JPH03192105A - Production of new polymer - Google Patents

Abstract

PURPOSE:To obtain a new polymer having an intrinsic viscosity in a specified range and excellent in transparency, heat resistance, mechanical properties, dielectric characteristics, etc., by addition-copolymerizing a specified polycyclic monomer with ethylene in a specified molar ratio. CONSTITUTION:A polycyclic monomer (A) of formula I (wherein R<1> to R<12> are each H, alkyl or halogen; R<9> or R<10> and R<11> or R<12> may be combined together to form a ring; and n>=2) (e.g. formula II) is addition-copolymerized with ethylene (B). In this way, a new polymer having a molar ratio of component B unit to component A unit of 95/5 to 10/90, containing component A units in the form of a structure of formula III and having an intrinsic viscosity in the range of 0.005-20dl/g when measured in decalin at 135 deg.C is obtained. The obtained polymer can be used in many fields such as paper processing agents, rubber antioxidants, hot-melt adhesives, plastic lenses, and liquid crystal display substrates.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention has excellent transparency and a well-balanced mechanical property such as heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and rigidity. The purpose of this invention is to provide a method for producing a novel polymer.
The purpose of the present invention is to provide a method for producing a novel polymer.

...(I) (Here, R1-R1 is an alkyl group or a halogen, and each may be the same or different, and R or R
ts and R1 or RI2 may mutually form a ring. Further, n is a positive number of 2 or more, and R8-R* repeated multiple times may be the same or different. ) [Prior Art] Widely known synthetic resins with excellent transparency include polycarbonate, polymethyl methacrylate, and polyethylene terephthalate. 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 in that it is easily attacked by strong alkalis and has poor chemical resistance. Polymethyl methacrylate is easily attacked by ethyl acetate, acetone, etc.
It also has the problem of swelling in ether and 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, polyolefin 14, which is famous as a general-purpose resin, has excellent chemical resistance and solvent resistance, and many have excellent mechanical properties. Many have poor heat resistance, and because they are crystalline resins, they have poor transparency. . In general, 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.The effectiveness of these methods cannot be said to be sufficient. 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 also reduces the degree of crystallinity. Therefore, there is a risk that heat resistance and rigidity may also decrease.

[Object of the invention] Therefore, the present inventors have developed an IL that has transparency, heat resistance,
Air supply that has been researched to find a synthetic resin with a good balance of heat aging resistance, solvent resistance, dielectric properties, and mechanical properties.
It was discovered that a copolymer of ethylene and a specific bulky comonomer could achieve the purpose.
The present invention relates to an improvement of the technology proposed in the above-mentioned application, and further relates to a method for producing a polymer using a bulky hexamer.

[Means for solving the problem] That is, the present invention (A) is characterized in that the polycyclic monomer represented by the general formula (I) and ethylene are subjected to addition copolymerization, (B) ethylene component unit/ The polycyclic monomer component unit (molar ratio) is 9515 to 10/90, the polycyclic monomer component unit (C) has a structure substantially represented by the following general formula (T1), ...(n) (D ) Intrinsic viscosity measured in decalin at 135°C [η]
is o, o o s~20 dl/g.

This invention relates to a method for producing a novel polymer defined by:

Detailed Description of the Invention [Monomer Components] The monomers used in producing the polymer of the present invention are mainly polycyclic monomers represented by the above-mentioned general formula (R) or ethylene.

In the general formula representing a polycyclic monomer, R1-R12 are hydrogen, alkyl groups such as methyl, ethyl, propyl,
Chain alkyl such as isopropyl, butyl, tert-butyl, cycloalkyl such as cyclopentyl, cyclohexyl, or halogen such as fluorine, bromine, iodine, etc., which may be the same or different. Further, R9 or R111 and R1 or R12 may mutually form a ring, and examples thereof include general formulas (m) and (■).

... (m) ... (+v) (Here, RI3 to R21 are hydrogen or an alkyl group, and each time may be - or different.) Specific examples of such polycyclic monomers are shown in Table I below. Examples include:

In addition to these, any monomer represented by the general formula (r) may be used.N=2 or 3 is preferred, and polycyclic monomers where n=2 are particularly preferred.

[Polymerization method] In order to produce a novel polymer as described below by the method of the present invention, a polycyclic monomer or a polycyclic monomer and ethylene may be subjected to addition copolymerization using a well-known Ziegler catalyst. .

