JPH072810B2 - Method for producing new random multi-addition copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention has excellent transparency and mechanical properties such as heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties and rigidity. Aiming to provide a method for producing a balanced new random multi-component addition copolymer, more specifically, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8, 8a-octahydronaphthalene (also called tetradodecene:
DMONs may be abbreviated) and ethylene, a two-component monomer, and an α-olefin having 3 or more carbon atoms and / or a cycloolefin, a third component monomer and a fourth component monomer are added and polymerized. The present invention relates to a method for producing an original random addition copolymer or a quaternary random addition copolymer.

[Prior Art] Polycarbonate, polymethyl methacrylate, polyethylene terephthalate, and the like are known as synthetic resins having excellent transparency. For example, polycarbonate is a resin that is excellent in transparency, heat resistance, heat aging resistance, and impact resistance. However, there is a problem that it is easily attacked by a strong alkali and has poor chemical resistance. Polymethylmethacrylate is easily attacked by ethyl acetate, acetone, toluene, etc., swells in ether, and has a problem of low heat resistance. Further, although polyethylene terephthalate has excellent heat resistance and mechanical properties, it has a problem that it is weak against strong acids and alkalis and is easily hydrolyzed.

On the other hand, polyolefins, which are famous as general-purpose resins, often have excellent chemical resistance, solvent resistance, and mechanical properties, but many have poor heat resistance, and because they are crystalline resins, they are transparent. Inferior to. Generally, in order to improve the transparency of polyolefin, a method of stopping the growth of crystals by adding a nucleating agent to refine the crystal structure or quenching is used,
The effect is hard to say. Rather, the addition of a third component such as a nucleating agent may impair the excellent properties inherent to polyolefin, and the quenching method requires a large-scale equipment and lowers the crystallinity. Therefore, heat resistance and rigidity may be reduced.

Therefore, the present applicant has conducted repeated research to find out whether a synthetic resin having a good balance of heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and mechanical properties while having transparency can be obtained. It was found that a copolymer of ethylene and a specific bulky comonomer can achieve the object, and disclosed the technical content thereof in Japanese Patent Application No. 59-16995.

Regarding a copolymer of ethylene and a bulky monomer, for example, U.S. Pat. No. 2,883,372 discloses a copolymer of ethylene and 2,3-dihydrodicyclopentadiene. However, although this copolymer has an excellent balance of rigidity and transparency, it has a glass transition temperature around 100 ° C and is poor in heat resistance. A copolymer of ethylene and ethylidene norbornene also exhibits similar properties. However, the ethylene copolymer using DMONs as a comonomer found by the applicant is excellent in mechanical properties such as transparency, chemical resistance, solvent resistance, dielectric properties and rigidity, and generally has a glass transition temperature. 100
Since it is at least ℃, it is excellent in heat resistance, and since it has no unsaturated bond, it is also excellent in long-term heat aging resistance.
DMONs, which are the comonomers used by the applicant for copolymerization with ethylene, have already been disclosed in JP-B-46-14910 or JP-A-58-127728, which can be used as a monomer of a polymer. There is. However, the former relates to homopolymers of DMONs or copolymers of DMONs and norbornene-type comonomers, and the latter teaches the use of chain olefins as molecular weight regulators for homo- or copolymerization of DMONs. However, since it is intended for ring-opening polymers, it has a structure having an unsaturated bond in the polymer main chain as shown in the following general formula (a), and heat aging resistance is Only inferior can be obtained. On the other hand, the copolymer proposed by the applicant has a structure represented by the following general formula (II) as a main structure, and even if it has substantially no unsaturated bond or has an unsaturated bond, It is considered to be chemically stable and excellent in heat aging resistance because it is very small.

Thus, the copolymer proposed by the applicant and the polymers disclosed in JP-B-46-14910 and JP-A-58-127728 are completely different in structure, and the technical contents disclosed in both patent publications. However, the copolymer proposed by the applicant cannot be obtained.

The present invention relates to an improvement of the novel random copolymer proposed in the above-mentioned Japanese Patent Application No. 59-16995, that is, the monomer component of the previously proposed random copolymer further comprises an α-containing 3 or more carbon atoms. The present invention relates to a method for producing a ternary or quaternary copolymer by adding an olefin or a cycloolefin or both of them. And, regarding the method for producing this random multi-component copolymer of the present invention, it is not described at all in the prior art documents described so far, and even with the disclosure thereof, such a copolymer cannot be obtained. Of course.

