JPS61120816A - Novel addition copolymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention has excellent transparency and a balance of mechanical properties such as heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and rigidity. More specifically, the purpose is to provide a novel polymer having a polycyclic monomer component represented by the following general formula (1) as one of its constituent units. do.

(Here, R1 to R12 are hydrogen, an alkyl group, or a halogen, and may be the same or different, and Rq or RID and R11 or R12 may mutually form a ring. Furthermore, n is R5 to R9, which are positive numbers of 2 or more and are repeated multiple times, may be the same or different.)
[Prior Art] Polycarbonate, polymethyl methacrylate, polyethylene terephthalate, and the like are known as synthetic resins with excellent transparency. For example, polycarbonate is a resin that has excellent heat resistance, heat aging resistance, and impact resistance as well as transparency. However, there is a problem that it is easily attacked by strong alkalis and has poor chemical resistance. Methyl polytutyacrylate has problems in that it is easily attacked by ethyl acetate, acetone, etc., swells in ether, and has low heat resistance. Furthermore, although polyethylene terephthalate has excellent heat resistance and mechanical properties, it is susceptible to strong acids and alkalis and is susceptible to hydrolysis.

On the other hand, many polyolefins, which are famous as general-purpose resins, have excellent chemical resistance, solvent resistance, and mechanical properties, but many have poor heat resistance, and because they are crystalline resins, they lack transparency. Inferior. Generally, to improve the transparency of polyolefins, methods are used to refine the crystal structure by adding a nucleating agent, or to stop crystal growth by rapid cooling, but these methods cannot be said to be sufficiently effective. On the contrary, adding a third component such as a nucleating agent may impair the excellent properties originally possessed by polyolefins, and rapid cooling requires a large-scale equipment and may lead to a decrease in crystallinity. There is also a possibility that heat resistance and rigidity may decrease.

[Purpose of the invention]

Therefore, the present inventors have conducted repeated research to find out whether it is possible to obtain a synthetic resin that is transparent and has a good balance of heat resistance, heat aging resistance, solvent resistance, dielectric properties, and mechanical properties. It was discovered that a copolymer with a specific bulky comonomer could achieve the objective, and the technical contents thereof were disclosed in Japanese Patent Application No. 16995/1983.

The present invention relates to an improvement on the technology proposed in the above-mentioned application, and relates to polymers using bulkier monomer components.

[Means to solve the problem]

That is, the present invention provides: (A) a polycyclic monomer component represented by the general formula (1);
Furthermore, if necessary, a polymer consisting of ethylene, (B) an ethylene/polycyclic polymer component (molar ratio) of 951
5 to O/100, and (C) the polycyclic monomer component unit mainly has the following general formula (H
), and (D) the intrinsic viscosity measured in decalin at 135°C [
η] of 0.005 to 20 dl/g.

[Overview of the new type of combination]

The polymer of the present invention is substantially composed of a polycyclic monomer component or a polycyclic monomer component and ethylene. However, other copolymerizable monomer components may be copolymerized, for example, within a range of 50 mol % or less of the polycyclic monomer component units, as long as the object of the present invention is not impaired. Specific examples of such copolymerizable monomers include propylene, 1-butene, 3-methyl-1-butene, 1-
Pentene, 4-methyl-1-pentene, 1-hexene,
α-olefin having 3 or more carbon atoms such as 1-decene,
Cycloolefins such as cyclopentene, cyclohexene, and 3-methylcyclohexene; styrenes such as styrene and α-methylstyrene; norbornenes such as norbornene, methylnorbornene, ethylnorbornene, and isobutylnorbornene; 2.3,3a,7a-tetrahydro-4 ,7-methano-111-indene (general formula (
b)) ,3a,5,6.7a-tetrahydro-4,
Endomethylene compounds not included in the general formula (A) of the present invention, such as 7-methano-111-indene (general formula (B)) or compounds where n=1 in general formula (1), or 1,4- Quizadiene, dicyclopentadiene,
Mention may be made of polyenes such as 5-ethylidene-2-norbornene.

