JPH0414685B2 - - Google Patents

Description

[Detailed description of the invention]

The purpose of the present invention is to provide a new random copolymer that has excellent transparency and has well-balanced mechanical properties such as heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and rigidity. More specifically, ethylene and 1,4,5,8-dimethano-
The present invention relates to a random copolymer containing 1,2,3,4,4a,5,8,8a-octahydronaphthalenes (hereinafter abbreviated as DMONs) as a monomer component.
Another object of the present invention is to provide a method for producing the random copolymer. 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. Polymethyl methacrylate has problems in that it is easily attacked by ethyl acetate, acetone, toluene, etc., swells in ether, and has low heat resistance. Further, although polyethylene terephthalate has excellent heat resistance and mechanical properties, it has the problem of being weak against strong acids and alkalis and being susceptible to hydrolysis. On the other hand, polyolefins, which are famous as general-purpose resins, have excellent chemical resistance, solvent resistance, and mechanical properties, but many have poor heat resistance, and are transparent because they are crystalline resins. inferior to sex. 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.
It is hard to say that the effect is sufficient. On the contrary, adding a third component such as a nucleating agent may impair the excellent properties that polyolefin originally has.
In addition, the rapid cooling method requires a large-scale apparatus, and there is a risk that heat resistance, rigidity, etc. may also decrease as the degree of crystallinity decreases. Therefore, the present inventors conducted repeated research to find out whether it was possible to obtain a synthetic resin that was transparent and had a good balance of heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and mechanical properties. As a result, they discovered that a copolymer of ethylene and a specific bulky comonomer could achieve the objective. As for copolymers of ethylene and bulky comonomers, for example, US Pat. No. 2,883,372 discloses copolymers of ethylene and 2,3-dihydrodicyclopentadiene. However, although this copolymer has an excellent balance of rigidity and transparency, it has a glass transition temperature of around 100°C and is poor in heat resistance.
A copolymer of ethylene and ethylidenenorbornene also exhibits similar properties. However, the ethylene copolymers containing DMONs as comonomers discovered by the present inventors have excellent mechanical properties such as transparency, chemical resistance, solvent resistance, dielectric properties, and rigidity, and generally have a glass transition temperature of 100%. C or above, it has excellent heat resistance, and since it has no unsaturated bonds, it has excellent long-term heat aging resistance. DMONs, which are comonomers used by the present inventors to copolymerize with ethylene, have already been published in
It is disclosed in JP-A-14910 or JP-A-58-127728 that it can be used as a monomer for polymers. However, the former concerns homopolymers of DMONs or copolymers of DMONs with comonomers of the norbornene type, while the latter teaches the use of linear olefins as molecular weight modifiers for the homopolymers or copolymers of DMONs. However, since it is targeted at ring-opened polymers, it has a structure with unsaturated bonds in the polymer main chain, as shown in the general formula (a) below, and has poor heat aging resistance. You can only get things. On the other hand, the copolymer of the present invention has a structure in which the DMON units in the polymer chain are shown in the following general formula (), and has substantially no or no unsaturated bonds. Even if the amount is very small, it is considered to be chemically stable and excellent in heat aging resistance. In this way, the copolymer of the present invention and the
The copolymer of the present invention is completely different in structure from the polymers of No. 14910 and JP-A-58-127728, and the copolymer of the present invention cannot be obtained even with the technical content disclosed in both patent publications. do not have. That is, the present invention provides (A) ethylene and 1, represented by the following general formula ().
4,5,8-dimethano-1,2,3,4,4a,
A random copolymer consisting of 5,8,8a-octahydronaphthalenes (hereinafter abbreviated as DMONs), (Here, R ₁ and R ₂ are hydrogen, an alkyl group, and a halogen, and each may be the same or different.) (B) Ethylene/DMONs (molar ratio) is 20/80 to 90/10. , (C) The DMON class unit has a structure shown by the following general formula (), (D) Intrinsic viscosity [η] measured in decalin at 135℃
Regarding a new random copolymer defined by 0.3 to 10 dl/g,
Separately, ethylene and DMONs in a hydrocarbon medium,
The present invention relates to a method for producing the random copolymer, characterized in that the copolymerization is carried out in the presence of a catalyst formed from a hydrocarbon-soluble vanadium compound and a halogen-containing organoaluminum compound. The content ratio (mole ratio) of ethylene/DMONs is
20/80 to 90/10, preferably 20/80 to 90/10
It is 85/15. And DMONs are in the copolymer.