[Structure of the Invention] That is, the present invention provides (A) (i) 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octa represented by the following formula (I). Random addition polymerization of hydronaphthalene (hereinafter abbreviated as DMON), (ii) ethylene, and (iii) α-olefin and / or cycloolefin having 3 or more carbon atoms, (Here, R ¹ and R ² are hydrogen or an alkyl group and may be the same or different.) (B) Ethylene / DMONs (molar ratio) 95/5 to 5/95, (C) [Α-olefin and / or cycloolefin having 3 or more carbon atoms] / DMONs (molar ratio) is 80/20 to 5 /
95, (D) DMON unit has a structure substantially represented by the following formula (II), (E) The intrinsic viscosity [η] measured in decalin at 135 ° C is
It is a method for producing a novel random multi-component addition copolymer defined by 0.005 to 20 dl / g.

Although the gist of the present invention is as described above, in more detail, the random multi-addition copolymer obtained by the method of the present invention includes the following three modes.

(I) DMONs / ethylene / a terpolymer of α-olefin having 3 or more carbon atoms, (II) DMONs / ethylene / cycloolefin 3
Terpolymer, (III) quaternary copolymer composed of DMONs / ethylene / α-olefin having 3 or more carbon atoms / cycloolefin.

Furthermore, the novel random multi-component addition copolymer obtained by the present invention may contain a small amount of diene component.

In the present invention, the term cycloolefin includes styrenes and unsaturated polycyclic hydrocarbon compounds (which may have a crosslinking bond) in addition to the cycloolefin which is usually mentioned as described later in detail.

Hereinafter, various monomer components used in the method of the present invention, a method for producing a random multi-addition copolymer using the same, and properties of the obtained random multi-addition copolymer will be described in detail.

DMONs DMONs, which are a raw material for the random polyaddition polymer of the present invention, can be easily produced by condensing norbornenes and cyclopentadiene as shown in the following formula.

In this general formula, R ¹ and R ² are hydrogen or a straight chain, a branched chain,
The cyclic alkyl group or halogen is halogen and may be the same or different.

Specific examples of DMONs include, for example, 1,4,5,8-dimethano-1,2,3,4,4a, 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-octahydronaphthalene, 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-chloro-1,4,5,8- Dimethano-1,2,3,4,4a, 5,8,
8a-octahydronaphthalene, 2-bromo-1,4,5,8-
Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4,4a, 5,
8,8a-octahydronaphthalene, 2,3-dichloro-1,4,
5,8,8a-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, 5,8,8a-
Examples include octahydronaphthalene. Of these, preferred are those in which either R ¹ or R ² has 1 to 10 carbon atoms.
It is substituted with 20 alkyl groups.

Α-Olefins having 3 or more carbon atoms The α-olefins having 3 or more carbon atoms are linear or branched ones, such as propylene, isopropylene, 1-butene and 3-methyl-1. -Butene, 1
-Pentene, 3-methyl-1-pentene, 4-methyl-
1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like can be mentioned. Among these,
Α-Olefins having 3 to 12 carbon atoms, particularly 3 to 6 carbon atoms are preferred.

Cycloolefin A cycloolefin, which is one of the monomer components used in the present invention, includes a wide range of cycloolefins which are used in the usual sense as described above, as well as styrenes and unsaturated polycyclic hydrocarbon compounds. It is a concept word.

More specifically, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, styrene, α-methylstyrene, norbornene, methylnorbornene, ethylnorbornene. , Isobutyl norbornene, 2,3,3a, 7a-tetrahydro-4,7
-Methano-1H-indene, 3a, 5,6,7a-tetrahydro-
4,7-methano-1H-indene and the like can be mentioned. Among these, cycloolefins having a norbornene ring such as norbornene, methylnorbornene and ethylnorbornene are preferred.

In order to produce a novel random multi-addition copolymer using such a monomer component, the above-mentioned monomer component may be subjected to random addition polymerization with a well-known Ziegler catalyst.

More specifically, the random multi-element addition copolymer to be obtained by the method of the present invention is (I) a terpolymer of DMONs / ethylene / α-olefin having 3 or more carbon atoms, (II) ) DMONs / Ethylene / Cycloolefin 3
A terpolymer, or (III) a quaternary copolymer composed of DMONs / ethylene / α-olefin / cycloolefin having 3 or more carbon atoms, and further, a copolymer containing a small amount of a diene component. In this case, the monomer component as described above may be used corresponding to each copolymer.

The Ziegler-based catalyst used in the present invention is a catalyst comprising a methane compound supported on a magnesium compound known as a highly active catalyst, or a vanadium-based compound and a reducing agent such as an alkylaluminum-based compound.

