JPH0299505A - Ethylene/polycyclic monomer copolymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer with a low birefringence excellent in transparency, heat resistance and stiffness by copolymerization of ethylene and a specified polycyclic monomer in the presence of a catalyst composed of a V compound soluble in a hydrocarbon solvent and a halogen-containing organoaluminum compound in the above-mentioned solvent. CONSTITUTION:Ethylene and a polycyclic monomer represented by formula I (l, m and n are 0 or 1; p is integer of >=0; R1-R4 are H, 1-10C alkyl, cycloalkyl or aryl) are copolymerized in (90/10)-(10/90) molar ratio in the presence of a catalyst composed of a hydrocarbon-soluble V compound and a halogen- containing organoaluminum compound in a hydrocarbon solvent to obtain a random copolymer with 0.2-15dl/g intrinsic viscosity [eta] in decalin at 135 deg.C containing a structural unit expressed mainly by formula II as the unit derived from the polycyclic monomer represented by formula I.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a random copolymer of ethylene and a polycyclic monomer and a method for producing the same. This random copolymer has excellent transparency, optical homogeneity, low birefringence, flexibility, well-balanced heat resistance,
It has chemical resistance, dimensional stability, rigidity and other mechanical properties. [Prior art] Polystyrene, polymethyl methacrylate, polycarbonate, and polycarbonate have traditionally been used as resins with excellent transparency.
4-methylpentene-1 and the like are known. Polystyrene has excellent transparency, good dimensional stability, and high rigidity, but it has problems in that it is easily attacked by ketones, esters, and aromatic hydrocarbons, and it also has low heat resistance. Polymethyl methacrylate has excellent transparency and high mechanical strength, but it has low heat resistance and is highly resistant to ketones, esters, and aromatic compounds.
Easily attacked by group hydrocarbons. Although polycarbonate has excellent transparency, heat resistance, dimensional stability, and mechanical properties, it is weak against alkalis and has problems such as) high summer refraction and high optical anisotropy. Since poly-4-methylpentene-1 is crystalline, it has problems such as poor mechanical stability and large birefringence. Until now, we have achieved a satisfactory balance of transparency, optical properties, heat resistance, chemical resistance, dimensional stability, and mechanical properties.
There are no known resin materials that do this. [Problems to be Solved by the Invention] In view of the above circumstances, an object of the present invention is to achieve excellent transparency.
However, the object of the present invention is to provide a resin material that has excellent heat resistance, chemical resistance, dimensional stability, and mechanical properties in addition to optical properties such as optical homogeneity and low birefringence. [Means for Solving the Problems] In its aspects, the present invention provides (A) ethylene and the following general formula (I): [wherein j,
m and n are O or 1, p is an integer of 0 or more,
R,, R2, R3 and R4 are a hydrogen atom or an alkyl group having at most 10 carbon atoms, and each is the same or 51
It may be IH, or R3 and R4 may mutually form a ring. ] A random copolymer having a repeating unit derived from a polycyclic monomer represented by ()3) in which the molar ratio of ethylene/polycyclic monomer represented by general formula (1) is 90. /10 to 10/90, and (C) the Cl position derived from the polycyclic monomer represented by general formula (1) mainly provides the following general formula (n) random copolymer. In another aspect of the present invention, in the presence of a catalyst formed from a hydrocarbon i1J-soluble vanadium compound and a norogen-containing organoaluminum compound, in a hydrocarbon solvent, ethylene and a compound represented by the general formula (1) A method for producing the random copolymer by copolymerizing polycyclic monomers is provided. In the random copolymer of the present invention, the polycyclic monomer represented by the general formula (1) copolymerized with ethylene has a structure represented by the general formula (II) as a base, and the polycyclic monomer shown by the general formula (II) has the following general formula (V ) [Ω in the formula, “, n+ p, R1+ R2+ R