(a) (b) The polymers defined in the present invention can be broadly classified into homopolymers of polycyclic monomer components and random copolymers of polycyclic monomer components and ethylene, depending on the type of constituent monomer components. , the latter is preferred since it provides a well-balanced polymer for the purpose of the present invention.

The content ratio (molar ratio) of ethylene/polycyclic monomer component in the polymer of the present invention is from 9515 to 0/100. Among these, for a high molecular weight substance to have an excellent balance of physical properties, 90/
A range of 10 to 10/90, particularly 85/15 to 20/80, is preferred.

The polycyclic monomer component is mainly polymerized in the structure shown in the general formula (TI) in the polymer. Since the polycyclic monomer component mainly has the above structure, the iodine value of the polymer of the present invention is usually 5 or less, and most of them are 1 or less. Moreover, having the above structure means '3C-NM
This is also supported by R. Therefore, the polymer has a chemically stable structure and excellent heat aging resistance.

The polymer has an intrinsic viscosity [η
] is 0.005 to 20 dl/g. In particular, when used for hard resin applications, 0.3 to 2 Qdl/g, particularly 0.3 to LO dl/g, and more preferably 0.8 to 8 dl/g. Also, when used for wax purposes, 0.
01 to less than 0.3 dl/g, and even 0.05 to 0.2
Setting/g is preferred.

Another property of the polymer is that it is non-porous or has low crystallinity, preferably non-crystalline. Therefore, transparency is good. In general, the degree of crystallinity by X-rays is 5% or less,
It is preferably 0%, and in many cases the melting point is not observed using a differential scanning calorimeter (DSC).

Other properties of polymers include high glass transition and softening temperatures. In other words, the dynamic viscoelasticity measurement needle (D
Glass transition temperature (Tg) according to MA) is usually 80 to 24
0°C, mostly measured in the range of 100-200'C. Also, TMA (thermo-mechanic
alAnalyser (manufactured by DuPont) under the conditions of a load of 49 g and a heating rate of 5°C/min using a quartz needle (diameter 0.635+nm), the temperature at which the needle penetrates 0.1 mm, that is, the softening temperature, is usually 70 to 220°C. , mostly 9
Measured within the range 0-190°C.

In addition, the thermal decomposition temperature of a polymer is usually 35°C, assuming that the temperature at which weight loss starts is raised at a rate of 10°C/min using a thermobalance (TGA: manufactured by Rigaku Denki Co., Ltd.) under a nitrogen stream.
0 to 420°C, mostly within the range of 370 to 410°C.

The density of the polymer was determined by the density gradient tube method (ASTM 0
1505) T: Usually 0.86-1.10 g/
aa, most of which are within the range of 0.88 to 1.08 g/ca. Also, the refractive index (ASTM D 542) is 1.4
7 to 1.58, mostly in the range of 1.48 to 1.56.

Regarding the electrical properties of polymers, the dielectric constant (IKHz) according to ASTM D150 is 1.5-3.0, and most are 1.9-2.
．． 6. Dielectric loss tangent is 1 x 10 to 5 x 10-゜, mostly 5 x
It is within the range of 10-8X10'.

Pencil hardness (JI) as a measure of the surface hardness of polymers
SK5401) is 3B or more and 3H or less.

[Application field]

An example of a specific field of application of the new combination of the present invention is as follows:
Taking advantage of its excellent physical properties, the low molecular weight product can be used in many fields such as waxing, pine wood impregnating agent, paper processing agent, sizing agent, rubber anti-aging agent, and corrugated board. Water resistance agents, chemical fertilizer slowing agents, heat storage materials, ceramic binders, paper capacitors, electric wires,
Electrical insulation materials for cables, neutron moderation rate, textile processing aids, water repellent for building materials, paint protection agents, polishing agents, thixotropy agents, lead hardening agents for pencils and crayons, carbon ink bases, for electrostatic copying. Examples include toner, lubricant for synthetic resin molding, mold release agent, resin coloring agent, hot melt adhesive, and lubricating grease. In addition, in the case of high molecular weight substances, plastic lenses, optical discs, optical fibers,
Optical field such as glass window applications, electrical field such as transparent conductive films and sheets, liquid crystal display substrates, high frequency circuit boards, water tanks for electric irons, microwave oven supplies, medical field such as syringes, pipettes, animal gauges, etc., and chemical field It can be used in various fields such as camera bodies, various instrument housings, plastic magnets, films, sheets, and helmets.

