JPS61115912A - Novel random multicomponent copolymer - Google Patents

Abstract

PURPOSE:The titled copolymer excellent in heat resistance, chemical resistance, solvent resistance, dielectric characteristics, rigidity, etc., prepared by adding a specified third component and/or a specified fourth component monomer to a two-component mixture comprising a specified polycyclic monomer component and ethylene and polymerizing the resulting monomer mixture. CONSTITUTION:A random multicomponent copolymer comprising a 1,4,5,8- dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene (DMON) of formula I (wherein R<1> and R<2> are each H, an alkyl or a halogen), ethylene, a 3C or higher alpha-olefin and/or a cycloolefin, wherein the ethylene/DMON molar ratio is 95/5-5/95, the molar ratio of the total of the C3 or higher alpha-olefin and/or the cycloolefin to DMON is 95/5-20/80, the DMON unit chiefly has a structure of formula II, and the intrinsic viscosity eta as measured in decalin at 135 deg.C is 0.005-20dl/g.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention has excellent transparency, and has excellent mechanical properties such as heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and rigidity. The purpose is to provide a new well-balanced random copolymer, and more specifically, 1. 4. 5.8-
Dimethano-1m 2.3s 4.4at 51818a
- Two component monomers of octahydronaphthalenes (or tetradodecenes; hereinafter sometimes abbreviated as DMONs) and ethylene, a third component of α-olefin and/or cycloolefin having 3 or more carbon atoms, and a fourth component It relates to a tertiary random copolymer or a quaternary random copolymer obtained by polymerization by adding component monomers.

[Prior art]

Polycarbonate, polymethyl methacrylate, polyethylene terephthalate, and the like are known as synthetic resins with excellent transparency. For example, polycarbonate is a resin that is not only transparent but also has excellent heat resistance, heat aging resistance, and impact resistance. 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. Furthermore, although polyethylene terephthalate has excellent heat resistance and mechanical properties, it has a problem in that it is weak against strong acids and alkalis and is susceptible to hydrolysis.

On the other hand, many polyolefins, which are famous as general-purpose resins, have excellent chemical resistance, solvent resistance, and mechanical properties, but many have poor heat resistance, and because they are crystalline resins, they have poor transparency. <Inferior. Generally, to improve the transparency of polyolefins, methods are used to refine the crystal structure by adding a nucleating agent, or to stop crystal growth by rapid cooling.
Its effect cannot be overstated. On the contrary, adding a third component such as a nucleating agent may impair the excellent properties originally possessed by polyolefins, and the rapid cooling method not only requires large-scale equipment, but also reduces the degree of crystallinity. Therefore, there is a possibility that heat resistance and rigidity may also be reduced.

As a result of repeated research, the applicant has conducted research into whether it is possible to obtain a synthetic resin that is transparent, yet has a good balance of heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and mechanical properties. discovered that a copolymer of ethylene and a specific bulky comonomer could achieve the purpose, and filed a patent application in 1983-169.
The technical contents were disclosed in No. 95.

As for copolymers of ethylene and bulky monomers, for example, U.S. Pat. No. 2,883,372 discloses copolymers of ethylene and 2,6-cyhydrodicyclobentadiene. However, although this copolymer has an excellent balance of rigidity and transparency, its glass transition temperature is 100°C.
It is close to that and has poor heat resistance. A copolymer of ethylene and ethylidenenorbornene also exhibits similar properties. However, the ethylene copolymers containing DMONs as comonomers discovered by the present applicant 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. Because of the above, it has excellent heat resistance, and because it does not have unsaturated bonds, it also has excellent long-term heat aging resistance. DMON, which is a comonomer used by the present applicant for copolymerization with ethylene, has already been disclosed in Japanese Patent Publication No. 14910/1983 or Japanese Patent Application Laid-open No. 58-1989.
127728 discloses that it can be used as a monomer for polymers. However, the former concerns homopolymers of DMONs or copolymers of DMONs with norbornene type comonomers, and the latter concerns DMONs.
Although the teaching teaches the use of a chain olefin as a molecular weight modifier for the homopolymerization or copolymerization of MONs, since the target is ring-opening polymers, polymers as shown in the following general formula (a) are used. It has a structure with unsaturated bonds in the main chain, and only products with poor heat aging resistance can be obtained. On the other hand, the copolymer proposed by the applicant has a structure as shown in the following general formula [11] as its main structure, and has substantially no unsaturated bonds, or even if it does have unsaturated bonds, it has very few unsaturated bonds. It is thought that because of its small amount, it is chemically stable and has excellent heat aging resistance.