3 and R4 have the structure shown above], and (D) the intrinsic viscosity measured in decalin at 135°C [
η] or 0.2 to 15dl! /g, [Ω in the formula
1ml n, p, RII R2I and R4 are as described above] The structure resulting from ring-opening polymerization represented by R3 and is substantially absent, or even if it is present, it is in a very small amount. Therefore, the random copolymer of the present invention is chemically stable. In the present invention, general formula (1) copolymerized with ethylene
Typical examples of polycyclic monomers represented by the following general formula (
(2): Hexadecytyl-6-enes (PCHDs), which are units derived from the polycyclic monomer or are mainly derived from the general formula (IV
) [In the formula, N+n is 0 or 1, R1, R2゜R and R4 are hydrogen atoms or alkyl groups having at most 10 carbon atoms, and each may be the same or different, and R3 and R4 may mutually form a ring. ] Pentacyclo[10.2.1.15°8.0
2°1j04゛9) [In the formula, l, n, R1, R2, R
3 and R4 have the structure shown above], and the structure resulting from ring-opening polymerization is substantially absent, or even if H is present, it is in a very small amount. PCHDs represented by the general formula (1) can be prepared, for example, according to the following reaction formula: tricyclo[G, 2.1. O'') It is synthesized by the Diels-Alder reaction between undec-4-enes (Vl) and cyclopentagenes (■). (V[) (■) [In the formula, D, n, R1, R2 . Pentagenes may be used as a raw material. The molar ratio of tricyclo CB, 2.1.0") undec-4-enes (Vl) and cyclopentagenes (■) is 1:1 to 10. :1 (2:1 to 20:1 when dicyclopentadines are used).In general, as this ratio increases, selectivity, conversion, and yield increase, especially at isothermal conditions. The ratio also increases, but when the ratio exceeds 5:1 (IO:1 when dicyclopentadines are used), the selectivity continues to increase but the conversion and yield decrease slightly. Therefore, the preferred ratio is 2:1 to 5:1 (4:1 to IO:1 when using dicyclopentadines). The reaction temperature is between 100 and 300 °C, preferably 200 and 250 °C. The reaction time varies depending on the reaction temperature, but in any case from 10 minutes to 40 hours, preferably from 30 minutes to 30 hours.
It's time. For these reactions, hydroquinone,
It is also possible to suppress the formation of polymers by adding a polymerization inhibitor such as tart-butylcatechol or p-phenylenediamine. These reactions may also be carried out in a solvent that does not inhibit the reaction, such as a lower alcohol such as methanol or ethanol, a hydrocarbon such as toluene or cyclohexane, or a halogenated hydrocarbon such as chloroform or carbon tetrachloride. To carry out the reaction, batch method,
Either semi-batch or continuous reaction mode can be employed. The fact that the substance produced in this way has the structure represented by formula (III) is confirmed by its 'H-NMR and 13C-NMR.
It can be easily confirmed by MR spectrum. Historically, its mass spectrum also supports that it has the structure of formula (III). In the present invention, general formula CI) copolymerized with ethylene
Other examples of polycyclic monomers shown in Table 1 are shown. (The following is a blank space) Polycyclic monomers as shown in Table 1 are bentashikuo (8
,6,1"8.1""3.02",0"J4) -