[Molding processing and stabilizers]

The polymers of the present invention are processed by well-known methods.

For example, single screw extruder, Ghent type extruder, twin screw extruder, conical twin screw extruder, conical screw extruder, plateificator, mixtruder, twin screw conical screw extruder, planetary screw extruder, gear type extruder, Extrusion molding, injection molding, blow molding, rotational molding, etc. are performed using screwless extruders. In addition, during the molding process, well-known additives such as heat stabilizers,
Light stabilizers, antistatic agents, slip agents, antiblocking agents, antifog agents, lubricants, synthetic oils, natural oils, inorganic and organic fillers, dyes, pigments, etc. may be added.

One example of such an additive is a phenolic or sulfur antioxidant. Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, stearyl (3,3-dimethyl-
4-hydroxybenzyl)thioglycolate, stearyl-β-(4-hydroxy-3,5-tert-
Butylphenol) propionate, distearyl-3
, 5-tert-butyl-4-hydroxybenzylphosphonate, 2', 4. '6. - ) Squirrel (3',
s'-diter t-butyl-4'-hydroxybenzylthio)-L3,5-) riazine, distearyl (4
-Hydroxy-3-methyl-5-tert-butylbenzyl)malonate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol>, 4.47-
Methylenebis(2,6-tert-butylphenol), 2,2'-methylenebis(6-(1-methylcyclohexyl) p-cresol), Bis[3,5-bis(4-hydroxy-3-tert-butylphenyl) ) Butyric acid coglycol ester, 4,4-butylidenebis(6-tert-butyl-m-cresol)
1.1,1.3-■ Tris(2-methyl-4-hydroxy-5-tert-
butylphenyl)butane, bis(2-tert-phthyl-4-methyl-6-(2-hydroxy-3-tert)
7'thyl-5-methylbenzyl)phenylcoterefucrate, 1,3.5-)lis(2,6-dimethyl-3-hydroxy-4,-tert-butyl)benzyl isocyanurate, 1,3.5-) Lis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4
, 6-trimethylbenzene, tetrakis[methylene-3
=(3,5-di-tert-butyl-4-hydroxyphenyl)propionate comethane, L3; 5-)lis(3,5, di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3.5 − ) Squirrel (
(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
-) phenolics such as riazine, 4,4'-thiobis(6-tert-butyl-m-cresol) and 4,4
'-Butylidene bis(2-tert-butyl-5-methylphenol) carbonate oligoester (for example, polymerization degree 2
, 3,4,5,6,7°B, 9.10, etc.).

Examples of sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl, simiristyl, and distearyl, and butyl, octyl, lauryl, and the like.
Polyhydric alcohols of alkylthiopropionic acids such as sterolyl (e.g. glycerin, trimethylolethane,
trimethylolpropane, pentaerythritol, trishydroxyisocyanurate) (eg pentaerythritol tetralauryl thioprobionate).