The titanium compound supported on the magnesium compound is a complex containing at least magnesium, titanium and halogen, and is preferably a compound obtained by bringing the magnesium compound and the titanium compound into intimate contact by means such as heating or co-grinding. Means that the halogen / titanium molar ratio contained in the composite exceeds about 4, and the titanium compound is not substantially desorbed by the hexane washing means at room temperature.

A good composite has a halogen / titanium (molar ratio) of about 4
, Preferably about 5 or more, more preferably about 8 or more, magnesium / titanium (molar ratio) about 3 or more, preferably about 5 to about 50, and when the complex contains an electron donor, electron donor / Titanium (molar ratio) is about 0.2 to about 6,
It is preferably about 0.4 to about 3, more preferably about 0.8 to about 2, and its specific surface area is about 3 m ² / g or more, more preferably about 40 m ² / g or more, further preferably about 100 m ² / g or more. Is. In addition, whether the X-ray spectrum of the complex shows amorphousness regardless of the starting magnesium compound, or that it is in a much more amorphous state than that of the usual commercially available magnesium dihalide. Is desirable.

As an example of means for producing the composite, for example, Japanese Patent Laid-Open No. 48-16
986, JP-A-50-108385, JP-A-50-12659
No. 0, JP-A-51-20297, JP-A-51-28189, JP-A-51-92885, JP-A-51-127185, JP-A-51-136625, JP-A-52-87489, JP-A-52-100596, JP-A-52-104593, JP-A-52-147688, JP-A-53-2580,
Means described in the Italian patent application dated November 12, 1975 can be exemplified.

The vanadium _{compound, VCl 4, VBr 4, VCl} 3, VBr 3 and halogenated _{vanadium, VOCl 3, VOBr 3, VOCl} 2, VOBr 2
Vanadium oxyhalide or VO (OR) nX _3-
n (however, R is a hydrocarbon group, X is a halogen, 0 <n ≦
A vanadium compound represented by the formula 3) is exemplified.
Among these, a hydrocarbon-soluble vanadium compound, particularly a vanadium oxyhalide or a compound represented by VO (OR) nX3 _- n is preferable. In the compound represented by VO (OR) nX3 _- n, R is an aliphatic, alicyclic or aromatic hydrocarbon group, preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Especially, those of 1 to 3 are preferable. Fork n
Is in the range of 0 <n ≦ 3, preferably 1 ≦ n ≦ 1.5.
An example of such a vanadium compound is VO (OCH ₃ )
Cl ₂ , VO (OCH ₃ ) ₂ Cl ₂ , VO (OCH ₃ ) ₃ , VO (OC ₂ H ₅ ) C
l ₂ , 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 (Oiso-C 4
_{H 9) 2 Cl, VO (} Osec-C 4 H 9) 3, VO (OC 5 H 11) 1.5 Cl 1.5
Alternatively, a mixture thereof or the like can be given. These react with VOCl ₃ and alcohol, or VOC
It can be easily obtained by reacting l ₃ with VO (OR) ₃ .

The alkylaluminum compound has the general formula R'mAlX'3 _- m
(However, R'is a hydrocarbon group, X'is a halogen, 0 <m≤
3). This alkyl aluminum compound is
Examples thereof include trialkylaluminum, dialkylaluminum halide, alkylaluminum dihalide, arbitrary mixtures thereof, and mixtures of these with alkylaluminum trihalides.

The polymerization is carried out in a hydrocarbon medium. For example, hexane, heptane, octane, aliphatic hydrocarbons such as kerosene, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene are used alone or as a mixture as a solvent. be able to.

Polymerization is adjusted so that the concentration of the former is 0.001 to 10 mmol / mole, preferably 0.01 to 5 molmol / mole in the reaction medium in the case of titanium compound and alkylaluminum compound, and the latter is Al / Ti (mole). The ratio is 5 or more, preferably 1000 or less, and particularly preferably 10 to 100. In the case of vanadium compounds and alkylaluminum compounds, the former is 0.01-50 mmol /
The concentration is preferably adjusted to 0.01 to 10 mmol / mol, and the latter has an Al / V (molar ratio) of 2 or more, preferably
It is adjusted to 50 or less, particularly preferably 3 to 20. Among these catalyst systems, the latter one using the vanadium system is particularly preferable.