It is copolymerized with the structure [Formula]. Since DMONs have the above structure, the iodine value of the copolymer of the present invention is usually 5 or less, and most of them are 1 or less. Therefore, the polymer has a chemically stable structure and excellent heat aging resistance. The structure of the DMON units in the copolymer chain can be determined by preparing a copolymer sample using the following procedure, measuring the ¹³ CFT-NMR spectrum of this sample, and analyzing the spectrum obtained using a conventional method. Identification confirmed. Sample preparation (a) Put the polymer together with the solvent hexachlorobutadiene into a sample tube for NMR measurement with a diameter of 10 mm.
The amount of polymer and solvent is 200mg/polymer/1.5
ml-solvent concentration to be obtained. (b) After leaving the sample tube at 120℃ for 12 hours, further heat it to about 250℃.
for 2-3 minutes to completely and evenly dissolve the polymer. (c) Further leave the solution at 120°C for 1 to 2 hours. ¹³ CFT-NMR spectrum measurement Measured at 120℃ using 500MHz ¹³ CFT-NMR (manufactured by JEOL). The new polymers have an intrinsic viscosity [η] of 0.3 to 10 dl/g, preferably 0.8 to 8 dl/g, measured in decalin at 135°C. When [η] is within the above range, workability, heat resistance and mechanical properties are all good. The novel polymers of the present invention are generally amorphous or poorly crystalline, preferably amorphous. Therefore, transparency is good. In general, the degree of crystallinity measured by X-rays is 5% or less, often 0%, and the melting point measured by differential scanning calorimetry (DSC) is usually 126° C. or less, which is often not observed. When the ethylene ratio is greater than 90, crystallinity based on ethylene chains appears, and transparency, which is a characteristic of amorphous polymers, is impaired. If the ethylene ratio is less than 20, the polymerization activity and molecular weight will be significantly reduced, and the resulting polymer will have low transparency. The fact that the novel polymer of the present invention has excellent heat resistance is that
This is supported by the fact that the glass transition temperature is high.
That is, the glass transition temperature of DMA is usually measured to be in the range of 80 to 220°C, and in many cases in the range of 100 to 200°C. In addition, the pyrolysis temperature is defined as the temperature at which weight loss starts when the temperature is raised at a rate of 10°C/min under a nitrogen stream using a thermobalance (TGA: manufactured by Rigaku Denki Co., Ltd.), and is usually 350 to 420°C, often 370 to 410°C. ℃
within the range of Density was determined by the density gradient tube method (ASTM D
1505), usually 0.86 to 1.30g/cm ³ , often 0.94
to 1.30g/cm ³ , especially 0.96 to 1.10g/cm ³
Many of them are in the range of . As for electrical properties, the dielectric constant (1KHz) according to ASTM D 150 is usually 1.5 to 4.0, often 1.7 to 2.6, and the dielectric loss tangent is 5 × 10 ^-3 to 5 × 10 ^-5 .
Most are in the range of 5 x 10 ^-4 to 8 x 10 ^-5 . The novel polymer of the present invention has excellent transparency, heat resistance, heat aging resistance, mechanical properties, dielectric properties, chemical resistance, and solvent resistance.