Alternatively, phosphorus-containing compounds may be added, such as trioctyl phosphite, trilauryl phosphite,
Tridecyl phosphite, octyl-diphenyl phosphite, tris(2,4-tert-butylphenyl) phosphite, triphenyl phosphite, tris(butoxyethyl) phosphite, tris(nonylphenyl) phosphite, distearyl Pentaerythritol diphosphite, tetra (+-lysosyl)-1,
1,3-tris(2-methyl-5-mert-butyl-
4-hydroxyphenyl)butane diphosphite, tetra(tridecyl) alkyl-4,4-isopropylidene diphenyl phosphite, tetra(tridecyl)
-4,4'-butylidene bis(3-methyl-5-te
rt-butylphenol) diphosphite, trisph 3
, 5-di-tert-butyl-4-hydroxyphenyl) phosphite, tris(mono-dimixed nonylphenyl) phosphite, hydrogenated-4,4-known isopropylidene diphenol polyphosphite, bis(octylphenyl) bis [4,4'-Butylidenebis(3-methyl-5
-t'ert-butylphenol)) ・1. ．． 6-
Hexanediol diphosphite, phenyl 4.4
'-Isopropylidene diphenol pentaerythritol diphosphite, bis(2,4-diter t-
butylphenyl) pentaerythritol diphosphite, bis(2,6-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tris[4□4'-isopropylidene bis(2-tart-butylphenol)]phosphite phyto, phenyl diisodecyl phosphite, di(nonylphenyl) pentaerythritol diphosphite, tris(1i3-di-stearoyloxyisopropyl) phosphite, 4,4'-
Isopropylidene bis(2-tert-butylphenol) di(nonylphenyl) phosphite, 9.10
-di-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-t
Examples include er t-butylphenyl)-4,4'-biphenylene diphosphonite.

Also, 6-hydroxychroman derivatives such as α, β, γ
, various tocopherols of δ and mixtures thereof, 2-(4
2,5-dimethyl substituted product of -methyl-pent-3-enyl)-6-hydroxychroman, 2, 5. 8-trimethyl substituted product, 2,5,7.8-tetramethyl substituted product,
2,2.7-trimethyl-5-tert-butyl-
6-hydroxychroman, 2,2.5-)limethyl-7-tert-phthyl-6-hydroxychroman, 2,
2,,5-)dimethyl-5-tert-butyl-6-hydroxychroman, 2,2-dimethyl-5-tert
-butyl-6-hydroxychroman, etc. Another example is the general formula % (where M is Mg, Ca or ZnSA is an anion other than a hydroxyl group, x, y and 2 are positive numbers, and a is 0 or a positive number. (011)+6 Go?・4+120, Mgg
A12 (Oil); zo CO3 ・511; +O.

Mg,A12(011)+4COu・41120,Mg
+oA12'(0.1F)-'22 (Co-3
) ・41120, MgcA12 (OB)14
HPO4・4+120, Ca6^12 (Off)+
g co 3 ・41120, Z'n & Alz (Of
f)+c COq・41170, ZngAI7 (01
1) +g S04- 4H20, Mg, Alz (O old +bSO4・4H20, MgiALz (Off) +z
CJ・31120, etc. may be blended.

In addition, 2-
Benzofuranone compounds, such as 3-phenyl-2-
Benzofuranone, 3-phenyl-5,7-di, monobutyl-2-benzofuranone, etc. may be blended.

Examples of light stabilizers include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone-2,2'-di-hydroxy-4-methoxybenzophenone, 2. Hydroxyhensiphenones such as dihydroxybenzophenone, 2-(2'
-Hydroxy-3'-tert-butyl-5'-methylphenyl-5-chlorobenzotriazole, 2-(2'
-Hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-
Hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3i 5'-diter
Benzotriazoles such as t-amylphenyl)benzotriazole, phenyl salicylate, p-ter
t-butylphenyl salicylate, 2,4-ter
t-Butylphenyl-3,5-di-tert-phthyl-4-hydroxybenzoate, hexadecyl-3,5-
Henshades such as tert-butyl-4-hydroxybenzoate, 2,2'-thiobis(4-te
rt-octylphenol) Ni salt, (2,2'-thiobis(4-tert-octylphenol)-n-butylamine lJi, (3,5-di-tert-butyl~4-hydroxyhensyl)monoethyl phosphonate Nickel compounds such as ester old salts, α-cyano-β-
Substituted acrylonitriles such as methyl-β-(p-methoxyphenyl)acrylate and N'-2-methylphenyl-N-2-ethoxy-5-tert-butylphenyl oxalic acid diamide, N-2-ethylphenyl- N
Oxalic acid dianilides such as '-2-ethoxyphenyl oxalic acid diamide, bis(2,2,6,6-titramethyl-4-piperidine)sepacade, polyC((6-
(1,1゜3.3-tetramethylbutyl)imino) -
],,3.5-) riazine-2,4-diyl(4-(
2,2,6,6-titramethylpiveridyl)imino)hexamethylene], 2-(4-hydroxy-2,2,6,
Examples include hindered amine compounds such as a condensate of 6-te[·ramethyl-1-piperidyl)ethanol and dimethyl succinate.