When DMONs and ethylene, and α-olefins having 3 or more carbon atoms and / or cycloolefins are copolymerized,
The charging ratio of these monomer components varies depending on the composition of the desired random multi-component addition copolymer, the type of reaction medium, the polymerization temperature, the pressure, the type of catalyst, but generally the molar ratio of ethylene / DMONs in the reaction medium is 1 / 100-100 / 100, preferably 1
/ Adjust 10 to 10/1, and [α-olefins with 3 or more carbon atoms and / or cycloolefins] / DMON
The molar ratio of the compounds is adjusted to 100/1 to 1/100, preferably 10/1 to 1/50. The polymerization temperature is -50 to 300 ° C, preferably -30 to 200 ° C, and the polymerization pressure is 0 to 100 kg / cm ² , preferably 0.
Maintained at ~ 50Kg / cm ² .

A molecular weight modifier such as hydrogen may be optionally present to adjust the molecular weight of the polymer.

Random multi-component copolymer, DMONs having 3 or more carbon atoms obtained by such a method
The random multi-component addition copolymer composed of the above α-olefin, cycloolefin and ethylene is (B)
Ethylene / DMONs (molar ratio) 95/5 to 5/95, especially 90/10
In the range of 20 to 80, and the ratio of (C) [α-olefin having 3 or more carbon atoms and / or cycloolefin] / DMONs (molar ratio) is 80/20 to 5/95, especially 70/30. It is in the range of ~ 10/90. And (D) DMONs are substantially contained in the random multi-addition copolymer. Are copolymerized in the following structure. Even if a bridged unsaturated polycyclic hydrocarbon compound similar to DMONs is used as the cycloolefin of the third component, the ring-opening reaction does not occur and the structure is mainly the same as that of DMONs. Therefore, the iodine value of the random multi-component addition copolymer obtained in the present invention is usually 5 or less, and most of them is 1 or less. Moreover, ¹³ C-NMR confirms that the structure as described above is taken. Therefore, the random multi-addition copolymer obtained by the present invention has a chemically stable structure and is a polymer having excellent heat aging resistance.

The new random multi-component addition copolymer has an intrinsic viscosity [η] of 0.005 to 20 dl / g measured in decalin at 135 ° C. Especially when it is used for wax, it is preferably 0.01 to 0.3 dl / g, more preferably 0.05 to 0.2 dl / g. For general synthetic resin applications, especially 0.5-10dl / g,
The range of 0.8 to 8 dl / g is preferable.

The novel novel random multi-addition copolymer is generally amorphous or low crystalline, preferably amorphous. Therefore, the transparency is good. Generally, X-ray crystallinity is 5
% Or less, most of them are 0%, and many of them have no melting point observed by a differential scanning calorimeter (DSC).

Another property of the novel random multi-component addition copolymer is high glass transition temperature and softening temperature. That is, the glass transition temperature (T
g) is usually measured in the range of 80-190 ° C, and most often 100-190 ° C. In addition, TMA (Thermo-mechanical Analyser: manufactured by DuPont) uses a quartz needle (diameter: 0.635 mm) with a load of 49 g and a heating rate of 5 ° C / min. ~ 180 ℃, mostly 90-180 ℃
It is measured within the range of.

In addition, the thermal decomposition temperature is usually 350-420 ℃, if the thermal decomposition temperature is the weight loss start temperature raised at a rate of 10 ° C / min under a nitrogen stream using a thermal balance (TGA: manufactured by Rigaku Denki Co., Ltd.). Is 370
Within the range of ~ 400 ℃.

As a mechanical property, the flexural modulus is usually 1 × 10 ^{4 to} 3 × 10 ⁴ kg.
/ in the range of cm ^2, bending yield strength typically 300～1500Kg /
Within the range of cm ² .

Density is usually determined by density gradient tube method (ASTM D 1505)
0.86 to 1.10 g / cm ³ , most of which is in the range of 0.88 to 1.08 g / cm ³ . The refractive index (ASTM D 542) is 1.47 to 1.58, and most
Since it is in the range of 1.48 to 1.56 and is substantially amorphous, the haze (haze: ASTM D 1003) is usually 20% or less, and most are 10
% Or less.

As an electrical property, the permittivity (1KHz) according to ASTM D 150 is
1.5-3.0, mostly 1.9-2.6, dielectric loss tangent 9 × 10 ^-4 -8 ×
10 ^-5 , often within the range of 3 × 10 ^{-4 to} 9 × 10 ^-5 . It also has excellent chemical resistance and is virtually unaffected by acids and alkalis.

Further, the novel random multi-element addition copolymer obtained by the present invention shows a high glass transition point even if the content of DMONs is reduced as compared with the one disclosed in Japanese Patent Application No. 59-16995. That is, comparing those with the same glass transition point,
Compared to the DMONs / ethylene composition, the composition of (i) DMONs / (ii) ethylene / [(iii) α-olefin and / or cycloolefin] makes it possible to reduce DMONs having a higher unit price. .