It can be applied to optical fields such as optical fibers and glass windows, electrical fields such as water tanks for electric irons and microwave oven products, and medical and chemical fields such as syringes, pipettes, and animal gauges. The novel polymers of the present invention are processed by well-known methods. For example, single-screw extruder, vented extruder, twin-screw extruder, conical twin-screw extruder, co-kneader, plateifier,
Extrusion molding, injection molding, blow molding, rotary molding, etc. are performed using mixtruders, twin-screw conical screw extruders, planetary screw extruders, gear type extruders, screwless extruders, etc. In addition, during the molding process, well-known additives such as heat stabilizers, light stabilizers, antistatic agents, slip agents, anti-blocking agents, antifogging agents, lubricants, inorganic and organic fillers are added as necessary. Agents, dyes, pigments, etc. may be added. Examples of such additives include phenolic or sulfur antioxidants. 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-di-tert-butylphenol)
Propionate, distearyl-3,5-di-
tert-butyl-4-hydroxybenzylphosphonate, 2,4,6-tris(3',5'-di-tert-
Butyl-4'-hydroxybenzylthio)-1,3,
5-triazine, distearyl (4-hydroxy-3-methyl-5-tert-butylbenzyl) malonate, 2,2'-methylenebis(4-methyl-6
-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,
2'-methylenebis[6-(1-methylcyclohexyl)p-cresol], bis[3,5-bis[4-hydroxy-3-tert-butylphenyl]
Butiric acid] glycol ester, 4,
4'-Butylidenebis(6-tert-butyl-m-cresol), 1,1,3-tris(2-methyl-
4-Hydroxy-5-tert-butylphenyl)butane, bis[2-tert-butyl-4-methyl-6
-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 1,
3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butyl)benzyl isocyanurate, 1,3,5-tris(3,5-di-tert-
Butyl-4-hydroxybenzyl)-2,4,6
-trimethylbenzene, tetrakis[methylene-
3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 1,3,
5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,
5-Tris [(3,5-di-tert-butyl-4-
hydroxyphenyl)propionyloxyethyl]isocyanurate, 2-octylthio-4,
6-di(4-hydroxy-3,5-di-tert-butyl)phenoxy-1,3,5-triazine,
Phenols such as 4,4'-thiobis(6-tert-butyl-m-cresol) and carbonic acid oligoesters of 4,4'-butylidenebis(2-tert-butyl-5-methylphenol) (for example, polymerization degree 2,
Examples include polyhydric phenol carbonate oligoesters such as 3, 4, 5, 6, 7, 8, 9, 10, etc.). Examples of sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl, dimyristyl, and distearyl; and polyhydric alcohols of alkylthiopropionic acids such as butyl, octyl, lauryl, and stearyl (e.g., glycerin, trimethylolethane, trimethylolpropane, and pentyl). Erythritol, trishydroxyethyl isocyanurate) (eg pentaerythritol tetralauryl thiopropionate). Alternatively, phosphorus-containing compounds may be added, such as trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-diphenyl phosphite, tris(2,4-
di-tert-butylphenyl) phosphite, triphenyl phosphite, tris(butoxyethyl) phosphite, tris(nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra(tridecyl)-1,1,
3-tris(2-methyl-5-tert-butyl-4
-hydroxyphenyl)butane diphosphite,
Tetra( _C12 - _C15 mixed alkyl)-4,4'-isopropylidene diphenyl diphosphite, Tetra(tridecyl)-4,4'-butylidenebis(3-methyl-6-tert-butylphenol) diphosphite, Tris (3,5-di-tert-butyl-4-
hydroxyphenyl) phosphite, tris(mono-dimixed nonylphenyl) phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis(octylphenyl) bis[4,4'-butylidene bis(3- Methyl-6-tert
-butylphenol)]・1,6-hexanediol diphosphite, phenyl・4,4′-isopropylidene diphenol・pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, tris[4,4'-isopropylidene bis(2
-tert-butylphenol)] phosphite, phenyl diisodecyl phosphite, di(nonylphenyl)pentaerythritol diphosphite), tris(1,3-di-stearoyloxyisopropyl)phosphite, 4,4'-isopropylidene bis(2 -tert-butylphenol)・