Examples of lubricants include aliphatic hydrocarbons such as paraffin wax, polyethylene wax, and polypropylene wax, higher fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, araxic acid, and behenic acid, or these. metal salts, such as lithium salts, calcium salts, sodium salts, magnesium salts, potassium salts, aliphatic alcohols such as valmityl alcohol, cetyl alcohol, stearyl alcohol, caproic acid amide, caprylic acid amide, capric acid amide, Aliphatic amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, esters of fatty acids and alcohols, fluoroalkyl carboxylic acids or their metal salts,
Examples include fluorine compounds such as fluoroalkylsulfonic acid metal salts.

Fillers include glass fiber, silver or aluminum coated glass T8Jl1m, stainless steel fiber, aluminum fiber, potassium titanate fiber, carbon fiber, Kevlar.
Fibers, inorganic or organic fibrous fillers such as ultra-high modulus polyethylene fibers, curcum, calcium carbonate, magnesium hydroxide, calcium oxide, magnesium sulfate, graphite, nickel powder, silver powder, copper powder, carbon black,
Examples include powdered, granular, and flaky inorganic or organic fillers such as silver-coated glass beads, aluminum-coated glass beads, aluminum flakes, stainless steel flakes, and nickel-coated graphite.

[Blend with other polymers]

Furthermore, the new type of polymer of the present invention can also be used in combination with various known high-molecular weight or low-molecular weight polymers.

Examples of such polymers include (a) polymers derived from hydrocarbons having one or two unsaturated bonds, specifically polyolefins such as polyethylene, polypropylene, which may have a crosslinked structure, Polyisobutylene, polymethylbutene-1, poly4-methylpentene-1, polybutene-1, polyisoprene, polybutadiene, polystyrene, or copolymers of monomers constituting the above polymers, such as ethylene and propylene co-1
propylene-butene-1 copolymer, propylene-isobutylene copolymer, styrene-isobutylene copolymer, styrene-butadiene copolymer, ethylene and propylene with dienes such as hexadiene, cyclopencdiene, ethylidene norbornene, etc. (b) Halogen-containing vinyl polymers, such as original copolymers, or blends, graft polymers, and block copolymers of these polymers, specifically polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, and polychloroprene. , chlorinated rubber, etc. (c) Polymers derived from α,β-unsaturated acids and their derivatives, specifically polyacrylate, polymethacrylate-1-,
Polyacrylamide, polyacrylonitrile, or copolymers of monomers constituting the above polymers with other copolymerizable monomers, such as acrylonitrile-butadiene-styrene copolymers, acrylonitrile-styrene copolymers, acrylonitrile-styrene copolymers,
(d) Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as acrylic ester copolymers, specifically polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, and polymalein. vinyl acid, polyvinyl butyral, polyallyl phthalate, polyallylmelamine, or a copolymer of the monomer constituting the above polymer with other copolymerizable monomers, such as ethylene/vinyl acetate copolymer, (e) From epoxide (to) polyacetals, specifically polyoxymethylene, polyoxyethylene,
Polyoxymethylenes containing ethylene oxide as a comonomer, (g) polyphenylene oxide, (h) polycarbonate, (l) polysulfone, (n) polyurethane and urea resin, (l) diamine and dicarboxylic acid and/or aminocarboxylic acid. or polyamides and copolyamides derived from the corresponding lactams, in particular nylon 6, nylon 66, nylon 11,
Polyesters derived from dicarboxylic acids and dialcohols and/or oxycarboxylic acids or corresponding lactones, such as nylon 12, in particular polyethylene terephthalate, polybutylene terephthalate, poly 1,4-dimethylol cyclohexane terephthalate, etc. (iv) Polymers with a crosslinked structure derived from aldehyde and phenol, urea or melamine, specifically phenol/formaldehyde + A4 fat, urea/formaldehyde resin, melamine/formaldehyde resin, etc. (I) Alkyd resin, specifically In particular, unsaturated polyester resins derived from copolyesters of (y) saturated and unsaturated dicarboxylic acids and polyhydric alcohols, such as glycerin/phthalic acid resins, and obtained using vinyl compounds as crosslinking agents, and halogen-containing modified resins. Examples include natural resins, natural polymers, specifically cellulose, rubber, proteins, and derivatives thereof such as cellulose acetate, cellulose propionate, and cellulose ether. Furthermore, when used as a synthetic wax, it goes without saying that various known waxes may be mixed.