However, other copolymerizable monomers may be included as long as the purpose 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,
σ-olefins having 3 or more carbon atoms such as 1-decene, cycloolefins such as cyclopentene, cyclohexene, 3-methylcyclohexene, styrene, styrene such as a-methylstyrene, norbornene, methylnorbornene, ethylnorbornene, isobutylnorbornene, etc. norbornene gL2,3,3a,7a-tetrahydro-4,7-methano-IH-indene (general formula (a)), 3a, 5.6.7a-tetrahydro-4,
Endomethylene compounds not included in the general formula (I) of the present invention, such as 7-methano-IH-indene (general formula (B)) or compounds where n=1 in general formula (1), or 1,4- xadiene, dicyclopentadiene, 5-
Mention may be made of polyenes such as ethylidene-2-norbornene.

(a) (b) The polymer obtained in the present invention can be broadly classified into homopolymers of polycyclic monomers and random copolymers of polycyclic monomers and ethylene depending on the type of constituent monomers. This is preferred because it provides a well-balanced polymer for the purpose of the invention.

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

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 means that does not substantially remove titanium compounds at room temperature.

A good composite has a halogen/titanium (molar ratio) of about 4
more than about 5, preferably about 5 or more, more preferably about 8 or more, magnesium/titanium (molar ratio) of about 3 or more, preferably about 5 to about 50; titanium (molar ratio) from about 0.2 to about 6, preferably from about 4 to about 3, -layer preferably from about 0.8 to about 2, with a specific surface area of about 3 m27
It is preferably about 40 m2/g or more, more preferably about 100 m2/g or more. In addition, the X-ray spectrum of the composite may exhibit poor quality irrespective of the starting magnesium compound, or may be in a highly amorphous state compared to that of ordinary commercially available magnesium cybaride. desirable.

As an example of means for producing a composite, for example,
Public grudge No. 16986 JP-A No. 50-108385
JP-A-50-126590 revolution JP-A-51-202
No. 97 public grudge JP-A-51-28189 public grudge JP-A No. 5
Public grudge No. 1-92885 Publication of JP-A-51-127185 Publication of JP-A-51-136625 JP-A-52-8
Public beast No. 7289 JP-A-52-100596 revolution JP-A-52-104593 revolution JP-A-52-1476
No. 88 Japanese Patent Publication No. 53-2580 Public IL 1975
An example is the means described in the Italian patent application dated November 21, 2013.

As a vanadium compound, ttvct, , VBr, , VC
Vanadium halides such as I, VBr, etc., VOCl
, VOBr, VOCl2, VOBr2, and other vanadium oxyhalides or vanadium compounds represented by VO(OR) nX5- (where R is a hydrocarbon & X is a halogen, 0<n≦3). Among these, hydrocarbon-soluble vanadium compounds, particularly vanadium oxyhalides or compounds represented by VO(OR)nX3-n, are preferred.

Said VO(OR). In the compound represented by X 2- n , R is an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group having 1 carbon atom
-20, especially 1-3.

Further, n is in the range of Own≦3, preferably 1≦n≦1.5. Examples of such vanadium compounds include VO(OCHs) C12, VO(OCH,)
2CI.

VO(OCH3) z, VO(OC2Hs)C12
, VO(OC2Hs)+, sCl+, s.

VO(OC2Hs) 2CL VO(OC*Hs)2
, VO(OC2Ha)+, 5Br11, VO(QC,H,) C12, VO(OCsHv)+, sCl+, 5-vO(QC3H
y)2Cl, VO(OCtHy)z, VO(On-C
,H,)C12, VO(On-CaH*) 2c 11 VO(Oiso-C4H*)2C1°V O(O5ee-Ca H9) s.

Examples include V O (OCsH++) +, sCl+, s Aruiha cholera f) mixtures, and the like. These can be easily obtained by reacting V OCl a with alcohol, or reacting vOCl with vo(OR).

The alkylaluminum compound used with the titanium-based catalyst or vanadium-based compound is represented by the general formula % halogen, 0<m≦3). Examples of this alkyl aluminum compound include trialkylaluminium, dialkylaluminum halide, alkyl aluminum civalide, any mixture thereof, or a mixture of these and aluminum trihalide. Dai: From the viewpoint of ease of polymerization, a vanadium compound/alkyl aluminum compound system is preferred. When this system is used, the ratio of Al/V (molar ratio) used is preferably 1 or more, preferably 30 or less, and 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 Benzene,
Aromatic hydrocarbons such as toluene and xylene can be used alone or in combination as a solvent.