Di(nonylphenyl)phosphite, 9,10-di-hydro-9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide, tetrakis(2,4-di-tert-butylphenyl)-4,4' −
Examples include biphenylene diphosphonite. Also, 6-hydroxychroman derivatives such as various tocopherols α, β, γ, δ and mixtures thereof, 2-(4-methyl-pent-3-enyl)
2,5-dimethyl substituted product, 2,5,8-trimethyl substituted product, 2,5, -6-hydroxychroman
7,8-tetramethyl substituted product, 2,2,7-trimethyl-5-tert-butyl-6-hydroxychroman, 2,2,5-trimethyl-7-tert-butyl-6-hydroxychroman, 2,2 , 5-trimethyl-6-tert-butyl-6-hydroxychroman, 2,2-dimethyl-5-tert-butyl-6
-Hydroxychroman, etc. Alternatively, the general formula MxAly(OH)2x+3y-2z(A)z・aH ₂ O (where M is Mg, Ca or Zn, A is an anion other than a hydroxyl group, and x, y and z are positive (a represents 0 or a positive number), such as Mg ₆ Al ₂ (OH) ₁₆ CO ₃・4H ₂ O, Mg ₈ Al ₂ (OH) ₂₀ CO ₃・5H ₂ O, Mg ₅ Al ₂ (OH) ₁₄ CO ₃・4H ₂ O, Mg ₁₀ Al ₂ (OH) ₂₂ (CO ₃ ) ₂・4H ₂ O, Mg ₆ Al ₂ (OH) ₁₆ HPO ₄・4H ₂ O, Ca ₆ Al ₂ (OH) ₁₆ CO ₃・4H ₂ O, Zn ₆ Al ₂ (OH) ₁₆ CO ₃・4H ₂ O, Zn ₆ Al ₂ (OH) ₁₆ SO ₄・4H ₂ O, Mg ₆ Al ₂ (OH) ₁₆ SO _{3.4H 2} O, Mg ₆ Al ₂ (OH) ₁₂ CO _{3.3H 2} O, etc. may be blended. Examples of light stabilizers include 2-hydroxy-
4-methoxybenzophenone, 2-hydroxy-
4-n-octoxybenzophenone-2,2'-di-hydroxy-4-methoxybenzophenone,
Hydroxybenzophenones such as 2,4-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
Benzotriazoles such as -(2'-hydroxy-3',5'-di-tert-amyl phenyl)benzotriazole, phenyl salicylate, p-tert-butylphenyl salicylate, 2,4-di-tert-
Butylphenyl-3,5-di-tert-butyl-4
-Hydroxybenzoate, hexadecyl-3,
Benzoates such as 5-di-tert-butyl-4-hydroxybenzoate, 2,2'-thiobis(4-tert-octylphenol) Ni salt, [2,
2'-thiobis(4-tert-octylphenolate)]-n-butylamine Ni, (3,5-di-tert
Nickel compounds such as -butyl-4-hydroxybenzyl)phosphonic acid monoethyl ester Ni salt, substituted acrylonitriles such as methyl α-cyano-β-methyl-β-(p-methoxyphenyl)acrylate, and N′- 2-ethylphenyl-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-tetramethyl-4-piperidine) sebaciate, poly[{(6-(1,1,3,3-tetra methylbutyl)imino}-1,3,5-triazine-2,4
-diyl{4-(2,2,6,6-tetramethylpiperidyl)imino}hexamethylene], 2-(4
-hydroxy-2,2,6,6-tetramethyl-
Examples include hindered amine compounds such as a condensate of 1-piperidyl)ethanol and dimethyl succinate. Examples of lubricants include aliphatic hydrocarbons such as paraffin wax, polyethylene wax, and polypropylene wax, and higher fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, and behenic acid. or their metal salts, i.e. lithium salts, calcium salts, sodium salts,
Magnesium salts, potassium salts, etc., aliphatic alcohols such as palmityl alcohol, cetyl alcohol, stearyl alcohol, capronic acid amide, caprylic acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide Examples include aliphatic amides such as, esters of aliphatic and alcohol, fluorine compounds such as fluoroalkylcarboxylic acid or its metal salt, and fluoroalkylsulfonic acid metal salt. Fillers include inorganic or organic fibrous fillers such as glass fiber, silver-coated glass fiber, stainless steel fiber, aluminum fiber, potassium titanate fiber, carbon fiber, and Kevlar fiber, talc, calcium carbonate, magnesium hydroxide, and oxidized Inorganic or organic fillers in powder, granular, or flake form, such as calcium, magnesium sulfate, graphite, nickel powder, silver powder, copper powder, carbon black, silver coated glass beads, aluminum coated glass beads, aluminum flakes, stainless steel flakes, etc. can be exemplified. Furthermore, the novel copolymer of the present invention can also be used in combination with various known 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. Poly-4-methylpentene-1, polybutene-1, polyisoprene, polybutadiene, polystyrene, or copolymers of monomers constituting the above-mentioned polymers, such as ethylene-propylene copolymer, propylene-butene-1 copolymer copolymers, propylene/isobutylene copolymers, styrene/isobutylene copolymers, styrene/butadiene copolymers, terpolymers of ethylene and propylene with dienes such as hexadiene, cyclopentadiene, ethylidene norbornene, or polymers thereof. Blends, graft polymers, block copolymers, etc. (b) Halogen-containing vinyl polymers, specifically polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene,