Furthermore, the new type combinations of the present invention having different molecular weights may be mixed.

[Monomer component]

The monomer component constituting the polymer of the present invention is mainly a polycyclic monomer represented by the above-mentioned general formula (1) or ethylene.

In the general formula representing a polycyclic monomer component, R1 to R1
2 is hydrogen, an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, cycloalkyl such as cyclopentyl, cyclohexyl, or halogen such as fluorine, chlorine, bromine, iodine, etc. - or may be different. Also R
q or RIO and R11 or R12 may mutually form a ring, for example, in the general formula (Ill), (,IV)
For example,

(Here, R13 to R26 are hydrogen or alkyl groups, and may be the same or different.) Specific examples of such polycyclic monomer components include those shown in Table I below.

In addition to these, any monomer component may be used as long as it is represented by the general formula (1), but n-2 or 3 is preferable, and a polycyclic monomer component where n=2 is particularly suitable.

[Polymerization method]

In order to produce the new type of combination of the present invention, a polycyclic upper Zummer component or a polycyclic upper Zummer component and ethylene may be polymerized using a well-known Ziegler catalyst.

The Ziegler catalyst used in the present invention is a titanium compound supported on a magnesium compound, which is known as a highly active catalyst, or a catalyst consisting of a vanadium compound and a reducing agent such as an alkyl aluminum compound. be.

The titanium compound supported on the magnesium compound is preferably a complex containing at least magnesium, titanium and halogen, and is preferably a compound obtained by bringing a magnesium compound and a titanium compound into close contact by means such as heating or co-pulverization. is one in which the molar ratio of halogen/titanium contained in the composite exceeds about 4,
A hexane cleaning method at room temperature that does not substantially remove titanium compounds from moonlight.

A good composite has a halogen/titanium (molar ratio) of about 4
2, magnesium/titanium (molar ratio) is greater than about 3, preferably about 5 to about 50, preferably about 5 or more, more preferably about 8 or more. body/titanium (molar ratio) is about 0.2 to about 6, preferably about 0.4 to about 3, more preferably about 0.8 to about 2, and the specific surface area is about 3n(
7 g or more, more preferably about 4 On (7 g or more, even more preferably about 4 On/g or more. It is desirable that sybaride be in a highly amorphous state compared to that of ordinary commercially available products.

As an example of means for producing a composite, for example,
No. 16986, JP-A-5 oltos3es, JP-A-Sho 5
0-126590, JP-A-5'l-20297, JP-A-51-28189, JP-A-51-F92885,
JP-A-51-127185, JP-A-5], -1366
No. 25, JP-A-52-87489, JP-A-52-10
No. 0596, JP-A-52-104593, JP-A-52
= No. 147688, JP-A-53-2580, 1975
An example is the means described in the Italian patent application dated November 21, 2013.

Vanadium compounds include VCI4, VBr4, VC
I,, VBr) etc. vanadium halides, VOCl3
, VOBrl, VOCl2, VOBrz, and other vanadium oxyhalides or VO(OR)Ji-v, (where R is a hydrocarbon group, X is a halogen, and 0<, 1≦3) can be mentioned. . Among these, hydrocarbon-soluble vanadium compounds, especially vanadium oxyhalides or VO(OR), X? Compounds represented by - are preferred. Said V() (OR)A
In the compound represented by XJ-1,L, R is an aliphatic, alicyclic or aromatic hydrocarbon group, preferably an aliphatic hydrocarbon group with 1 to 20 carbon atoms 1~
3 is good. Also, n is 0<n≦3, preferably 1≦
The range is n≦1.5. Examples of such vanadium compounds include VO(OCI+3) C12, VO(OCI+3)
CI+3)2CI, VO(OClb)5, VO(Q
C, Hs ) CI2, VO (QC2II 2 >,
15C115, VO (OC2115bc), VO (QC
, Ilh ) 3, VO (OC2115) 1. qBr1, VO (OCI11wa)' C12, VO (OC311
? 7) b5c] 1. I5, VO(OC3117)2C
L VO(OChH7)1, VO(On-C4119)
C12, VO(On-C411Q)2C].