Polymer L Taking a vanadium compound/alkylaluminum compound catalyst system as an example, the vanadium compound is added in a concentration of 0.05 to 20 mmol/Q, preferably 0.1 to 10 mmol/2 in the reaction medium. It is preferable to Also, alkyl aluminum compound cutting allowance
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.

When producing a random copolymer of a polycyclic monomer and ethylene, the amount of rain monomer charged into the reaction medium varies depending on the composition of the desired copolymer, the type of reaction medium, and the polymerization temperature. The molar ratio of ethylene/polycyclic monomer in the medium is 1/100 to 100/1.
Preferably, the ratio is adjusted to 1150 to 50/1.

The polymerization temperature is -50 to 300°C, preferably -30 to 20°C.
0℃, polymerization pressure is generally O~50kg/cIIf1
Preferably, it is maintained at 0 to 20 kg and 7 cm2.

Further, a molecular weight regulator such as hydrogen may be present as appropriate to adjust the molecular weight of the polymer.

[Overview of Folded Polymer] The folded polymer obtained by the production method of the present invention is substantially composed of polycyclic monomer component units or polycyclic monomer component units and ethylene component units. However, to the extent that the object of the present invention is not impaired, component units derived from other copolymerizable monomers may be used, such as polycyclic monomers.
It may be contained within a range of 50 mol% or less of the component units.

Specific examples of such seven-mer component units include propylene, 1-butene, 3-methyl-1-butene, 1-
Pentene, 4-methyl-1-pentene, 1-hexene,
a-olefins having 3 or more carbon atoms such as 1-decene, cycloolefins such as cyclopentene, cyclohexene, 3-methylcyclohexene, styrene, styrene milk such as a-methylstyrene, norbornene, methylnorbornene, ethylnorbornene, inbutylnorbornene Norbornene lji, such as 2, 3, 3a, 7
a-cheetrahit O-4,7-methano-IH-indene (-formula % formula % IH-indene (-formula (b)) or -formula (1)
Endomethylene compounds not included in the general formula (I) of the present invention, such as compounds where n=1, or 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-
Mention may be made of component units derived from polyenes such as 2-norbornene.

(a) (b) The polymer defined in the present invention can be broadly classified into a homopolymer of a polycyclic polymer component and a random copolymer of a polycyclic polymer component and ethylene, depending on the type of constituent monomer component units. The latter is preferred because it yields a well-balanced polymer for the purpose of the present invention.

The content ratio (mole ratio) of ethylene component units/polycyclic monomer component units in the polymer of the present invention is from 9515 to 10/90. Among these, high molecular weight substances with excellent balance of physical properties are 1490/10 to 10/90, especially 85/15 to 20.
A range of /80 is preferred.

The polycyclic monomer components are mainly polymerized in the structure shown in formula (n) above.

Since the polycyclic monomer component substantially has the above structure, the iodine value of the polymer of the present invention is usually 5 or less, and most of them have an iodine value of 1.
It is as follows. Further, the fact that it has the above structure is also supported by C-NMR. Therefore, it has a chemically stable structure and is a polymer with excellent heat aging resistance.

Polymer price: Intrinsic viscosity measured in decalin at 135°C [V
] is 0.005 to 20 dl/g. In particular, when used for hard resin applications, it is 0.3 to 20 dl/g, particularly 0.3 to 10 dl/g, and even 0.8 to 8 dl/g.
g is preferred. In addition, when used for wax purposes, 0.01 to 0.3 dl/g, and even 0.05 to 0
．． 2 dl/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, a dynamic viscoelasticity meter (D
Glass transition temperature (Tg) according to MA) is usually 80 to 24
0°C, mostly within the range of 100-200°C.

Also, TMA (Thermo-mechanica)
l Analyser: Manufactured by DuPont) with load 4
9g, using a quartz needle (diameter 0.635mm) at a heating rate of 5°C/min, the temperature at which the needle penetrates 0.1mm, that is, the softening temperature, is usually 70-220°C, often 90-1
Measured within 90°C.

In addition, the thermal decomposition temperature of a polymer is usually 3°C when the weight loss starting temperature is defined as the temperature at which the 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.).
50-420°C, mostly in the range of 370-410°C.