chlorinated rubber, etc. (c) Polymers derived from α,β-unsaturated acids and their derivatives, specifically polyacrylate, polymethacrylate, polyacrylamide, polyacrylonitrile, or monomers constituting the above polymers. and other copolymerizable monomers, such as acrylonitrile/butadiene/styrene copolymer, acrylonitrile/styrene copolymer, acrylonitrile/styrene/acrylate ester copolymer, (d)unsaturated alcohol and Polymers derived from amines or their acyl derivatives or acetals, specifically polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine, or a copolymer of the monomer constituting the polymer and other copolymerizable monomers, such as ethylene/vinyl acetate copolymer, (e) a polymer derived from an epoxide, specifically polyethylene oxide or bis (f) Polyacetals such as polymers derived from glycidyl ether, specifically polyoxymethylene, polyoxyethylene, polyoxymethylene containing ethylene oxide as a comonomer, (g) polyphenylene oxide, (th) polycarbonate , (li) polysulfones, (n) polyurethane and urea resins, (l) polyamides and copolyamides derived from diamines and dicarboxylic and/or aminocarboxylic acids or corresponding lactams, in particular nylon 6, nylon 66, Nylon 11, nylon 12, etc., dicarboxylic acids and dialcohols and/or
or polyesters derived from oxycarboxylic acids or the corresponding lactones, in particular polyethylene terephthalate, polybutylene terephthalate, poly1,4-dimethylol cyclohexane terephthalate, etc. (iv) polyesters derived from aldehydes and phenols, urea or melamine Polymers with a crosslinked structure, specifically phenol/formaldehyde resin, urea/formaldehyde resin, melamine/
Formaldehyde resins, etc. (f) Alkyd resins, specifically glycerin phthalate resins, etc. (b) Derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols, using vinyl compounds as crosslinking agents. unsaturated polyester resins and halogen-containing modified resins obtained by can be exemplified. In order to produce the random copolymer of the present invention, ethylene and DMONs may be copolymerized in the presence of a catalyst consisting of a well-known panadium compound and a reducing agent such as an alkyl aluminum compound. In the present invention, ethylene was selected as the α-olefin to be copolymerized with DMONs.
The above α-olefins cannot be polymerized using a panadium-based catalyst, and when polymerized using a well-known titanium-based catalyst, only α-olefin homopolymers are preferentially polymerized, resulting in copolymers with DMONs. This is due to the fact that it is difficult to be exposed to. DMONs as raw materials can be easily produced by condensing norbornenes and cyclopentadiene as shown in the following formula. Specific examples of DMONs include 1,
4,5,8-dimethano-1,2,3,4,4a,
In addition to 5,8,8a-octahydronaphthalene,
2-methyl-1,4,5,8-dimethano-1,
2,3,4,4a,5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydro Naphthalene, 2-propyl-1,4,5,
8-dimethano-1,2,3,4,4a,5,8,
8a-octahydronaphthalene, 2-hexyl-
1,4,5,8-dimethano-1,2,3,4,
4a,5,8,8a-octahydronaphthalene, 2
-stearyl-1,4,5,8-dimethano-1,
2,3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-
Dimethano-1,2,3,4,4a,5,8,8a-
Octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethano-1,2,3,
4,4a,5,8,8a-octahydronaphthalene,
2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,
8-dimethano-1,2,3,4,4a,5,8,
Examples include 8a-octahydronaphthalene.