It can be easily obtained by the Diels-Alder reaction between g-xadec-4-enes and cyclopentadiene. In the random copolymer of the present invention, the ratio of units derived from ethylene to units derived from the polycyclic monomer represented by general formula (1) is 10/90 to 90/10 (molar ratio), preferably 20/ 8 (1 to 110/20).In addition, within the scope of the purpose of the present invention, other copolymerizable monomers may be added to ethylene and the polycyclic monomer represented by general formula (1). - may be copolymerized. Examples of monomers to be copolymerized include linear or branched α-olefins having 3 to 10 carbon atoms and cycloolefins having 5 to 18 carbon atoms. Specific examples of α-olefins include propylene, dobutene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-octene, and 1-decene. Among these, α-olefins having 3 to 6 carbon atoms are preferred. Specific examples of cycloolefin ρ1 include cyclopentene, cyclohexene, norbornene, methylnorbornene, ethylnorbornene, 4,7-methano-3a, 5,6
．． Examples include 7a-tetrahydro-1H-indene. J self α- on ethylene and the polycyclic monomer represented by the general formula (T) (especially PCHDs represented by the general formula (III))
In the case of a chimium copolymer consisting of an olefin and/or a cycloolefin, the proportion of each monomer unit in the copolymer is
Ethylene/PCHD! fl (molar ratio) is 10/90 to 9 (1/10, preferably 20/80 to 8Q
/20, [α-olefin and/or cycloolefin)/PCHDs (molar ratio) 90/10 to 15/85, preferably 80/20 to 25/
It is 75. In addition, a smaller amount (less than 15 mol 96 of the polycyclic monomer represented by general formula (1) in the copolymer) of other copolymerizable heptamers can be used. 11-fold O like this
Specific examples of functional seven-mers include styrenes such as styrene and α-methylstyrene, norbornenes such as norbornene, methylnorbornene, and ethylnorbornene, and 4,7-methano-3a, 5a, and 6.7a- Tetrahydro-IH-indene, 4,7-methano-2,3,3a
, norbornene-type compounds such as 7a-tetrahydro-IH indene, or dicyclopentadiene,
Examples include polyenes such as 5-ethylidene-2-norbornene and 1,4-hexadiene. The random copolymer of the present invention is prepared by combining ethylene, a polycyclic monomer represented by the general formula (1), and other monomers as necessary in a hydrocarbon solvent with a hydrocarbon ++ J-soluble /) sodium compound and a halogen-containing organic aluminum compound. It is obtained by copolymerizing a catalyst consisting of a compound (J) under cloth. The vanadium compound used at this time is V(1!
, VC”3 or the general formula VO(OR)

[3-L is an alkyl group having at most 10 carbon atoms, X is a halogen, and 0≦t≦3]. Examples of suitable compounds among these include vocΩ3. vOB "3゜VO (OCH3)CN 2゜VO (OCH3)2CfI. VO (OCH3) 3゜Vo (OC2H5) (D 2゜VO (QCH) C11 251,51,5' ■0 (OC2H5) 20g. VO (OC2H5)3゜VO(OC3H7)C1) 2゜VO(QCH) CN 3 7 1.5 1.5'' VO(OC3H7)2ag. Examples include VO(OC3H7) 3゜VO(0・n-CH)CN2゜VO(0"n-C4H9)2(Jl. These compounds can be used alone or as a mixture of two or more. The halogen-containing aH aluminum compound used together with the vanadium compound has the general formula R'AΩX'3-u [where R' is an alkyl group having at most 10 carbon atoms, X' is a halogen, and 0 3) Among them, those in the range of 1≦U≦2 are preferably used. Examples of suitable ones include dimethylaluminum chloride, methylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, Examples include di-n-propylaluminum chloride, n-propylaluminum dichloride, diisobutylaluminum chloride, isobutylaluminum dichloride, etc.These compounds may be used alone or as a mixture of two or more dichlorides.Vanadium compounds and The proportion of halogen a Hfi machine aluminized material used is l/V (molar ratio) of 1 to 30, preferably 2 to 20. Copolymerization is carried out in a hydrocarbon solvent, but as a hydrocarbon solvent Examples include aliphatic hydrocarbons such as hexane, heptane, octane, decane, and kerosene, aromatic hydrocarbons such as benzene, toluene, and xylene, and alicyclic hydrocarbons such as cyclohexane.These can be used alone or as a mixture. In the copolymerization, the concentration of the vanadium compound used as a catalyst in the hydrocarbon solvent is 0.1 to 30 mmol/I.