In this way, the copolymer proposed by the applicant and Japanese Patent Publication No. 46-149
The structure is completely different from the polymers of Publication No. 10 and Japanese Patent Application Laid-Open No. 127728/1982, and the copolymer proposed by the applicant cannot be obtained even with the technical contents disclosed in both patent publications. .

The present invention relates to an improvement of the novel random copolymer proposed in the above-mentioned Japanese Patent Application No. 16995/1983, namely, in addition to the monomer component of the previously proposed random copolymer, α- Ternary or quaternary compound obtained by adding olefin or cycloolefin or both
Regarding the original copolymer. The random multicomponent copolymer of the present invention is not described at all in the prior art documents described so far, and it goes without saying that it cannot be obtained even with the contents disclosed therein.

[Structure of the invention]

That is, the present invention provides a compound represented by the following formula II). L% 5% 8.8a
- A random multicomponent copolymer consisting of octahydronaphthalenes (DMONs) and ethylene and an α-olefin and/or cycloolefin having 3 or more carbon atoms, (where R+ and R2 are hydrogen, alkyl, halogen and may be the same or different.) tB) Z terene/DMONs (molar ratio) Z > f9515 to 5/95, (C) [α-olefin having 3 or more carbon atoms and/or Cycloolefin)/DMONi (molar ratio) 9515
~20/80, the DMON units mainly have a structure represented by the following formula (II), and (E) the intrinsic viscosity r measured in decalin at 135°C
v) is 0.005 to 20 dl/9, and is a novel random multicomponent copolymer defined as follows.

The gist of the present invention is as described above, but to explain in more detail, the random multi-component copolymer of the present invention includes the following six types of embodiments.

[11DMONs/Ethylene/α- having 3 or more carbon atoms
Tertiary copolymer consisting of olefin, ll1I Six-component copolymer consisting of DMONs/ethylene/cycloolefin color, @) Quaternary copolymer consisting of DMONs/ethylene/α-olefin having 6 or more carbon atoms/cycloolefin Combined.

Furthermore, the novel random multicomponent copolymer of the present invention may contain a small amount of diene component.

Further, in the present invention, the term cycloolefin includes styrenes and unsaturated polycyclic hydrocarbon compounds (which may have a cross-linked bond) in addition to the commonly-used cycloolefins, which will be described in detail later.

Hereinafter, various monomer components constituting the random multi-element copolymer of the present invention and properties of the polymer will be explained in detail.

DMONs DMONs, which are raw materials for the random multicomponent polymer of the present invention, can be easily developed by condensing with norbornenes and cyclopentadiene as shown in the following formula.

In this general formula, R1 and R2 are hydrogen, a linear, branched, or cyclic alkyl group, or a halogen, and may be the same or different.

As a specific example of DMON, for example, 1,4゜5
．． 8-dimethano-i, 213t 414a, 5.8
．． In addition to 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+ 3.44a,
5.8.8a-Octahydronaphthalene, 2-propyl-1,4,5,8-dimethano-1* 2.3.4.4
a, 5.8+ 8a-octahydronaphthalene, 2-
Hexyl-1,4,5,8-dimethano-1,2°3,4
．． aa, 5.8+ 8a-octahydronaphthalene, 2-stearyl-1,4,5,8-dimethano-1,2
, 3゜4, 4a, 5.8.8a -off fi Hydronatsuta L/7.2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4゜4a+ 5v 8+ 8a-
Octahydronaphthalene, 2-methyl-3-ethyl-1
,4,5,8-dimethano-1,2,3゜4,4fa,
5.8.8 & -octahydronatsuta v:y,'l-chloro1.4.5.8-dimethano-L 2+ 31+'
4t 4a.

5,8.8&-octahydronaphthalene, 2-promo 1,4.5.8-dimethano-1+ 2+ 3+ 44a
, 5+ 8,8a.

-Octahydronaphthalene, 2-fluoro-1,4゜5
．． 8-dimethano-192T 3y 4.42L, 5.
8.8a-octahydronaphthalene, 2.3-17 chloro1.4.5゜8.8a-dimethano-L 2+ 3,
44a, sla, 8a-octahydronaphthalene, 2-cyclohexyl-1°4, 5.8-dumethanol 1
．． 2.3.4.4a, 5+ 8.8a-octahydronaphthalene, 2-inbutyl-1,4゜5.8-dimethano-1,213,4,4a, 5.818a-octahydronaphthalene, etc. . Preferred among these are those in which either 11f or a2 is substituted with an alkyl group having 1 to 20 carbon atoms.