VO(O4soC41+q)2CI, VO(OsecC
411q)3, VO(QC et H++),,t5C11
Examples include the stomach and a mixture of these.

These can be easily obtained by reacting VOCl3 and alcohol or by reacting VOCl3 and VO(OR)3.

The alkylaluminum compound used with the titanium-based catalyst or vanadium-based compound has the general formula R'mAIX')
-t, , (where R' is a hydrocarbon group, x't is a halogen, and Q<m≦3). Examples of the alkyl aluminum compound include trialkyl aluminum, dialkyl aluminum halide, alkyl aluminum civalide, any mixture thereof, or a mixture of these and aluminum trihalide.

Among the catalyst systems shown above, a vanadium compound/alkyl aluminum compound system is preferred from the viewpoint of ease of polymerization. When using this system, the usage ratio of both is ^
1/V (molar ratio) is preferably 1 or more, preferably 30 or less, particularly preferably 2 to 20.

Polymerization takes place in a hydrocarbon medium. For example, hexane
Aliphatic hydrocarbons such as heptane, octane, and kerosene, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as henzene, toluene, and xylene are used alone or in combination as a solvent.

be able to.

For example, in the case of a catalyst system of a vanadium compound/alkyl aluminum compound, the amount of the vanadium compound in the reaction medium is 0.05 to 20 mmol/7! , preferably at a concentration of 0.1 to 10 mmol/β. Further, the alkylaluminum compound is adjusted so that the A1/V (molar ratio) is 1 or more, preferably 30 or less, and particularly preferably 2 to 20, as described above.

When producing a random copolymer of a polycyclic monomer component and ethylene, the amount of both monomer components charged into the reaction medium varies depending on the composition of the desired copolymer, the type of reaction medium, and the polymerization temperature. , generally the molar ratio of ethylene/polycyclic monomer component in the reaction medium is from 1/100 to 100.
/1, preferably 1150 to 50/1.

The polymerization temperature is -50 to 300°C, preferably -30 to 20°C.
The 0°C1 polymerization pressure is generally maintained at 0 to 50 kg/c, preferably 0 to 20 kg/CJ. Further, a molecular weight regulator such as hydrogen may be present as appropriate to adjust the molecular weight of the polymer.

〔Example〕

The content of the present invention will be explained below using preferred examples, but the present invention is not limited to these examples.
Of course, any form can be adopted as long as the purpose is not impaired.

Example 1 A stirring blade, a gas blowing pipe, a temperature needle, and a dropping funnel were attached to a thoroughly dried 500 ml Separate flask, and the flask was sufficiently purged with nitrogen.

250 mn of toluene that had been dehydrated and dried using a molecular sieve was placed in this flask.

In a flask under nitrogen flow, add 7.5 g of compound A in Table 1.
Add 2.5 mmol of ethylaluminum sesquichloride and 0.0 mmol of dichloroethoxyoxovanadium to the dropping funnel.
．． 25 mmol was added.

Ethylene lQ7 dried through a gas blowing pipe! /hr.

Nitrogen 407! /hr of mixed gas was passed through the flask controlled at 10°C for 10 minutes.

The copolymerization reaction was started by dropping ethylaluminum sesquichloride from the dropping funnel, and the copolymerization reaction was carried out at 10°C for 30 minutes while passing the mixed gas.

The solution during the copolymerization reaction was homogeneous and transparent, and no copolymer precipitation was observed.

The copolymerization reaction was stopped by adding 5 ml of methanol to the polymer solution.

