as good solvents, and organic solvents that can dissolve 0g or more are classified as poor solvents.

In the present invention, the poor solvent (A
) and good solvent (B) in a volume ratio of (A)/(B)=97
The cyclic olefin polymer is washed by contacting with a solvent mixed in a ratio of /3 to 75/25, preferably 95/5 to 80/20.

That is, by bringing a solid cyclic olefin polymer into contact with the above-mentioned specific mixed solvent, the oligomer component contained in a small amount in the cyclic olefin polymer can be efficiently and rationally extracted. Can be done. Since this mixed solvent contains a poor solvent for the cyclic olefin polymer in a specific ratio, the cyclic olefin polymer itself to be treated is not eluted and is maintained in a solid state. Therefore, if the amount of good solvent mixed in the mixed solvent used in the method of the present invention is too large, a part of the polymer will dissolve during extraction and washing, causing a blocking phenomenon, and the polymer and mixed solvent will be brought into continuous contact with each other. During the treatment, the transportability of the mixture of the cyclic olefin polymer and the mixed solvent in this contact step decreases, so that it may not be possible to continuously treat the cyclic olefin polymer. Furthermore, the recovery rate of the polymer decreases, making it impossible to efficiently extract oligomer components. Furthermore, if the amount of the good solvent is too small, the oligomer component will be difficult to dissolve in this mixed solvent, making it difficult to effectively remove the oligomer component.

Although the above-mentioned cyclic olefin polymer and mixed solvent can be brought into contact at room temperature, it is preferable to heat the mixed solvent. However, as the temperature of the mixed solvent increases, the solubility of the cyclic olefin polymer to be treated increases, making it easier for polymer blocking to occur, so the heating temperature should be set in consideration of the solubility of the mixed solvent used in the polymer. . The heating temperature of the mixed solvent is usually 150°C or lower, preferably 100°C or lower. The contact time between the cyclic olefin polymer and the mixed solvent can be appropriately set in consideration of the contact conditions such as the temperature of the mixed solvent, but is usually 10 to 300 minutes, preferably 15 to 180 minutes. Further, the cyclic olefin polymer and the mixed solvent can be brought into contact with each other continuously or batchwise.

The oligomer component extracted by contacting the mixed solvent with the cyclic olefin polymer in this way is a low molecular weight component contained in the cyclic olefin polymer, and specifically, the oligomer component extracted by contacting the mixed solvent with the cyclic olefin polymer is a low molecular weight component contained in the cyclic olefin polymer. The converted number average molecular weight (Mn) is approximately 3,000 or less, and the weight average molecular weight (Mw) is approximately 7,000 or less.

The amount of the oligomer component extracted and removed in this way is usually in the range of 0.05% to 1.0% by weight based on the cyclic olefin polymer subjected to the extraction operation. The cyclic olefin polymer brought into contact with the mixed solvent is then separated from the mixed solvent and further washed if necessary. Note that it is also possible to bring the mixture into contact with a new mixed solvent again.

[0093]

Effects of the Invention Since the cyclic olefin polymer produced by the method of the present invention does not substantially contain oligomers consisting of ethylene and/or cyclic olefin, it can be used repeatedly in the molding of optical discs, for example. It is also suitable for the field of optical materials, such as optical memory disks and optical fibers, where the mold is less likely to become contaminated and even the slightest foreign matter cannot be allowed to enter. Furthermore, since the frequency of cleaning the mold during molding is reduced, it also has the advantage that the continuous molding time becomes longer.

[0094]

EXAMPLES Next, the method of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

[0095]

[Example 1] Using a 1 liter polymerization vessel equipped with a stirrer, ethylene and tetracyclo[4.4.0.1
2,5.17,10 ]-3-dodecene (hereinafter referred to as “TCD
A copolymerization reaction was carried out.

That is, a cyclohexane solution of TCD-3 is poured from the top of the polymerization vessel until the TCD-3 concentration in the polymerization vessel is 6.
A cyclohexane solution of VO(OC2H5)Cl2 was added as a catalyst to 0.4 liters per hour so that the vanadium concentration in the polymerization vessel was 0.5 mmol/liter. The supplied vanadium concentration is 2.86 times the concentration in the polymerization vessel), ethylaluminum sesquichloride (Al(C2H
5) A cyclohexane solution of 1.5Cl1.5) was added to the polymerization vessel at a rate of 0.4 liters per hour and cyclohexane was added at a rate of 0.7 liters per hour so that the aluminum concentration in the polymerization vessel was 4.0 mmol/liter. was continuously supplied.

On the other hand, the polymerization solution in the polymerization vessel was continuously drawn out from the lower part of the polymerization vessel so that the volume was always 1 liter (that is, the average residence time was 0.5 hours). Further, ethylene was supplied to the polymerization system using a bubbling tube at a rate of 20 liters per hour, nitrogen at 10 liters per hour, and hydrogen at a rate of 0.5 liters per hour.