α-olefin having 6 or more carbon atoms The α-olefin having 3 or more carbon atoms is linear or branched, such as propylene, isopropylene, 1-butene, 3-methyl-1- Butene, 1
-Pentene, 3-methyl-1-pentene, 4-methyl-
Examples include 1-pentene, 1-hexene, 1-octene, 1-decene, and 1-dodecene. Among these,
Alpha-olefins having 6 to 12 carbon atoms, particularly 3 to 6 carbon atoms, are preferred.

Cycloolefin Cycloolefin, which is one of the monomer components constituting the random multi-component copolymer of the present invention, includes cycloolefins used in the usual sense as described above, as well as nutylene numbers and unsaturated polycyclic hydrocarbons. It is a word with a broad concept that also includes compounds.

! Respecific Kld, cyclobutene, cyclopentene,
Cyclohexene, 3,4-dimethylcyclopentene, 6
-Methylcyclohexene, 2-(2-methylbuty/L"
l -1-Cyclohexene, styrene, α-methylstyrene, norbornene, methylnorbornene, ethylnorbornene, isobutylnorbornene, 2.3°a,
7a-tetrahydro-4,7-methano-1H-indene, 3a, 5t 6.7a-tetrahydro-4,7-
Examples include methano-1H-indene. Among these, cycloolefins having a norbornene ring such as norbornene, methylnorbornene, and ethylnorbornene are preferred.

Properties of the random multi-component copolymer: the DMONs, an α-olefin having 6 or more carbon atoms,
The properties of the random multi-component copolymer composed of cycloolefin and ethylene include (B) ethylene/DM
ONs (molar ratio) is 9515 to 5/95, especially 90/
10 to 20/80, and 1 cI r α-olefin and/or cycloolefin having 6 or more carbon atoms]/DMON (molar ratio) is 9515 to 20/80,
In particular, it is in the range of 90/10 to 30/70. (and) DMONs are copolymerized in the main structure in the random multi-component copolymer. Furthermore, even if a cross-linked unsaturated polycyclic hydrocarbon compound similar to DMONs is used as the third component cycloolefin, no ring-opening reaction occurs and the entire structure is mainly similar to DMONs.

Therefore, the iodine value of the random multicomponent copolymer of the present invention is usually 5 or less, and most of them are 1 or less. The fact that it has the above structure is also supported by C1C13-N. Therefore, the random multicomponent copolymer of the present invention has a chemically stable structure and is a polymer with excellent heat aging resistance.

The new random multi-component copolymer has an intrinsic viscosity [η] of 0.005 to 20 dlyy as measured in decalin at 135°C. Especially when used for wax applications, 0.01~
0.3 dl/V is preferable, and more preferably 0.05 to 0.2 dl
A range of /P is preferred. In the case of ordinary synthetic resin applications, it is particularly 0.5 to 10 dl/r, and more preferably 0.8 to 8 dl/r.
The range of i/r is preferably 0. The novel random multicomponent copolymer is generally amorphous or low crystallinity, and is preferably immaculate. Therefore, transparency is good. In general, the degree of crystallinity measured by X-rays is 5% or less, in many cases it is 0%, and in many cases the melting point cannot be observed by differential scanning calorimeter (DSC).

Another property of the new random multicomponent copolymer is a high glass transition temperature and high softening temperature.

That is, the glass transition temperature (Tf) measured by a dynamic viscoelasticity analyzer (DMA) is usually 80 to 190°C, often 100 to 1
Measured within 90°C. Also TMA (Ther
m.

-Mechanical Analyser: Manufactured by DuPont, with a load of 492 and a quartz needle (diameter 0.635)
771) at a heating rate of 5°C/min, the temperature at which the needle penetrates 0.1"m, that is, the softening temperature, is usually 70°C.
-180°C, mostly within the range of 90-180°C.

The thermal decomposition temperature is usually 350 to 40°C, assuming that the temperature at which the weight loss starts is raised at a rate of 10°C/win using a heat-filled bottle (TGA: manufactured by Rigaku Denki Co., Ltd.) under a nitrogen stream.
20°C, mostly within the range of 670-400°C.

As for mechanical properties, the bending elastic modulus is usually lX10'~6xl
It is within the range of Q'Ky/-, and the bending yield strength is usually 30
It is within the range of 0 to 1500 Ki/crA.

Density was determined using the density gradient tube method (ASTM D1505
) is usually 0.86 to 1.1Of/csl, most of which are 0.
．． It falls within the range of 88 to 1.0817 cd. Also, the refractive index (
ASTM D542) is 1.47 to 1,58, mostly 1
．． It is within the range of 48 to 1.56, and since it is substantially amorphous, its haze (ASTM D1003) is usually 20 degrees or less, often 10 degrees or less.