Among these, preferred are those in which either R ₁ or R ₂ is substituted with an alkyl group having 1 to 20 carbon atoms. Vanadium compounds used when copolymerizing the above DMONs and ethylene include VCl ₄ ,
Vanadium halides such as VBr ₄ , VCl ₃ , VBr ₃ , vanadium oxyhalides such as VOCl ₃ , VOBr ₃ , VOCl ₂ , VOBr ₂ or VO(OR) _o
X _3-o (where R is a hydrocarbon group, X is a halogen,
Examples include vanadium compounds represented by the formula (0<n≦3). Among these, hydrocarbon-soluble vanadium compounds, particularly vanadium oxyhalides or compounds represented by VO(OR) _o x _3-o, are preferred. In _the compound represented by VO(OR) _o , especially 1 to 3
The one is good. Further, n is in the range of 0<n≦3, preferably 1≦n≦1.5. Examples of such vanadium compounds include VO( _OCH3 ) _Cl2 , VO
( _OCH3 ) _2Cl , VO( _OCH3 ) ₃ , VO( _OC2H5 ) _{Cl2 ,}
VO(OC ₂ H ₅ ) _1.5 Cl _1.5 VO(OC ₂ H ₅ ) ₂ Cl, VO
(OC ₂ H ₅ ) ₃ , VO (OC ₂ H ₅ ) _1.5 Br _1.5 , VO (OC ₃ H ₇ )
Cl ₂ , VO (OC ₃ H ₇ ) _1.5 Cl _1.5 , VO (OC ₃ H ₇ ) ₂ Cl, VO
(OC ₃ H ₇ ) ₃ , VO(On−C ₄ H ₉ )Cl ₂ , VO(On−
C ₄ H ₉ ) ₂ Cl, VO (OisoC ₄ H ₉ ) ₂ Cl, VO
Examples include (OsecC ₄ H ₉ ) ₃ , VO(OC ₅ H ₁₁ ) _1.5 Cl _1.5 or a mixture thereof. these are
Reacting VOCl ₃ with alcohol, or
It can be easily obtained by reacting VOCl3 and VO(OR _{)3 .} Alkylaluminum compounds used with vanadium compounds have the general formula R′mAlX′ _3-n (where
R′ is a hydrocarbon group, X′ is a halogen, 0<m≦3)
It is indicated by. In particular, in the above formula, it is preferable that the average value of m is in the range of 1≦m≦2, particularly 1.2≦m≦1.8. Examples of the alkylaluminum compound include trialkylaluminium, dialkylaluminum halide, alkylaluminum dihalide, aluminum trihalide, or any mixture thereof. The ratio of Al/V (molar ratio) used between the alkyl aluminum compound and the panadium compound must be 1 or more, preferably 30 or less, and particularly preferably 2 to 20. Copolymerization is carried out in a hydrocarbon medium. For example, aliphatic hydrocarbons such as hexane, heptane, octane, and kerosene, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as benzene, toluene, and xylene may be used alone or in combination as a solvent. I can do it. The copolymerization is preferably carried out at a concentration of the vanadium compound in the reaction medium of 0.05 to 20 mmol/, preferably 0.1 to 10 mmol/. In addition, alkyl aluminum compounds are
As already mentioned, the Al/V (molar ratio) is adjusted to be 1 or more, preferably 30 or less, and particularly preferably 2 to 20. Ethylene and DMONs differ depending on the composition of the desired copolymer, the type of reaction medium, polymerization temperature, etc., but generally the molar ratio of ethylene/DMONs in the reaction medium is 1/1 to 1/1.
Adjusted to 1/100. The polymerization temperature is -
The temperature is 50 to 100°C, preferably -30 to 50°C, and the polymerization pressure is generally maintained at 0 to 50 kg/cm ² , preferably 0 to 20 kg/cm ² . For controlling the molecular weight of the copolymer, a molecular weight controlling agent such as hydrogen may be present as appropriate. Hereinafter, the content of the present invention will be explained in more detail using Examples, but the content of the present invention is not limited to these Examples, and any embodiment is possible as long as the purpose is not impaired. Example 1 A stirring blade, a gas blowing pipe, a thermometer, and a dropping funnel were attached to a sufficiently dried separable flask No. 3, and the flask was sufficiently purged with nitrogen. Toluene 1, which had been dehydrated and dried using a molecular sieve, was placed in this flask. In a flask under nitrogen flow, 2 mmol of dichloroethoxyoxovanadium, DMONs (2-methyl-1,4,5,8-dimethano-1,2,3,
4,4a,5,8,8a-octahydronaphthalene)
and 20 mmol of ethylaluminum sesquichloride were added to the dropping funnel. Dry ethylene 40/
hr, and a mixed gas of 160/hr of nitrogen 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 10 ml of methanol to the polymerization solution. After stopping the reaction, the polymer solution was poured into a large amount of methanol to precipitate a copolymer, and after further washing with methanol, vacuum drying was carried out at 60°C overnight to obtain 35g of copolymer.