The novel random multi-addition copolymer obtained by the present invention has a good balance of transparency, heat resistance, heat aging resistance, mechanical properties, dielectric properties, chemical resistance, and solvent resistance. For example, its low molecular weight is used as a synthetic wax for candles, match stem impregnating agents, paper processing agents, sizing agents, rubber anti-aging agents, corrugated water resistance agents, chemical fertilizer retarding agents, heat storage agents, ceramic binders, paper capacitors, Electric wires, electrical insulating materials such as cables, neutron moderators, fiber processing aids, water repellents for building materials, paint protection agents, polishes, thixotropy agents, pencil / crayon core hardness agents,
It can be used in the fields of corbon ink base materials, electrostatic copying toner, synthetic resin molding lubricants, release agents, resin colorants, hot melt adhesives, lubricating greases, and the like. In addition, its high molecular weight products are used in optical fields such as optical lenses, optical disks, optical fibers, glass windows, electric iron water tanks, microwave oven products, liquid crystal display substrates, printed circuit boards, high-frequency circuit boards, transparent conductive sheets and It can be used in various fields such as electric fields such as films, medical fields such as syringes, pipettes and animal gauges, chemical fields, camera bodies, various instrument housings, films, sheets and helmets.

The novel random multi-component addition copolymer obtained by the present invention is molded by a known method. For example, single-screw extruder, vented extruder, twin-screw extruder, conical twin-screw extruder, co-kneader, practicator, mixer, extruder, twin-screw conical screw extruder, planetary screw extruder, gear type extruder Extrusion molding, injection molding, blow molding, rotational molding, etc. using a screwless extruder or the like. In the molding process, known additives such as heat stabilizers, light stabilizers, antistatic agents, slip agents, antiblocking agents, antifog agents, lubricants, inorganic and organic fillers, dyes and pigments are used as necessary. Etc. may be added.

Examples of such additives include phenol-based or sulfur-based antioxidants. Examples of the phenolic antioxidant 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-methyl Cyclohexyl) p-cresol], bis [3,5-bis [4-hydroxy-3-t]
ert-Butylphenyl) butyric 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, 4,4 ′
-Phenols such as thiobis (6-tert-butyl-m-cresol) and 4,4'-butylidene bis (2-tert
Examples include polyhydric phenol carbonic acid oligoesters such as carbonic acid oligoesters of -butyl-5-methylphenol) (for example, degree of polymerization 2,3,4,5,6,7,8,9,10).

Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl-, dimyristyl-, and distearyl-, and butyl-, octyl-, lauryl-,
Alkylthiopropionic acid polyhydric alcohols such as stearyl- (eg glycerin, trimethylolethane,
Trimethylolpropane, pentaerythritol, trishydroxyethylisocyanate) ester (for example, pentaerythritol tetralauryl thiopropionate).

Further, the obtained phosphorus-containing compound may be blended with a phosphorus-containing compound as described above, and examples of the phosphorus-containing compound include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-diphenyl. Phosphite, tris (2,4-di-tert-butylphenyl) phosphite, triphenylphosphite, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra ( Tridecyl)
-1,1,3-tris (2-methyl-5-tert-butyl-4)
- hydroxyphenyl) butane diphosphite, tetra (C ₁₂ -C ₁₅ mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, tetra (tridecyl) -4,
4'-butylidene bis (3-methyl-6-tert-butylphenol) diphosphite, tris (3,5-di-tert
-Butyl-4-hydroxyphenyl) phosphite, tris (mono / di mixed nonylphenyl) phosphite, hydrogenated-4,4'-isopropylidenediphenol 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- ter
t-Butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tris [4,4′-isopropylidenebis (2-tert-butylphenol) )] Phosphite, phenyl diisodecyl phosphite, di (nonylphenyl) pentaerythritol diphosphite), tris (1,3-di-stearoyloxyisopropyl) phosphite, 4,4′-isopropylidene bis (2-tert -Butylphenol) -di (nonylphenyl) phosphite, 9,10-di-hydro-9-
Oxa-10-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-tert-butylphenyl)-
4,4'-biphenylene diphosphonite and the like can be mentioned.