As for electrical properties, the dielectric constant (1KHz) according to ASTM D 150 is 1.5 to 3.0, often 1.9 to 2.6.
, the dielectric loss tangent is in the range of 9 x 10-' to 8 x 10-', often in the range of 3 x 10-' to 9 x 10-5. It also has excellent chemical resistance and is virtually unaffected by acids and alkalis.

In addition, the novel random multicomponent copolymer of the present invention has D
Even if the content of MONs is reduced, it shows a high glass transition temperature. In other words, when comparing those with the same glass transition point, D
The novel random multi-component copolymer of the present invention, in which the composition of DMONs/ethylene/α-olefin and/or cycloolefin has a higher unit price than the composition of MONs/ethylene, may be able to reduce the amount of DMONs. , has an excellent balance of transparency, heat resistance, heat aging resistance, mechanical properties, dielectric properties, chemical resistance, and solvent resistance.For example, its low molecular weight product can be used as a synthetic wax for waxing purposes, or for waxing purposes. Wood impregnating agents, paper processing agents, sizing agents, rubber anti-aging agents, cardboard waterproofing agents, chemical fertilizer slowing agents, heat storage agents, ceramic binders, paper capacitors, electrical insulation materials such as electric wires and cables, neutron moderators, Textile processing aid, building material water repellent,
Paint protectants, polishing agents, thixotropy agents, pencil/crayon lead complexity agents, carbon ink base materials, toners for electrostatic copying, lubricants for synthetic resin molding, mold release agents, resin colorants, hot melt adhesives It can be used in fields such as lubricating grease. In addition, the polymer is used in optical fields such as optical lenses, optical disks, optical fibers, and glass window applications, water tanks for electric irons, microwave oven supplies, liquid crystal display substrates, printed circuit boards, high frequency circuit boards, transparent conductive sheets, etc. The novel random multi-component copolymer of the present invention can be used in various fields such as electrical fields such as films, medical fields such as syringes, pipettes, and animal gauges, chemical fields, camera bodies, various instrument housings, films, sheets, and helmets. It is molded using a well-known method. For example, single screw extruder, vented extruder, twin screw extruder, conical twin screw extruder, co-kneader, platificator, mixtruder, twin conical screw extruder, planetary screw extruder, gear extruder Extrusion molding, injection molding, blow molding, rotational molding, etc. are performed using screwless extruders.

In addition, in 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, dyes, pigments, etc. are added as necessary. etc. may be added.

Examples of such additives include phenolic or sulfur antioxidants. Examples of phenolic antioxidants include 2,6-tert-butyl-p-cunzol, stearyl (3,3-dimethyl-4
-hydroxybenzyl)thioglycolate, stearyl-β-(4-hydroxy-3,5-di-tert-butylphenol)propionate, distearyl-5,5
-di-tert-butyl-4-hydroxybenzylphosphonate, 2.4.6- ) lis(3', 5'-
tert--ff-4-hydroxybenzylthio)-1,! 1.5-triazine, distearyl (4-
Hydroxy-3-methyl-5-tert-butylbenzyl) Maloney), 2,2'-methylenebis(4-methyl-6-tart-butylphenol), 4,4'-methylenebis(216-di-tert-butylphenol)
, 2'-methylenebisC6-(1-methylcyclohexyl)p-cresol], bis[3゜5-bisr4-
Hydroxy-3-tert-butylphenyl)butyric acidocoglycol ester, 4,4'-butylidenebis(6-tert-butyl-m-cresol),
1,1.3-)lis(2-methyl-4-hydroxy-5
-tert-butylphenyl)butane, bis! "2-t
19rt-Butyl-4-methyl-6-(2-hydroquiic-3-tart-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3.5-)lis(2,6-
dimethyl-3-hydroxy-a-tert-butyl)benzyl isocyanurate s 1r 5t :) )
Lis(3,5-butyl-4-hydro-thousandiphenyl)-2,4,6-)listylbenzene, Tetrakis[methylene-3-(3,5-butyl-4-hydro-thousandiphenyl)globionate 〕methane.

1,3.5-)lis(3,5-di-tert-butyl-4-hydroxybenzyl)in cyanurate, 1,3.
5-Tris r(3,5-di-tert-butyl-4-hydroxyphenyl)globionyloxyethyl]isocynurate, 2-octylthio-4,6-di(4-hydroxy-6,5-di-tert-butyl) ) Phenoxy
1,3,5-)riazine, 4,4-thiobis(6-te
Phenols such as rt-butyl-m-cresol) and 4,4'-butylidenebis(2-tert-butyl-
Examples include polyhydric phenol carbonate oligoesters such as carbonate oligoesters (for example, polymerization degree of 2.3.4.5.6.7.8.9.10) of 5-methylphenol.