I got it. The ethylene composition in the copolymer measured by ¹³ C-NMR analysis was 60 mol%, the limit value [η] measured in decalin at 135°C was 1.9, and the iodine value was 1.0. In addition, in order to measure mechanical properties, 230℃ hot
A press molded sheet with a thickness of 1 mm or 2 mm was produced using a press. When X-ray diffraction was performed using these sheets, no scattering due to crystals was observed, and the crystallinity was 0%. Also, transparency is
Haze according to ASTM D 1003-52
A total of 10% was measured on a 1 mm sheet. The bending elastic modulus and bending yield strength were measured using a 2 mm thick press sheet according to ASTM D 790, and were 2.2 x 10 ⁴ Kg/cm ² and 730, respectively.
It was Kg/ ^cm2 . The glass transition temperature Tg was measured using a Dynamic Mechanical Analyzer (DMA) manufactured by DuPont.
The loss modulus E'' was measured at a heating rate of 5℃/min, and the peak temperature was determined to be 130℃.
It was hot. Furthermore, the melting point Tm is 990 manufactured by Dupont.
- type DSC at a heating rate of 10℃/min.
When measured in the range of 120℃ to 400℃, the melting curve (peak) was also measured using a thermobalance (TGA) manufactured by Rigaku Denki Co., Ltd.
The thermal decomposition temperature was measured at 380°C. The electrical properties were measured at 1 KHz using a dielectric loss measuring device manufactured by Ando Electric, and the dielectric constant was 1.9 and the dielectric loss tangent (tan δ) was 9.1×10 ^-5 . moreover,
To examine chemical resistance, press-formed products were heated at room temperature with sulfuric acid (97%), aqueous ammonia (20%), acetone,
When the appearance was observed after soaking in ethyl acetate etc. for 20 hours, no changes in color, decreased transparency, deformation, dissolution, or cracks were observed. The density was measured according to ASTM D 1505 and was found to be 1.021 g/cm ³ . Examples 2 to 17, Comparative Examples 1 to 2 The same operations as in Example 1 were performed except that the copolymerization reaction conditions were changed as shown in Table 1, and the results shown in Table 2 were obtained. In addition, in Example 17, N ₂ 140/hr was used instead of N ₂ 160/hr in Example 1.
/hr and H ₂ 20/hr to obtain a copolymer with an [η] value of about 0.4.

【table】

【table】

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【table】

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Claims (1)

[Claims] 1 (A) Ethylene and 1,4,5,8-dimethano-1,2,3,4, represented by the following general formula ();
A random copolymer consisting of 4a,5,8,8a-octahydronaphthalenes (hereinafter abbreviated as DMONs), (Here, R ₁ and R ₂ are hydrogen or alkyl groups, and may be the same or different.) (B) Ethylene/DMONs (molar ratio) is 20/80 to 90/10, (C ) The DMON class unit takes the structure shown by the following general formula (), (D) Intrinsic viscosity [η] measured in decalin at 135℃
A novel random copolymer defined by 0.3 to 8 dl/g. 2. Ethylene and DMONs in a hydrocarbon medium,
(A) ethylene and 1 represented by the following general formula (), characterized by copolymerizing in the presence of a catalyst formed from a hydrocarbon-soluble vanadium compound and a halogen-containing organoaluminum compound;
4,5,8-dimethano-1,2,3,4,4a,
A random copolymer consisting of 5,8,8a-octahydronaphthalenes (hereinafter abbreviated as DMONs), (Here, R ₁ and R ₂ are hydrogen or alkyl groups, and may be the same or different.) (B) Ethylene/DMONs (molar ratio) is 20/80 to 90/10, (C ) The DMON class unit takes the structure shown by the following general formula (), (D) Intrinsic viscosity [η] measured in decalin at 135℃
A method for producing a novel random copolymer defined by 0.3 to 8 dl/g.