I, preferably 0.2 to 10 mmol/fl. The charging ratio of ethylene and the polycyclic monomer represented by the general formula (1) varies depending on the composition of the copolymer, the polymerization temperature, or the type of solvent, but in general, the ethylene/polycyclic monomer (molar ratio) is l/ l -1/100. In addition, ethylene and a polycyclic monomer represented by the general formula (1) (especially,
When copolymerizing PCHDs represented by general formula (III) with α-olefin and/or cycloolefin, generally ethylene/PCHDm (molar ratio) −1/
l to I/+00, (α-olefin and/or cycloolefin)/PCHDs (molar ratio) -10/1 or less, preferably 1150 to 10/l. The polymerization temperature is usually -60 to 100°C, preferably -30 to 50°C. Polymerization pressure is generally O~50k
g/cd, preferably 0 to 30 kg/c-. In the present invention, hydrogen can be used to adjust the molecular weight of the copolymer. The intrinsic viscosity [η] of the copolymer of the present invention measured in decalin at 135° C. is 0.2 to 15 dJ/g, preferably 0.5 to 8 dU/g. In order to balance heat resistance, mechanical properties, and moldability, [η] is preferably within the above range. Although the novel random copolymer of the present invention is usually immaculate or has low crystallinity, it is preferably crystalline in order to exhibit excellent transparency. The degree of crystallinity measured by X-rays is less than 5%, and in many cases it is 0%, and in many cases differential scanning thermal ff
No melting point is observed at i:t (D SC). Also,
The copolymers of the present invention exhibit high glass transition temperatures and DS
The glass transition IR degree due to C is usually 80 to 230°C, and most of them are 100 to 200°C, and have excellent heat resistance. Among the polycyclic monomers represented by general formula (1), p-
A copolymer produced using a polycyclic monomer with p −0 (i.e., a polycyclic monomer with the general formula <m
＞The glass transition point is higher when the ethylene ratio is the same. In addition, copolymerization of ethylene, PCHDs, α-olefin and/or cycloolefin, ethylene and PCH
Compared to a copolymer containing only Group D, even if the number of PCHDs is reduced, it shows a high glass transition point, and the amount of PCHDs, which have a high unit price, can be reduced. The novel random copolymer of the present invention can be molded into various shapes by methods used for general synthetic resins, such as compression molding, extrusion molding, injection molding, and blow molding. At this time, additives such as light, heat, oxygen and ozone stabilizers, flame retardants, plasticizers, lubricants, 1) antistatic agents, fillers, colorants, and reinforcing agents may be added as necessary. Can be blended. Furthermore, the novel random copolymer of the present invention can also be used in combination with various known polymers. Examples of these polymers include, for example, ethylene, propylene, butene-1, hexene-1,4-methylpentene-1
Polyolefins such as Chinese-German polymers of α-olefins such as and copolymers composed of two or more of these seven polymers, polystyrene, polyα-methylstyrene,
Styrenic polymers such as acrylonitrile-styrene copolymer, acrylonitrile butadiene-styrene copolymer, polydienes such as polybutadiene and polyisoprene, polyesters such as polyethylene terephthalate and polyethylene terephthalate, nylon 6, nylon 66, nylon 11° nylon Halogen-containing a! polyamides such as No. 12, polyvinyl chloride, polyvinylidene chloride, etc. Poly(meth)acrylates such as ff combination, polymethyl acrylate, polymethyl methacrylate,
Examples include polycarbonate and polyacetal. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 Tricyclo(6.2.1.02”)undec-4ene (4,04kK, 27.21001), dicyclopentadiene (0, [ikg, 4.54mol)] in ION
After charging the autoclave and replacing with nitrogen, 23
Heat and stir at 0° C. for 10 hours at a maximum pressure of 2.2 kg/c−. The reaction mixture was distilled under reduced pressure to a boiling point of 107°C/2mI.
Take the fraction of Jl1g °C pentacycloC10.2.1.
i"8.0"", 0"9]hexadec-6-ene to 1.
I gained 35kg. The above compound has a GC-MASS spectrum,
' Confirmed by H-NMR and I3C-NMR. A 101 four-bottle flask equipped with a polymerization stirrer, a thermometer, a dropping funnel, and a gas blowing tube was thoroughly purged with nitrogen and charged with 5 g of dehydrated toluene. Then, 700 g of PCHD SVO (
,92(OEL)IOmlol into the flask,
A toluene solution containing 320 mmof of E[3Ag2CfI] was charged into the dropping funnel. From the gas blowing pipe, ethylene 140ff/hr, nitrogen 40
01)/hr of mixed gas was passed through a flask cooled to 10° C. with ice water for 15 minutes. //E from J lower funnel
The copolymerization reaction was started by dropping t3AΩ2CΩ3, and the copolymerization reaction was carried out at 10° C. for 30 minutes. During the copolymerization reaction, the interior of the polymerization system was uniform, and no copolymer precipitation was observed. The copolymerization reaction was stopped by adding 60 ml of methanol. The copolymer was precipitated by pouring the IQ solution into a large amount of methanol, and after washing with methanol,
By vacuum drying at 0° C., 350 g of a copolymer was obtained. According to 13C-NMR analysis, the ethylene composition in the copolymer was 55 mol%, and 4p1 in decalin at 135°C.