Also, 6-hydroxychroman derivatives such as α, β,
γ, δ various tocophenols and their mixtures, 2-
(4-Methyl-pent-3-enyl) -6-hydroxychroman substituted with 2,5-dimethyl, 2,5,8-trimethyl substituted, 2,5,7,8-tetramethyl substituted, 2, 2,7-trimethyl-5-tert-butyl-6-hydroxychroman, 2,2,
5-trimethyl-7-tert-butyl-6-hydroxychroman, 2,2,5-trimethyl-6-tert-butyl-6-
Hydroxy chromans, 2,2-dimethyl -5-tert-butyl-6-hydroxy chromans such, also the general formula MxAly (OH) 2x + 3y- 2z (A) z · aH 2 O ( where M is a different Mg, Ca or Zn, A is an anion other than a hydroxyl group, x, y and z are positive numbers, and a is 0 or a positive number), for example 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 4 · 4H 2 O, Mg 6 Al 2 (OH) 12 CO 3 · 3H 2 O or the like may be blended.

Further, if necessary, 3-phenyl-2-benzofuranone as disclosed in Japanese Patent Publication No. 55-501181,
An antioxidant having a 2-benzofuranone skeleton such as 3-phenyl-4,6-di-t-butyl-2-benzofuranone may be added.

Examples of the light stabilizer include 2-hydroxy-4-mexoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone and the like. Hydroxyhenzophenones, 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-amylphenyl) benzotriazole, phenyl salicylate, p-tert-butylphenyl salicylate, 2,4-di-tert-butylphenyl-3 , 5-
Benzoates such as di-tert-4-hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,2′-thiobis (4-tert
-Octylphenol) Ni salt, [2,2'-thiobis (4
-Tert-octylphenolate)]-n-butylamine
Ni, nickel compounds such as (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonic acid monoethyl ester Ni salt, α-cyano-β-methyl-β- (p-methoxyphenyl) methyl acrylate Substituted acrylonitriles and N'-2-ethylphenyl-N-ethoxy-
5-tert-butylphenyl oxalic acid diamide, N-2-
Oxalic acid dianilides such as ethylphenyl-N'-2-ethoxyphenyl oxalic acid diamide, bis (2,2,6,6
-Tetramethyl-4-piperidine) sebacate, poly [{(6- (1,1,3,6-tetramethylbutyl) imino}
-1,3,5-triazine-2,4-diyl {4- (2,2,6,6-
Tetramethylpiperidyl) imino} hexamethylene],
2- (4-hydroxy-2,2,6,6-tetramethyl-1-
Examples thereof include hindered amine compounds such as a condensate of piperidyl) ethanol and dimethyl succinate.

Examples of the lubricant include aliphatic hydrocarbons such as paraffin wax, polyethylene wax, polypropylene wax, capric acids, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid and the like, or higher fatty acids thereof. Metal salts of lithium salts, calcium salts, sodium salts, magnesium salts, potassium salts, etc., fatty alcohols such as palmitin alcohol, cetyl alcohol, stearyl alcohol, caproic acid amide, caprylic acid amide, capric acid amide, lauric acid Amides, myristic acid amides, palmitic acid amides, stearic acid amides and other aliphatic amides, fatty acid-alcohol esters, fluoroalkylcarboxylic acids or metal salts thereof, fluoroalkyl Fluorine compounds such as sulfonic acid metal salts.

As the filler, an inorganic or organic fibrous filler such as glass fiber, silver or aluminum-coated glass fiber, stainless fiber, aluminum fiber, potassium titanate fiber, carbon fiber, Kevlar ^TM fiber, ultra-high elastic polyethylene fiber, etc., Talc, calcium carbonate, magnesium hydroxide,
Calcium oxide, magnesium sulfate, graphite, nickel powder, silver powder, copper powder, carbon black, silver-coated glass beads, aluminum-coated glass beads, aluminum flakes, stainless flakes, nickel-coated graphite and other powdered, granular, or flake-shaped inorganic or An organic filler can be illustrated.