The density of the polymer was determined by the density gradient tube method (ASTMD
1505) and is usually 0.86 to 1.10 g/crl, most of which is within the range of 0.88 to 1.08 g/cm3.

Moreover, the refractive index (ASTM D 542) is 1.47 to 1.
58, mostly in the range of 1.48-1.56.

Regarding the electrical properties of polymers, the dielectric constant (IKHz) according to ASTM D 150 is 1.5 to 3.0, and most are 1.9.
~2.6, the dielectric loss tangent is I x 10-3 ~ 5xlO-s
Many are in the range of 5 x 10-' to 8 x 10-'.

Pencil hardness (JI) as a measure of the surface hardness of polymers
S K 5401) is 3B or more and 3H or less.

[Field of Application] To give an example of a specific field of application of the new type of coalescence obtained by the method of the present invention, by taking advantage of its excellent physical properties, in the case of a low molecular weight substance, it can be used in a field where it can normally be used with synthetic wax. Namely, lumber impregnation for waxing, paper processing, size, rubber anti-aging agent, water-resistant cardboard, chemical fertilizer, slow-acting heat storage material, ceramic binder, electrical insulation material for paper capacitors, electric wires, cables, etc. , neutron moderator, textile processing artery, building material water supply, paint protection vessel
Glossy L. Chikit lobby imparted L. Pencil/crayon lead hardness imparted L. Carbon ink base Toner for electrostatic copying Synthetic resin molding lubricant*k Release port Resin coloring L.
Examples include hot-melt adhesive lubricating grease. In addition, in the case of high molecular weight substances, it is used in the optical field such as plastic lenses, optical disks, optical fiber glass windows, transparent conductive films and sheets, liquid crystal display substrates, high frequency circuit boards, electric iron water tanks, microwave oven supplies, etc. It can be used in a variety of fields, including the medical field, syringe pipettes, animal gauges, etc., the chemical field, camera bodies, housings for various instruments, plastic magnets, films, sheets, and helmets.

[Molding Process and Stabilizer] The polymer obtained by the method of the present invention is molded by a well-known method. For example, single screw extruder, vented extruder, twin screw extruder, conical twin screw extruder,
Co-kneader, Platificator, Mixtruder, Two-wheeled conical screw extruder, Planetary screw extruder, Gear type extruder, Screwless extruder, etc. are used to perform extrusion molding, injection molding, plow adult pigs, rotational molding, etc. In addition, in the molding process, well-known additives such as heat-resistant and stable additives may be added as necessary.Light-stabilizing berthsAnti-static slip berthsAnti-butting berthsAnti-fog berthSliding synthetic pondsNatural sourcesInorganic and organic filling berthsDye, pigments, etc. may be added.

Examples of such additives include phenol-based or sulfur-based antioxidants. Used as a phenolic antioxidant, such as 2,6-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-hydroxybenzylphosphonate,
ert-butyl-4°-hydroxybenzylthio)-1
,3,5-)riazine, distearyl(4-hydroxy-3-methyl-5-tert-butylbenzyl)malonate, 2.2°-methylenebis(4-methyl-6-te
rt-butylphenol), 4.4°-methylenebis(
2,6-tert-butyl 7z/-l), 2.2'
-methylenebis[6-(1-methylcyclohexyl)p
-cresol], bis[3,5-bis(4-hydroxy-3-tert-butylphenyl)butyric acid coglycol ester, 4.4°-butylidene bis(6-
tert-butyl-m-cresol), 1.1.3-
) Lis(2-methyl-4-hydroxy-5-tert
-butylphenyl)butane, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert
-butyl-5-methylbenzyl)phenylcoterephthalate, 1,3.5-tris(2,6-dimethyl-3-hydroxy-4-tert-butyl)benzylisocyanurate, 1,3.5-)lis(3° 5-G tert-
butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, tetrakis[methylene-3-(3,5
-di-tert-butyl-4-hydroxyphenyl)propionate comethane, 1.3.5-tris(3,5-
di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-)lis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, 2-octylthio-4,6- di(4-hydroxy-3,5-ter
t-butyl)phenoxy-1,3,5-)riazine, 4
．． Phenols such as 4°-thiobis(6-7ert-butyl-m-cresol) and carbonic acid oligoesters of 4.4°-butylidenebis(2-tert-butyl-5-methylphenol) (for example, polymerization degree 2.3). .4.5.6
．． Examples include polyhydric phenol carbonate oligoesters such as 7.8.9.10, etc.).