The determined limiting viscosity [η] is 1.2 dl! /g. The wood value, which is a measure of non-vesicular phase bonding, was 0.6. Transparency was determined using a disc with a diameter of 50 mm and a thickness of 11 mm made by injection molding.
According to JIIJ based on 1003-52, Haz
e -8%. The birefringence was determined as ΔP1 by the ellipsometer method (light source wavelength 830 ni) using the same test piece, and was found to be 7 nm. Furthermore, the melting point T
When l11 and glass transition temperature Tg were measured, no melting polarity was observed in the range of -30°C to 400°C, and Tg was 150°C. The flexural modulus and yield strength were measured using a 2-inch thick press sheet.
When measured based on STM D790, each was 2. OX 10' kg/cd, 910 kg/c-. In order to further evaluate the chemical resistance, 1m+wJv breath sheets were prepared at room temperature using acetone, ethyl acetate, sulfuric acid (98%
), immersed in ammonia water (28%) for 20 hours and observed changes in appearance, there was no change in color, transparency, etc.
No deformation or cracking was observed. The infrared absorption spectrum of this copolymer is as shown in FIG. Examples 2 to 7 The results of Table 21 and Table 3 were obtained in the same manner as in Example 1 except that the copolymerization conditions were changed as shown in Table 2, with no copolymerization reaction <-i. (Hereinafter referred to as "Kinpaku") Examples 8 to 10 Same as Example 1, except that in place of PCHD, the seven-piece shown in Table 41 was used. ,
The N reaction was carried out and the results shown in Table 21 and Table 3 were obtained. (Leaving space below) Example 1: Copolymerization of ethylene, PCHD, and propylene A 10 g four-bottle flask equipped with a stirrer, a thermometer, a dropping funnel, and a gas blowing tube was sufficiently purged with nitrogen, and 5 g of dehydrated toluene was added. . Then, PCHD synthesized in the same manner as in Example 1
500g. 210 mmol of VO(OE,t)CΩ was charged into a flask, and E t a Al) 2 CI) was added to the dropping funnel.
320I! I prepared 1IIlol. Ethylene 140R/hr from the gas blowing pipe. A mixed gas of propylene tgoΩ/hr and nitrogen 100 p/hr was placed in a flask cooled to 10°C with ice water.
It went through for a minute. The copolymerization reaction was started by dropping Et3AΩ2"3 from the dropping funnel, and the copolymerization reaction was carried out for 3υ minutes at 10°C. During the copolymerization reaction, the inside of the polymerization system was uniform, and the copolymer was not precipitated. was not observed.The Jlj polymerization reaction was stopped by adding 60ml of methanol.The copolymer was precipitated by adding Ifi'N SoluiiJ? to a large amount of methanol, and after further washing with methanol, By vacuum drying at 50'C,
Both! lI! 310 g of the combined product was obtained. According to 13C-NMR analysis, the ethylene composition in the copolymer was 45 mol%, and the intrinsic viscosity [η] measured in decalin at 135°C was 2.3. When the physical properties of the copolymer were measured in the same manner as in Example 1, H
aze = 896, and the birefringence was 10 mm. No melting curve was observed in the range from -30°C to 400°C, and the glass transition point Tg was 125°C. The flexural modulus was 1.7 x 10' kg/cd and the yield strength was 800 kg/cd. When immersed in acetone, ethyl acetate, sulfuric acid (98%), and ammonia (2896) for 20 hours at a repress sheet temperature of 1 mm mm, and observing changes in appearance, there was no change in color or transparency, and there were no deformations or cracks. I couldn't see it. Examples 12-21 Example 1 except that the copolymerization conditions were changed as shown in Table 5.