The copolymerization reaction was carried out at 10° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization vessel. When the copolymerization reaction is carried out under the above conditions, ethylene and
A polymerization reaction mixture (polymerization liquid) containing the TCD-3 random copolymer was obtained. [Addition of alcohol] Methanol (water content: 310 ppm) was added to 1 liter of polymerization liquid extracted from the upper part of the polymerization vessel.
) was added and stirred vigorously for 5 minutes. [Deashing] After that, add 5 ml of agricultural hydrochloric acid to 1 liter of water.
The aqueous solution to which was added was brought into contact with the polymerization solution at a ratio of 1:1 under strong stirring using a homomixer, and the catalyst residue was transferred to the aqueous layer. The above mixture was allowed to stand, and after removing the aqueous layer, it was further washed twice with distilled water to purify and separate the polymerization liquid. [Precipitation and drying of polymer] The polymerization solution obtained in the above deashing operation was brought into contact with three times the amount of acetone under strong stirring, and the solid portion was collected by filtration and thoroughly washed with acetone. After that, the solid part was collected by filtration, and heated at 130°C under nitrogen flow.
130℃, 1mmHg for 12 hours at 200mmHg
It was dried for 12 hours.

[0099] In the above manner, ethylene/TCD-3
A copolymer (cyclic olefin random copolymer) was obtained in an amount of 96 g/hour (ie 48 g/liter). The obtained copolymer had an ethylene content of 61.5 mol%, an intrinsic viscosity [η] of 0.54 dl/g, and an M value determined by GPC measurement.
w/Mn is 2.50, crystallinity by X-ray diffraction is 0%,
The glass transition temperature (Tg) measured by DSC method was 137°C. [Extraction operation of oligomer component] Using an autoclave, an operation for extracting the oligomer component contained in the ethylene/TCD-3 copolymer obtained in the above operation was performed. That is, the copolymer was mixed with an acetone/cyclohexane mixed solvent (mixing ratio = acetone/cyclohexane = 90/1) so that the slurry concentration of the copolymer was 20 g/liter.
0 (volume ratio)), and an extraction operation was performed at 75°C for 2 hours with stirring. Then, collect the solid part by filtration,
It was dried at 130° C. and 200 mmHg for 24 hours under nitrogen flow. When the filtrate was concentrated using a rotary evaporator, 0.156% by weight of oligomer was recovered based on the initially charged polymer.

[0100] The molecular weight of the extracted oligomer component is determined by GP
When measured by C (polystyrene equivalent), Mn=
480, Mw=700. These results are shown in Table 1. [Evaluation of mold staining during molding] The above copolymer from which oligomer components have been extracted is heated to a cylinder temperature of 220°C using a single screw extruder.
The mixture was melted and extruded using a pelletizer and pelletized using a pelletizer. The obtained polymer was put into an injection molding machine IS- manufactured by Toshiba Machine Co., Ltd.
55EPN, a disk plate with a thickness of 1 mm and a diameter of 80 mm [one side is mirror-finished, the other side is grooved (spacing 1.4μ
m, 0.09 μm deep, 0.5 μm wide spiral)]
was molded, and the number of shots until mold contamination could be visually confirmed was determined.

[0101] As a result, it was found that mold staining occurred from about 1,100 times. These results are shown in Table 1.

[0102]

[Examples 2, 3, 4 and Comparative Examples 1, 2] Using the ethylene/TCD-3 copolymer obtained in the same manner as in Example 1, the contact conditions with the mixed solvent were changed to those shown in Table 1. Except for the above, the oligomer component was extracted in the same manner as in Example 1 to produce a cyclic olefin polymer.

A disk was produced in the same manner as in Example 1 using the obtained cyclic olefin polymer. Table 1 summarizes the amount of oligomer components extracted, Mn, and the number of shots until mold staining occurs during disk molding.

[0104]

[Table 1]

Claims (2)

[Claims] Claim 1: A cyclic olefin-based random copolymer prepared by copolymerizing (a) ethylene and (b) at least one cyclic olefin represented by the following formula [I] and/or [II]. combination, or (b) the following formula [I
] and/or [II] A cyclic olefin-based ring-opening polymer prepared by ring-opening polymerization of at least one cyclic olefin represented by [II] or a cyclic olefin-based polymer consisting of a hydrogenated product of the ring-opening polymer; , (A) a voracious solvent for the cyclic olefin polymer and (B) a good solvent for the cyclic olefin polymer from 95/5 to
A method for producing a cyclic olefin polymer, which comprises contacting a mixed solvent in a volume ratio of 80/20; [Formula [I], n is 0 or 1, m is 0 or a positive integer, r is 0 or 1, and R1 to R1
8, Ra, and Rb are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group, and R15 to R18 may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or The polycyclic ring may have a double bond, and R15 and R16 or R17 and R18 may form an alkylidene group]; [Formula [II], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R1 to
R19 each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and an alkoxy group, and R9 and R13 or R10 R11 may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when n=m=0, R15 and R12 or R15 and R19 may be bonded to each other to form a monocyclic or polycyclic ring. may form an aromatic ring]. Claim 2: (A) a voracious solvent for the cyclic olefin resin is a ketone, alcohol, ether or ester, and (B) a good solvent for the cyclic olefin resin is a hydrocarbon or a halogenated hydrocarbon. A method for producing a cyclic olefin polymer according to claim 1.