Examples of sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl, simiristyl, and distearyl, and butyl, octyl, lauryl, and the like.
polyhydric alcohols of alkylthiopropionic acids such as stearyl, such as glycerin, trimethylolethane,
Examples include esters of trimethylolpropane, pentaerythritol, trishydroxyethyl insialate (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) phosahite, triphenyl phosphite, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearyl Pentaerythritol diphosphite, tet→(tridecyl)-1,1,
3-) Lis(2-methyl-5-tert-butyl-4-
Hydroxyphenyl)butane diphosphite, tetra(
C12~G+5 mixed alkyl)-4,4'-isobropylidene diphenyl diphonufite, tetra(tridecyl)-4,4'-butylidene bis(3-methyl-6-te
rt-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′-impropylidenediphenol・pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol Diphosphite, bis(2)
,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, TrisC4,4'
-isopropylidene bis(2-tert-butylphenol)]phosphite, phenyl diindecylphosphite°, cy(nonylphenyl)pentaerythritol diphosphite), tris(1,3-di-stearoyloxyimprovil)phosphite , 4.4'-impropylidene bis(2-tert-butylphenol).
Di(nonylphenyl)phosphite, 9゜10-di-hydro-9-oxa-10-phos7affenanthrene-1
0-O thousand side, tetrakis (2,4-G tert-
butylphenyl)-4,4'-piphenylene diphosphonite and the like.

Also, 6-hydroxychroman derivatives such as α, β, γ
, various tocopherols of δ and mixtures thereof, 2-(4
2,5-dimethyl substituted product, 2,5.8-trimethyl substituted product, 2,5,7.8-tetramethyl substituted product of -methyl-pent-6-enyl)-6-hydroxychroman, 2.
2,7-dolimethyl-5-tert-butyl-6-hydroxychroman, 2,2,5-)limethyl-7-ter
t-Butyl-6-hydroxychroman, 2,2゜5-trimethyl-6-tert-butyl-6-hydroxychroman, 2,2-dimethyl-5-tart-butyl-6-
Hydroxychroman, etc., is also represented by the general formula % (where M is Mg, Ca or Zn, A is an anion other than a hydroxyl group, sXs'l and 2 are positive numbers, and a is 0 or a positive number). complex compounds such as Mg6A1
2(oH)16Co3・4H20, Mg, A/2(O
H)2oC○, , 5H5H2O1,kg 2(OH
),,Co,・4H20,Mg,oAt2(OH)2
2(Co,)2-4H20, Mg6A12(OH), 6
HPO4・4H20, Ca6Az 2(OH), 6Co
3-4H20゜Zn6Ar 2(OH), 6Go, -4
H20゜Zn6Az2(OH), 6S○4・4H20,
Mg6AJ2(OH), 6So4.4H20°Mg, 6
kl 2(OH), □Go, -3H20su,! :F combination L is good.

Furthermore, 6-phenyl-2-benzofuranone, 6-
An antioxidant having a 2-benzofuranone skeleton such as 7-enyl-4,6-di-t-butyl-2-benzofuranone may be blended.

Examples of light stabilizers include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-o, ctoxybenzophenone% 2.2'-di-hydroxy-
Hydroxybenzophenones such as 4-methoxybenzophenone and 2,4-dihydroxybenzophenone, 2-
(2'-hydroxy-3'-tert-butyl-5'
-methylphenyl)-5-chlorobenzotriacyl
2-(2'-hydroxy-3',5'-tert-
butylphenyl)-5-chlorobenzotriazole, 2
-(2'-hydroxy-5'-methyl7enyl)benzotriazole, 2-(2'-hydroxy-3',5'-
Benzotriazoles such as di-tert-amylphenyl) benzotriazole, phenyl salicylate, p
-tert-butylphenyl salicylate, 2,4-di-tert-butylphenyl-3,5-di-tert-
4-Hydroxybenzoate, hexadecyl-3,5-
Benzoates of di-tert-butyl-4-hydroxypenzenetonate, 2,2'-thiobis(4-te
rt-octylphenol) Ni salt, (2,2'-thiobis(4-tart-octylphenol)))
-n-butyl Ni, (6,5-di
Nickel compounds such as rt-butyl-4-hydroxybenzyl)phosphonic acid monoethyl ester N1 salt, α-
Substituted acrylonitriles such as methyl cyano-β-methyl-β-(p-methoxyphenyl)acrylate and HN'
-2-ethylphenyl-N-ethoxy-5-tert-
Oxalic acid dianilides such as butylphenyl oxalic acid diamide, N-2-ethylphenyl-N/2-ethoxyphenyl oxalic acid diamide, bis(2,2,6,6-
Tetramethyl-4-piperidine) Sepacade, Poly(
B 6-(1,,1,3,3-tetramethylbutyl)imino l-1,3,5-1-riazine-2゜4-diyl(
4-(2,2,6,6-titramethylpiperidyl)imino)hexamethylene), 2-(4-hydroxy-2,2
, 6,6-tetramethyl-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, valmitic acid, margaric acid, stenoic acid, agononic acid, alaxic acid, and behenic acid. or their metal salts, such as lithium salt, calcium salt, sodium salt, magnesium salt, potassium salt, etc., aliphatic alcohols such as palmityl alcohol, cetyl alcohol, stearyl alcohol, caproic acid amide, caprylic acid amide, capric acid amide, lauric acid amide, myristic acid amide, valmitic acid amide, aliphatic amide such as stearic acid amide, esters of fatty acids and alcohols, fluorine such as fluoroalkyl carboxylic acid or its metal salt, fluoroalkylsulfonic acid metal salt, etc. Compounds are grouped together.