A copolymerization reaction was carried out in the same manner as in 1, and the results shown in Table 51 and Table 6 were obtained. (Space below) Example 22 Polymerization of ethylene and the polycyclic monomer (a) in Table 1 (IO equipped with a stirrer, a thermometer, a dropping F funnel and a gas blowing pipe)
A four-hole N flask was sufficiently purged with nitrogen, and 5 g of dehydrated toluene was charged. Then, compound 700 of (a> in Table 1)
g, VO(OE t) CN 20 mmol was placed in a flask, and Et3Aj! was added to the dropping funnel. ,,CΩ3
20+nmol was charged. A mixed gas of 14 ON/hr of ethylene and 1000 Ω/11 r of nitrogen was passed from the gas blowing pipe into the flask cooled to 10° C. with ice water for 15 minutes. The copolymerization reaction was started by dropping EL3Ag2Cg3 from the dropping funnel, and the copolymerization reaction was carried out at 10° C. for 30 minutes. During the copolymerization reaction, the interior of the polymerization system was uniform, and no copolymer precipitation was observed. methanol 6
The copolymerization reaction was stopped by adding 0ml. The copolymer was precipitated by pouring the polymerization solution into a large amount of methanol, and after further washing with methanol, the copolymer was heated at 50°C.
By drying under vacuum at
The determined limiting viscosity [η] was 1.1. When the physical properties of the copolymer were measured in the same manner as in Example 1, H
aze-10%, and the birefringence was 1Oni. No melting curve was observed in the range from -30°C to 400°C, and the glass transition point Tg was 142°C. The bending modulus is 2.
4X 10' kg/cd, yield strength is 890k
g/cI#. 1. When a thick press sheet was immersed in acetone, ethyl acetate, sulfuric acid (9896), and ammonia (28%) for 20 hours at room temperature and changes in appearance were observed, there was no change in color or transparency, and no deformation or cracks were observed. No outbreak was observed. Examples 23 to 28 A copolymerization reaction was carried out in the same manner as in Example 22, except that the polycyclic monomer components and copolymerization conditions were changed as shown in Table 7, and the results shown in Tables 71 and 8 were obtained. (The following is a blank space) [Effects of the Invention] The random copolymer of the present invention exhibits well-balanced optical properties, mechanical properties, thermal properties, and chemical properties compared with conventional resin materials. That is, the Jj-polymer of the present invention has excellent transparency, is optically homogeneous, and has a small double mouthfeel (,
Moreover, it has excellent mechanical properties such as heat resistance, chemical resistance, dimensional stability, and rigidity. The copolymer of the present invention can be used, for example, in optical materials such as optical discs, optical fibers, plastic lenses, and optical filters, window glasses for buildings and vehicles, and medical and chemical fields such as Note 1.1 vessels, beakers, and graduated cylinders. It can be used for etc.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum of the copolymer of Example 1.