Disappointed as sulfur-based antioxidants Polyhydric alcohols of dialkylthiodipropionates such as dilauryl-cimyristyl-distearyl and alkylthiopropionic acids such as butyl-octyl-lauryl-stearyl (e.g. glycerin, trimethylolethane, trimethylol) esters of propane, pentaerythritol, trishydroxyisocyanurate) (e.g. pentaerythritol tetralaurylthiopropionate)
can be mentioned.

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, distearyl pentaerythritol diphosphite, tetra (tridecyl)-1,
1,3-)lis(2-methyl-5-tert-butyl-
4-Hydroxyphenyl)butane diphosphite, tetra(C,2~C+s blended alexyl=4.4°-isopropylidene diphenylphosphite, tetra(tridecyl)-4,4°-butylidene bis(3-methyl-6 -t
ert-butylphenol) diphosphite, tris(3,5-di-tert-butyl-4-hydroxyphenyl)phosphite, tris(mono-dimixed nonylphenyl)phosphite, hydrogenated-4,4゛-isopropylidene diphenol polyphosphite Phite, bis(octylphenyl) bis[4,4'-butylidenebis(3-methyl-6-tert-butylphenol)], 6-hexanediol diphosphite, phenyl 4,4'-
Isopropylidene diphenol bentaerythritol J
Resiphosphite, 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 Fight, 4.4°-
Isopropylidene bis(2-tert-butylphenol) di(nonylphenyl) phosphite, 9.10-
Di-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, tetrakis(2,4-dite
Examples include rt-butylphenyl)-4,4°-biphenylene diphosphonite.

Also, 6-hydroxychroman derivatives such as a.

β, γ, δ tocopherols and their mixtures
2.5-dimethyl substitution of -(4-methyl-penter-3-nonyl)-6-hydroxychroman & 2.5.8-
) Limethyl substitution imitation 2.5.7.8-tetramethyl substitution machine 2.2.7-drimethyl-5-tert-butyl-6-hydroxychroman, 2,2.5-trimethyl-
? -tert-butyl-6-hydroxychroman, 2.
2.5-trimethyl-6-tert-butyl-6-hydroxychroman, 2.2-dimethyl-5-tert-butyl-6-hydroxychroman, etc. Also, the general formula % formula % (where M is Mg, For example, Mga A is an anion other than a hydroxyl group, xl y and 2 are positive,
12 (OH) + * COs・4H2αMgs A
12 (OH)25 CO3・5H2αMgs A12
(OH) + a CO3・4H2αMg+. A12
(OH)22 (COs)・4H20゜Mge A1
2(OH) + e HPO4・4H2QCas Al
a (OH) + *CO3・4H2αZn6. A1
2 (OH) Ie CO3・4H2(IZn6 A1
2(OH) + s Son ・4H2αMge A1
2 (OH) + * SO4・4H2QMge A1
2(OH) l 2 COa.3H20 or the like may be blended.

In addition, 2-penzofuranone compounds disclosed in Japanese Patent Application Publication No. 55-501181, such as 3-phenyl-
2-benzofuranone, 3-phenyl-5,7-di-t-
Butyl-2-benzofuranone and the like may also be blended.

Examples of light stabilizers include hydroxyl stabilizers such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone-2,2°-di-hydroxy-4-methoxybenzophenone, and 2,4-dihydroxybenzophenone. Benzophenone Kai 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-3°, 5°-di-tert-
Phenyl salicylate, p-tert-butylphenyl salicylate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5- G-t
Benzoates such as ert-butyl-4-hydroxybenzoate [2,2°-thiobi2 (4-tert-octylphenol) Ni salt, [2,2′-thiobis(
4-tert-octylphenol]-]n-butylamine Ni, (3,5-di-tert-butyl-4-
Hydroxybenzyl)phosphonic acid monoethyl ester N
Nickel compounds such as K salts, substituted acrylonitriles such as methyl a-cyano-β-methyl-β-(p-methoxyphenyl)acrylate, and No-2-methylphenyl-N-2-ethoxy-5-tert-butyl Phenyl oxalic acid diamide, N-2-ethylphenyl-No-
Oxalic acid dianilides such as 2-ethoxyphenyl oxalic acid diamide, bis(2,2,6,6-tetramethyl-
4-Piperidine) Sepashade, Poly[((6-(1,
1,3,3-tetramethylbutyl)imino)-1,3,
5-triazine-2,4-diyl (4-(2,2,6,
6-titramethylbiveridyl)imino)hexamethylene], hindered amine compounds such as condensates of 2-(4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl)ethanol and dimethyl succinate can be mentioned.