As fillers, inorganic or organic fibrous fillers such as glass fibers, silver or aluminum coated glass fibers, stainless steel fibers, aluminum fibers, potassium titanate fibers, carbon fibers, Kepler fibers, ultra-high elastic polyethylene fibers, Talc, calcium carbonate, magnesium hydroxide,
Powdered, granular, flake inorganic or Examples include organic fillers.

Furthermore, the novel random multicomponent copolymer of the present invention may be used in combination with various known polymers. Examples of such polymers include: (a) having one or two unsaturated bonds; Polymers derived from hydrocarbons, specifically polyolefins, include polyethylene, polypropylene 7, polyimbutylene, polymethylbutene-1, poly4-methylpentene-1, which may have a crosslinked structure.
, Polypden-1. polyisoprene, polybutadiene,
Polystyrene, or a copolymer of monomers constituting the above polymers, such as ethylene/propylene copolymer, propylene lipten-1 copolymer, propylene/isobutylene copolymer, styrene/imbutylene copolymer, styrene/ Butadiene copolymer, ethylene and propylene and diene t
For example, terpolymers with hexadiene, cyclopentadiene, ethylidenenorbornene, etc., or blends, graft polymers, block copolymers, etc. of these polymers, (b) halogen-containing vinyl polymers, specifically is a polymer derived from Pi α,β-unsaturated acids and their derivatives, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene, chlorinated rubber, etc., specifically polyacrylate, polymethacrylate, poly Comonomers of acrylamide, polyacrylonitrile, or monomers constituting the above polymers with other copolymerizable monomers, such as acrylonitrile/butadiene/styrene copolymer, acrylonitrile/styrene copolymer, acrylonitrile/styrene/acrylic Acid ester copolymers, etc.) Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, specifically polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polymaleic acid Vinyl, polyvinyl butyral, polyallyl phthalate,
Polyarylmelamine, or copolymers of monomers constituting said polymers with other copolymerizable monomers, such as ethylene/vinyl acetate copolymers, etc.) Polymers derived from epoxides, specifically polystyrene Polyacetals such as polymers derived from cyto- or bisglycidyl ethers, specifically polyoxymethylene, polyoxyethylene,
Such as polyoxymethylene containing ethylene oxide as a comonomer.

Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or aminocarboxylic acids or corresponding lactams, in particular nylon 6. , nylon 66, nylon 11, nylon 12, etc.

(w) Polyesters derived from dicarboxylic acids and dialcohols and/or oxycarboxylic acids or corresponding lactones, in particular polyethylene terephthalate, polybutylene terephthalate, poly 1,4-dimethylol cyclohexane terephthalate, (aldehyde 7-enol and urea polymer have a cross-linked structure derived from melamine, specifically phenol-formaldehyde resin.

Wl alkyd resins such as urea/formaldehyde resin, melamine/formaldehyde resin.

Specifically, unsaturated polyester resins such as glycerin and phthalic acid resins (1. Examples include halogen-containing modified resins, natural polymers, specifically cellulose, rubber, proteins, or derivatives thereof, such as cellulose acetate, cellulose propionate, cellulose vinegar, and cellulose ether. When used as a synthetic wax, it goes without saying that various known waxes may be mixed.

Furthermore, the copolymers of the present invention may be completely mixed together. In order to produce the novel random multicomponent copolymer of the present invention, the above-mentioned monomer components may be polymerized using a well-known Ziegler catalyst.