Furthermore, the novel random multi-addition copolymer obtained by the method of the present invention can be used by blending with various known polymers. Examples of such a polymer include (a) a polymer derived from a hydrocarbon having one or two unsaturated bonds, specifically, a polyolefin such as polyethylene, polypropylene or poly which may have a crosslinked structure. Isobutylene, polymethylbutene-1, poly-4-methylpentene-
1, polybutene-1, polyisoprene, polybutadiene, polystyrene, or a copolymer of monomers constituting the above-mentioned polymer, for example, ethylene / propylene copolymer, propylene /
Butene-1 copolymer, propylene / isobutylene copolymer, styrene / isobutylene copolymer, styrene / butadiene copolymer, terpolymer of ethylene and propylene and a diene such as hexadiene, cyclopentadiene, ethylidene norbornene, etc., Alternatively, blends of these polymers, graft polymers, block copolymers, etc. (b) halogen-containing vinyl polymers, specifically polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene, chlorinated rubber (C) Polymers derived from α, β-unsaturated acids and their derivatives, specifically polyacrylates, polymethacrylates, polyacrylamides, polyacrylonitriles, or other monomers and other monomers that make up the polymers. Copolymer with copolymerizable monomer Eg to acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-
Acrylic ester copolymers and the like, (d) polymers derived from unsaturated alcohols and 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 copolymers of the above-mentioned polymer-constituting monomers with other copolymerizable monomers such as ethylene-vinyl acetate copolymers, and (e) epoxides. Polymers derived from, specifically polyethylene oxide or polymers derived from bisglycidyl ether, etc. (f) Polyacetal, specifically polyoxymethylene, polyoxyethylene,
Polyoxymethylene and the like containing ethylene oxide as a comonomer, (to) polyphenylene oxide, (thi) polycarbonate, (ri) polysulfone, (nu) polyurethane and urea resin, (l) diamine and dicarboxylic acid and / or aminocarboxylic acid Or polyamides and copolyamides derived from the corresponding lactams, specifically nylon 6, nylon 66, nylon 11, nylon 12, etc., (wo) dicarboxylic acids and dialcohols and / or oxycarboxylic acids or the corresponding lactones. Prepared polyesters, specifically polyethylene terephthalate, polybutylene terephthalate, poly 1,4-dimethylol. Polymers having a crosslinked structure derived from (wa) aldehyde and phenol, urea or melamine, such as cyclohexane terephthalate, specifically phenol / formaldehyde resin, urea /
Formaldehyde resin, melamine / formaldehyde resin, etc. (f) Alkyd resin, specifically glycerin / phthalic acid resin, etc. (yo) Derived from copolyester of saturated and unsaturated dicarboxylic acid and polyhydric alcohol, Unsaturated polyester resins and halogen-containing modified resins obtained by using vinyl compounds, (ta) natural polymers, specifically cellulose, rubber, proteins or their derivatives such as cellulose acetate, cellulose propionate, cellulose acetate , Cellulose ether, and the like. Needless to say, various known waxes may be mixed when used as a synthetic wax.

Furthermore, the copolymers of the present invention may be mixed together.

[Examples] Hereinafter, the contents of the present invention will be described in more detail with reference to the preferred examples. However, the contents of the present invention can take any form as long as the object thereof is not impaired, and are not limited to these examples. It is not something that will be done.

Example 1 A well-dried 500 ml separable flask and a stirring blade,
A gas blowing tube, a thermometer and a dropping funnel were attached and the atmosphere was sufficiently replaced with nitrogen.

250 ml of toluene dehydrated and dried with a molecular sieve was put into this flask.

Add (A) in Table 1 as DMONs to the flask under nitrogen flow.
8 g, 3.8 g of (f) in Table 1 as a cycloolefin, 2.5 mmol of ethylaluminum sesquichloride, and 0.25 vanadium oxytrichloride (VOCl ₃ ) in the dropping funnel.
Mmol was added.

Dry ethylene 20 / hr, nitrogen 40 through gas blowing pipe
A mixed gas of / hr was passed through the flask controlled at 10 ° C for 10 minutes.

Ethyl aluminum sesquichloride was added dropwise from the dropping funnel to start the copolymerization reaction, 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 uniformly transparent, and no precipitation of the copolymer was observed.

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

The polymer solution after termination of the reaction was poured into a large amount of methanol and acetone to precipitate a copolymer, which was further washed with acetone and vacuum dried at 60 ° C. for 24 hours to obtain 8.1 g of a copolymer. The ethylene composition in the copolymer measured by ¹³ C-NMR analysis was 55.
The intrinsic viscosity [η] measured in mol% and decalin at 135 ℃ is
It was 4.2 dl / g and the iodine value was 0.7. The density according to ASTM D 1505 was 1.09 g / cm ³ .

In addition, in order to measure mechanical properties, press-formed sheets with a thickness of 1 mm or 2 mm were prepared by hot pressing at 230 ° C. When X-ray diffraction was performed using these sheets, scattering by crystals was not observed and the crystallinity (Wc) was 0%. The transparency is 8% when measured on a 1 mm sheet with a haze meter according to ASTM D 1003-52.
Met. The refractive index (n ^D ) according to ASTM D 542 was 1.527. Flexural modulus and flexural yield strength, using a 2mm thick press sheet was measured in conformity with ASTM D 790, were respectively ^{2.2 × 10 4 kg / cm 2} , 950kg / cm 2. The glass transition temperature Tg is the Dynamic Mechanical Analyse manufactured by DuPont.
The loss elastic modulus E ″ was measured by r (DMA) at a temperature rising rate of 5 ° C./min, and was found to be 135 ° C. from the peak temperature. Further, the melting point Tm was measured by DuPont 990 type DSC. No melting curve (peak) was observed when measured at a temperature rising rate of 10 ° C / min in the range of -120 ° C to 400 ° C.
When the thermal decomposition temperature was measured with a thermal balance (TGA) 381
It was ℃.