After stopping the reaction, the polymerization solution was poured into a large amount of methanol to precipitate a copolymer, and after further washing with methanol, the mixture was heated at 60°C.
The copolymer was vacuum dried for one day and 5.3 g of copolymer was obtained.

The ethylene composition in the copolymer measured by '3C-NMR analysis was 59 mol%, the intrinsic viscosity [η] measured in 135'C decalin was 1.4, and the iodine value was 0.9.

In addition, in order to measure mechanical properties, 230°C hotpr
Press-molded sheets with a thickness of 1 mm or 2 mm were created using ess. When X-ray diffraction was performed using these sheets, no scattering due to crystals was observed, and the degree of crystallinity was 0.
%Met. In addition, transparency is AsTM D 1003
A 1 mm sheet was measured to have a haze of 9% using a haze meter conforming to the H-52 standard.

The bending elastic modulus and bending yield strength were measured using a 2 mm thick press sheet and subject to ASTM D790 standard 1, and were 2.5X 10 kg/cJ and 810 kg/cJ, respectively.
It was cJ. The glass transition temperature Tg is D manufactured by DuPont.
ynamic Mechanical＾nalyser
(D M A )・Loss elastic modulus E″ is 5°C
The temperature was measured at a heating rate of /min, and the peak temperature was determined to be 150°C.

Furthermore, the melting point A was measured from -120°C to 400°C at a heating rate of 10°C/min using DuPont 990 type DSC.
No melting curve (peak) was observed. The electrical properties were measured using an IKIIz dielectric loss measuring device manufactured by Ando Electric, and the dielectric constant was 1.
9, and the dielectric loss tangent (tan δ) was 2.3×10′. Furthermore, in order to examine chemical resistance and solvent resistance,
Press molded products at room temperature are treated with sulfuric acid (97%) and aqueous ammonia (
20%), acetone, ethyl acetate, etc. for 20 hours, and the appearance was observed, and no properties such as color change, decrease in transparency, deformation, dissolution, or cracking were observed.

In addition, DuPont's Thero mechanical
The thermal deformation temperature of one wholesaler sheet (5°C/min temperature increase, 49g load, quartz needle 0.635mm 0.1mm penetration temperature) was measured with lΔnalyser (TMA) and found to be 139°C. Further, the density determined by the density gradient tube method was 1.032, g/c+a, and the refractive index n9 determined by the Atsube refraction needle was 1.540.

Pencil hardness, which is an index of hardness, was H.

Examples 2 to 15 The same operations as in Example 1 were carried out except that the monomer components were changed as shown in Table 1 and the copolymerization conditions were changed as shown in Table 2.
I got the result. Note that Table 2.3 lists the conditions and results of Example 1.

〔Effect of the invention〕

As described above, the polymer of the present invention has transparency and
Heat resistance, heat aging resistance, chemical resistance, solvent resolving power, dielectric properties,
It exhibits high levels of mechanical properties and can be used in a wide range of fields as mentioned above, bringing great benefits to industry.

Claims (3)

[Claims] (1) (A) A polymer consisting of a polycyclic monomer component represented by the following general formula (I) and optionally ethylene, ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (where R^1 to R^1^2 are hydrogen, alkyl groups, or halogens, and may be the same or different, and R
^9 or R^1^0 and R^1^1 or R^1^2 may mutually form a ring. Furthermore, n is a positive number of 2 or more, and R^5 to R^8 that are repeated multiple times may be the same or different. ) (B) The ethylene/polycyclic monomer component (molar ratio) is 95/5 to 0/100, and (C) the polycyclic monomer component unit is mainly composed of the following general formula (I
It has the structure shown in I), and has mathematical formulas, chemical formulas, tables, etc.▼ (II) (D) Intrinsic viscosity measured in decalin at 135℃ [η]
A novel polymer defined by: 0.005 to 20 dl/g. (2) The novel polymer according to claim 1, further comprising a copolymerizable third monomer component. (3) The third monomer component is 5 polycyclic monomer component units.
The novel polymer according to claim 2, which has a content of 0 mol % or less.