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

The titanium compound supported on the magnesium compound is preferably a complex containing at least magnesium, titanium, and nologen, and is preferably a compound obtained by bringing a magnesium compound and a titanium compound into close contact with each other by means such as heating or co-pulverization. The halogen/titanium molar ratio contained in the composite is approximately 4, and the titanium compound is not substantially eliminated by hexane washing 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, and the magnesium/titanium (molar ratio) is about 3 or more, preferably about 5 to about 501. When the composite contains an electron donor, the electron donor/titanium c molar ratio) is about 0.2 to about 6. Preferably, the specific surface area is about 0.4 to about 6, more preferably about 0.8 to about 2, and the specific surface area is about 3rr.
f/P or more, more preferably about 40rn''/P or more, and even more preferably about 100rn''/2 or more. Also, the X-ray spectrum of the composite shows non-quality irrespective of the starting magnesium compound. As an example of means for producing a wax composite which is preferably in a highly amorphous state compared to that of ordinary commercial products of magnesium cybaride, for example, JP-A-48-
16986, JP-A-51-18385, % JP-A-50-126590, JP-A-51-20297, JP-A-51-28189, JP-A-51-92885,
JP-A-51-127185, JP-A-51-13662
No. 5, JP-A-52-87489, JP-A-52-100
596, JP-A-52-104593, JP-A-52-
No. 147688, Japanese Patent Application Laid-open No. 53-2580, Italian Special Patent Application dated November 12, 1975, etc.
I can show J.

Examples of Hanadi+7m compounds include VCl4, VBr4.
VCl3, V Br, etc./SO vanadium genide, V
OC6, VOBr, VOCl2. Vanadium oxyhalides such as VOBr2 or VO(OR)nX
, n (i, R is a hydrocarbon group, X is a halogen, Own
≦3) A vanadium compound represented by the formula is mentioned. Among these, hydrocarbon-soluble vanadium compounds, especially vanadium oxy-logenide or VO(OR)n
Compounds represented by X and -n are preferred. Said VO(O
R) In the compound represented by nX, -1, R is an aliphatic, alicyclic or aromatic hydrocarbon group, preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, particularly 1
~3 is good. Also, n is O<n=3, preferably 1≦
The range is n≦1.5. Examples of such vanadium compounds are Teha, VO(OCH, >C12, VO(OCH
,)2C1゜VO(OCR,),,VO(OC2H5)
(J2,VO(OC2H5),,5C11,5,VO(
QC2H,)2CLVO(OC2H5) 3,VO(O
C2H5)4.5Br1.5, VO(QC,H,)C6
,,VO(QC,H,) 4. s CL, s, VO(Q
C3H,)2CA, VO(QC3H,), .

VO (On-C, H7) C/12, vo (On c
aH? ) 2C1vVO (Oiso C4H9),
(J, VO(Osec C4H,), VO(QC5H,)
, 1) 1.5CI, 5 or a mixture of these can be mentioned.
Alkylaluminum compounds that can be easily obtained by reacting have the general formula R'mAJX',
-m (where R' is a hydrocarbon group, X' is a halogen, 0
・It is indicated by m≦3). Examples of the alkyl aluminum compound include trialkylaluminium, dialkylaluminum halide, alkyl aluminum civalide, any mixture thereof, and a mixture of these and alkyl aluminum trihalide.

Polymerization takes place in a hydrocarbon medium. That's it.

Aliphatic hydrocarbons such as hexane, heptane, octane, and kerosene, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as benzene, toluene, and xylene can be used as the solvent alone or in combination. .

The polymerization is carried out in a reaction medium, for example, in the case of a titanium compound and an alkyl aluminum compound, the former is 0.001 to 10
mmol/l, preferably] 7 or 0.01 to 5 mmol/l
The latter is adjusted so that the Aβ/Ti (molar ratio) is 5 or more, preferably 1Q00 or less, and most preferably 10 to 100.

7. In the case of a vanadium compound and an alkyl aluminum compound, the concentration of the former is adjusted to be 0.01 to 50 mmol/l, preferably 0.01 to 10 mmol/l;
The latter is adjusted so that the Al/V (molar ratio) is 2 or more, preferably 50 or less, and particularly preferably 6-20. Among these catalyst systems, the latter one using a vanadium system is particularly preferred.

DMONs and ethylene and α- having 3 or more carbon atoms
When copolymerizing olefins and/or cycloolefins, the charging ratio of these seven-mer components depends on the composition of the desired random multi-component copolymer and the type of reaction medium.