The electrical properties were measured with a dielectric loss measuring device manufactured by Ando Electric Co., Ltd. at 1 KHz, and the dielectric constant was 2.1. The dielectric loss tangent (tan δ) was 3.
It was 0 × 10 ^-4 . Furthermore, in order to check the chemical resistance,
Press-formed products at room temperature with sulfuric acid (97%), ammonia water (20%
%), Acetone, ethyl acetate, etc. for 20 hours, and the appearance was observed, and no properties such as color change, deterioration of transparency, deformation, dissolution and cracking were observed.

Examples 2 to 14 The same operation as in Example 1 was carried out except that the copolymerization reaction conditions were changed as shown in Table 2, and the results shown in Table 2 were obtained. The conditions and results of Example 1 are listed in Tables 2 and 3.

Example 15 In the polymerization of Example 1, 7.5 g of (A) and 7.5 g of (F) were used.
g, 25 mmol of ethyl aluminum sesquichloride,
2.5 mmol of dichloroethoxyoxovanadium was used instead of vanadium oxychloride, the flow rate of ethylene was 80 / hr, hydrogen was 80 / hr instead of nitrogen, and the polymerization temperature was 30 ° C. The reaction was carried out.

3.8 g of the copolymer can be obtained, the ethylene content in the copolymer is 59 mol%, the ethylnorbornene content is 20 mol%,
The intrinsic viscosity [η] measured in decalin at 135 ° C was 0.10, and the iodine value was 0.6. It was 1080 cp when measured at 750 rpm and 280 ° C. with an Emirer rotational viscometer (manufactured by Yagami).

The polymer was molded into a press sheet having a thickness of 1 mm at 200 ° C. to prepare a measurement test piece. The sheet was fairly brittle in nature. The crystallinity by X-ray diffraction was 0%, and when measured with a differential scanning calorimeter 990 (DSC) manufactured by DuPont at a temperature rising rate of 5 ° C / min, no melting peak was observed and the glass transition was observed. The temperature was 123 ° C. Dupont needle penetration measuring device (TMA: Thermomechanical Analyser, load 49 g, 0.
The softening temperature at a temperature rising rate of 10 ° C / min by a 025 inch quartz needle) was 120 ° C. The haze according to ASTM D 1003-52 was 12%. Furthermore, in order to investigate the solvent resistance, the test piece was immersed in 97% sulfuric acid, 20% ammonia water, acetone, methyl acetate, etc. for 20 hours, and then the appearance was observed. There wasn't.

[Effects of the Invention] As described above, the novel random multi-addition copolymer obtained by the production method of the present invention has a mechanical property such as heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric property, and rigidity. It has an excellent balance of physical properties, optical properties such as transparency, low molding shrinkage, water resistance, low moisture absorption, etc., and thus can be expected to be applied to various fields already described.

[Brief description of drawings]

FIG. 1 is a flow chart showing the steps for producing the copolymer according to the present invention.

Claims (4)

[Claims] 1. (A) (i) 1,4 represented by the following formula (I):
5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene (hereinafter abbreviated as DMON), (ii) ethylene, and (iii) having 3 or more carbon atoms By random addition polymerization of α-olefin and / or cycloolefin of (Here, R ¹ and R ² are hydrogen or an alkyl group and may be the same or different.) (B) Ethylene / DMONs (molar ratio) 95/5 to 5/95, (C) [Α-olefin and / or cycloolefin having 3 or more carbon atoms] / DMONs (molar ratio) is 80/20 to 5 /
95, (D) DMON unit has a structure substantially represented by the following formula (II), (E) The intrinsic viscosity [η] measured in decalin at 135 ° C is
A method for producing a novel random multi-component addition copolymer defined by 0.005 to 20 dl / g. 2. The method for producing a novel random multi-addition copolymer according to claim 1, which comprises DMONs, ethylene and an α-olefin having 3 or more carbon atoms. 3. A process for producing a novel random multi-component addition copolymer according to claim 1, which comprises DMONs and ethylene and cycloolefin. 4. A process for producing a novel random multi-addition copolymer according to claim 1, which comprises DMONs, ethylene, and an α-olefin having 3 or more carbon atoms and a cycloolefin.