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, valmitic acid, margaric acid, stearic acid, araxic acid, behenic acid, and metals thereof. Salty i.e. lithium salts, calcium salts, sodium salts, magnesium salts, potassium salts, etc., aliphatic alcohols such as valmityl alcohol, cetyl alcohol, stearyl alcohol, caproic acid amide, caprylic acid amide, capric acid amide, lauric acid amide, myristic acid. Esters of aliphatic amide milk fatty acids and alcohols such as acid amide, valmitic acid amide, stearic acid amide, fluoroalkyl carboxylic acid or its metal salt,
Examples include fluorine compounds such as fluoroalkylsulfonic acid metal salts.

1 as a filler Glass fiber paper Silver forks are aluminum coated glass fiber Stainless fiber paper Aluminum woven edge
Potassium titanate paper Carbon fiber Kevlar TI'l paper Inorganic or organic fibrous filling such as ultra-high elastic polyethylene fiber Talc, calcium carbonate, magnesium hydroxide, calcium oxide, magnesium sulfate, graphite, nickel powder, silver powder , copper powder, carbon black, silver coated glass pieces, aluminum coated glass pieces,
Examples include inorganic or organic fillers in the form of powder or flakes such as aluminum flakes, stainless steel flakes, and nickel-coated graphite.

[Blending with other polymers] Furthermore, the polymer obtained by the method of the present invention can be used by blending with various known high-molecular weight or low-molecular weight polymers. Examples of such polymers include polyolefins derived from hydrocarbons having one or two unsaturated bonds, such as polyethylene, polypropylene, and polyolefin, which may have a crosslinked structure. Isobutylene, polymethylbutene-L Poly4-methylbentene-L Polybutene-L Polyisoprene, polybutadiene, polystyrene, or copolymers of monomers that structure the above polymers, such as ethylene-propylene copolymerization propylene-butene-1 Copolymerization book Propylene/isobutylene copolymerization Styrene/isobutylene copolymerization Styrene/butadiene copolymerization Mimic ternary copolymerization of ethylene and propylene with dienes such as hexadiene, cyclopentadiene, ethylidene norbornene, or blends of these polymers (2) Halogen-containing vinyl copolymerization, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene, chlorinated rubber, etc. Polymerization arcs derived from saturated acids and their derivatives, specifically polyacrylate, polymethacrylate, polyacrylamide, polyacrylonitrile, or copolymers of monomers constituting the above polymers and other copolymerizable monomers. If.

Acrylonitrile/butadiene/styrene valve type combination Acrylonitrile/styrene valve type combination Acrylonitrile/styrene/acrylic acid ester copolymerization, etc. (d) Polymerization imitation derived from unsaturated alcohols and amines or their acyl derivatives or acetals is polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, polyallylmelamine, or the monomers constituting the above polymer and other copolymerizable monomers. Copolymers derived from (e)epoxides, such as ethylene-vinyl acetate copolymers, etc.
Polyacetals, such as polymers derived from polyethylene oxide or bisglycidyl ethers, specifically polyoxymethylene, polyoxyethylene,
(g) polyphenylene oxide, (th) polycarbonate, (s) polysulfone, (n) polyurethane and urea resin, (l) diamine and dicarboxylic acid and/or amino Polyamides and copolyamides derived from carboxylic acids or the corresponding lactams, in particular to nylons
(2) Polyesters derived from dicarboxylic acids and dialcohols and/or oxycarboxylic acids or corresponding lactones, specifically polyethylene terephthalate, polybutylene terephthalate, poly 1,4-dimethylol - Cyclohexane terephthalate, etc., polymers with a cross-linked structure derived from aldehyde and phenol, urea or melamine. Specifically, phenol/formaldehyde resin, urea/formaldehyde resin, melamine/formaldehyde resin, etc., (power) alkyd tree 11 Specifically, glycerin and phthalate resins are derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols, unsaturated polyester resins obtained using vinyl compounds as crosslinking agents, and halogens. Specific examples of the modified resins contained therein include cellulose, rubber, protein, or 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, new types of aggregates having different molecular weights obtained by the method of the present invention may be mixed.