Claims (8)

[Claims] (1) (A) Ethylene and the following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, l, m, and n are 0 or 1, and p is an integer of 0 or more. R_1, R_2, R_3 and R_4 are hydrogen atoms or alkyl groups having at most 10 carbon atoms and may be the same or different, and R_3 and R
_4 may form a ring with each other. ] A random copolymer having repeating units derived from a polycyclic monomer represented by (B) ethylene/polycyclic monomer represented by general formula (I) in a molar ratio of 90/10 to 10/90. Yes, (C
) The units derived from the polycyclic monomer represented by the general formula (I) are mainly the following general formula (II) ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (II) [In the formula, l, m, n, p, R_1 , R_2, R_3 and R_4 have the structure shown above], and (D) the intrinsic viscosity measured in decalin at 135°C [η]
A random copolymer having a water content of 0.2 to 15 dl/g. (2) The polycyclic monomer has the following general formula (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) [In the formula, l and n are 0 or 1, R_1, R_2R
_3 and R_4 are hydrogen atoms or have at most 1 carbon number
0 alkyl groups, each of which may be the same or different, and R_3 and R_4 may mutually form a ring. ] Pentacyclo [10.2.1.1^5^,^
8.0^2^,^1^1.0^4^,^9] Hexadec-6-enes (PCHDs), and the units derived from the polycyclic monomer are mainly represented by the following general formula (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) [In the formula, l, n, R_1, R_2, R_3 and R_4
is as described above.] The random copolymer according to claim (1), which has a structure shown in the following. (3) Substantially ethylene and pentacyclo [10.2.1.1^5^,^8.0^2^] represented by the general formula (III)
,^1^1.0^4^,^9] The random copolymer according to claim (2), comprising only repeating units derived from hexadec-6-enes. (4) (A) Ethylene, a polycyclic monomer represented by general formula (III), and at least one kind selected from α-olefins having 3 to 10 carbon atoms and cycloolefins having 5 to 18 carbon atoms. A random copolymer consisting of repeating units derived from monomers, wherein the molar ratio of (B) ethylene/polycyclic monomer represented by general formula (III) is 90/10 to 10/90, and (C
) The molar ratio of at least one monomer selected from α-olefins and cycloolefins/polycyclic monomer represented by general formula (III) is from 90/10 to 15/85, and (D) general formula ( The random copolymer according to claim (2), wherein the units derived from the polycyclic monomer represented by III) mainly have a structure represented by general formula (IV). (5) (A) In a hydrocarbon solvent in the presence of a catalyst formed from a hydrocarbon-soluble vanadium compound and a halogen-containing organoaluminium compound, (B) ethylene and the following general formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼(I) [In the formula, l, m, and n are 0 or 1, p is an integer of 0 or more, and R_1, R_2, R_3, and R_4 are hydrogen atoms or alkyl atoms having at most 10 carbon atoms. group, cycloalkyl group or aryl group], the molar ratio of (C) ethylene/polycyclic monomer represented by general formula (I) is 90/10 to 10/90. , (D
) The units derived from the polycyclic monomer represented by general formula (I) are mainly the following general formula (II) ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, l, m, n, p, R_1, R_2, R_3 and R_4 have the structure shown above], and (E) the intrinsic viscosity measured in decalin at 135°C [η]
A method for producing a random copolymer having a copolymer of 0.2 to 15 dl/g. (6) As a polycyclic monomer, the following general formula (III)▲mathematical formula,
There are chemical formulas, tables, etc. ▼ (III) [In the formula, l and n are 0 or 1, R_1, R_2,
R_3 and R_4 are a hydrogen atom or an alkyl group having at most 10 carbon atoms, and may be the same or different, and R_3 and R_4 may mutually form a ring. ] Pentacyclo [10.2.1.1^5^,^
8.0^2^,^1^1.0^4^,^9] Copolymerization using hexadec-6-enes (PCHDs), and the units derived from the polycyclic monomer mainly have the following general formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) [In the formula, l, n, R_1, R_2, R_3 and R_4
is as described above.] The method for producing a random copolymer according to claim 5, wherein a copolymer having a structure shown in the following is obtained. (7) Substantially ethylene and pentacyclo [10.2.1.1^5^,^8.0^2^] represented by the general formula (III)
,^1^1.0^4^,^9] The method for producing a random copolymer according to claim (6), wherein a monomer mixture consisting only of repeating units from which hexadec-6-enes are derived is copolymerized. . (8) (A) Ethylene, a polycyclic monomer represented by the general formula (III), and at least one kind selected from α-olefins having 3 to 10 carbon atoms and cycloolefins having 5 to 18 carbon atoms. By copolymerizing the monomers, the molar ratio of (B) ethylene/polycyclic monomer represented by general formula (III) is from 90/10 to 10/90, and (C
) The molar ratio of at least one monomer selected from α-olefins and cycloolefins/polycyclic monomer represented by general formula (III) is from 90/10 to 15/85, and (D) general formula ( The method for producing a random copolymer according to claim (6), wherein a copolymer is obtained in which units derived from the polycyclic monomer represented by III) mainly have a structure represented by general formula (IV).