[Examples] The content of the present invention will be explained below with preferred examples.It goes without saying that the present invention is not limited to these examples, and can take any form as long as the purpose is not impaired. It is.

Attach a stirring blade, a gas blowing tube, a thermometer, and a dropping funnel to a thoroughly dried 500 ml Separate flask, and replace the air with nitrogen. Transfer 7.5 g of compound A in Table 1 to the flow flask.
Add 2.5 mmol of ethylaluminum sesquichloride and 0.0 mmol of dichloroethoxyoxovanadium to the dropping funnel.
．． A mixed gas of 10 Q/box of dried ethylene and 4011/hr of nitrogen was added through a gas blowing tube containing 25 mmol of nitrogen.
The copolymerization reaction was started by dropping ethylaluminum sesquichloride from a dropping funnel that had been passed through a flask controlled at 10°C for 10 minutes.The copolymerization reaction was carried out at 10°C for 30 minutes while passing the mixed gas. The solution was homogeneous and transparent, and no precipitation of the copolymer was observed. 5 ml of methanol was added to the polymer solution to stop the copolymerization reaction. After precipitating the polymer and washing with methanol, the temperature was increased to 60°C.
The ethylene composition of the copolymer was 59 mol% as measured by 13C-NMR analysis, the intrinsic viscosity [V] as measured in decalin at 135°C was 1.4, and the iodine value was 53 g. was 0.9.In addition, to measure the mechanical properties, 230℃ hot p
Press-molded sheets with a thickness of 1 mm or 2 mm were created using ress.When X-ray diffraction was performed using these sheets, no scattering due to crystals was observed, and the degree of crystallinity was 0%. Transparency is ASTM D 100
The bending elastic modulus and bending yield strength were 9% when measured with a haze meter in accordance with 3-52. Using a 2 mm thick pressed sheet, the ASTM
When measured according to D 790, each was 2.5
X10'kg/cnf, 810kg/cm2
Glass transition temperature Tgl & DuPont Dynami
c Mechanical Analyzer (DM
According to A), the loss modulus E'' was determined from the peak temperature of the measured object at a heating rate of 5°C/min, and it was 150°C. Temperature speed - 12
When measured in the range of 0°C to 400°C, no melting curve (peak) was observed.Electrical Properties 1 & When measured at I KHz using a dielectric loss measuring device made by Ando Electric, the dielectric constant was 1.9. The dielectric loss tangent (tan δ) is 2.3X10-'.
7%), ammonia water (20%), acetone, ethyl acetate, etc. for 20 hours and observed the appearance, the color quality (
1. No symptoms such as reduced transparency, transformation, welding, cracking, etc. were observed.Also, DuPont's Ther
o mechanical analyzer (T
MA), heat distortion temperature of 1mmmm-t (5℃/mi
n risei load 49g, quartz needle 0.635mm 0.1
When the temperature (mm penetration temperature) was measured, it was 139℃ and r
= Sara & Mi Density L by density gradient tube method 1.0
It is 32g/cm3, and the refractive index HD is measured by an Arahe refractometer.
was 1.540, and the pencil hardness, which is an index of hardness, was +4. perform the operation,
The results shown in Table 3 were obtained. Table 2.3 lists the conditions and results of Example 1. By adopting a structure and composition that was completely unknown, we have achieved transparency, heat resistance, heat aging resistance, chemical resistance,
It exhibits high levels of solvent resistance, dielectric properties, and mechanical properties, and as mentioned above, it can be used in a wide variety of fields, bringing great benefits to industry.

Claims (2)

[Claims] (1) (A) ▲Mathematical formulas, chemical formulas, tables, etc. are available▼...(I) (Here In, R^1 to R^1^2 are hydrogen, alkyl groups or halogens, and each of them 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. Further, n is a positive number of 2 or more, and R^5 to R^6 repeated multiple times may be the same or different. ) (B) ethylene component unit/polycyclic monomer component unit (molar ratio) is 95/5 to 10/90, and (C) polycyclic monomer component unit substantially has the structure represented by the following general formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (D) Intrinsic viscosity measured in decalin at 135℃ [η]
0.005 to 20 dl/g, a method for producing a novel polymer defined by: (2) A method for producing a novel polymer according to claim 1, which further comprises copolymerizing a third copolymerizable monomer.