Although it varies depending on the polymerization temperature, pressure, and type of catalyst, the molar ratio of ethylene/DMON in the reaction medium is generally 1/1.
00 to 100/1, preferably 1/10 to 10/1, and further, the molar ratio of [α-olefin and/or cycloolefin having 3 or more carbon atoms]/DMONi is 100/1 to 1/100. ．． Preferably 10/1 to 115
Adjust so that it becomes 0. Polymerization temperature is -50~300℃,
Preferably -30~200℃, polymerization pressure 0~100''
In order to adjust the molecular weight of the polymer to be maintained at P/cA, preferably from 0 to 50, a molecular weight regulator such as hydrogen may be present as appropriate.

〔Example〕

The content of the present invention will be explained in more detail below using preferred examples, but the content of the present invention can be modified in any manner as long as the purpose is not impaired, and is not limited by these examples. isn't it.

Example 1 A sufficiently dried 500 ml Sebawopul flask was equipped with a stirring blade, a gas blowing tube, a thermometer, and a dropping rotor, and the flask was sufficiently purged with nitrogen.

To this flask was charged 250 mβ of toluene that had been dehydrated and dried using a molecular sheep.

In a flask under nitrogen flow, mi3 from Table 1 was added as DMON.
．． EH', cycloolefin in Table 1 (force 6.8
2. Add 2.5 mmol of ethylaluminum sesquichloride and vanadium oxytrichloride (Vo
cz,) was added in an amount of 0.25 mmol.

A mixed gas of 20 A/hr of dry ethylene and 40 #/hr of nitrogen was passed through the gas blowing pipe through the Flanuco controlled at 10°C for 10 minutes, and all of the ethylaluminum sesquichloride was added dropwise from the dropping funnel to start the copolymerization reaction. Then, a copolymerization reaction was carried out at 10° C. for 30 minutes while passing the above mixed gas.

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

Methanol 5m! is added to the polymerization solution to stop the copolymerization reaction, or the polymerization solution after the reaction is stopped is poured into a large amount of methanol and acetone to precipitate the copolymer, and after further washing with acetone, it is vacuum dried at 60°C overnight. and copolymer s, ir'
I got 6.

The ethylene composition in the copolymer determined by 13C-NMR analysis was 55 moles, the intrinsic viscosity [η] measured in decalin at 135° C. was 4.2 d6/P, and the elementary value of η was 0.7. Also, the density according to ASTM D1505 is 1.00
9 y/crIL3cl, huh? In addition, in order to measure the mechanical properties, press-molded sheets with a thickness of 1 or 2 balls were prepared by hotpressing at 230°C. When X-ray diffraction was performed using these sheets, no scattering due to crystals was observed. First, the crystallinity (Wc) was 0. The transparency of the 11IIK sheet was 8 when measured using a haze meter in accordance with ASTM D 1003-52.

Refractive height (nD) according to ASTM D 542 is 1.52
It was 7. Bending elastic modulus and bending yield strength are 21tN
2.2 x 10' MP each as measured in accordance with ASTN D 790 using thick pressed sheets
/cJ, 950IP/J. Glass transition temperature Tg
is Dynamic Mechanical manufactured by DuPont
The loss modulus E" was measured at a heating rate of 5°C/min using an analyzer (DMA), and the peak temperature was determined to be 135°C. Furthermore, the melting point Tm
! 1 by DuPont 990 type DSC
No melting curve (peak) was observed when the temperature was measured in the range of -120°C to 400°C at a heating rate of 0°C/min. When the thermal decomposition temperature was measured using a heat-immersed glass (TGA), it was 681°C.The electrical properties were measured using a dielectric loss measuring device made by Ando Electric, and it was 1 K.
When measured at Hy, the dielectric constant was 2.1 dielectric loss tangent (t
anδ) is 3. It was OX 10-'. Furthermore, in order to investigate chemical resistance, press-formed products were tested at room temperature with sulfuric acid (97%
%), aqueous ammonia (204), acetone, ethyl acetate, etc. for 20 hours and observed the appearance.
No symptoms such as decreased transparency, deformation, dissolution, or cracking were observed.

Examples 2 to 14 The same operations as in Example 1 were carried out except that the conditions in the copolymerization reaction were changed as shown in Table 2, and the results shown in Table 2 were obtained. Table 2 and Table 5 list the conditions and results of Example 1.

Example 15 In the polymerization of Example 1, (7) was added for 5 t, and (force) was added for 5 t.

25 mmol of ethylaluminum sesquichloride,
゛Instead of vanadium oxychloride, 2.5 mmol of dichloroethoxy quinpanadium was used, the flow rate of ethylene was 80 n/hr, and the flow rate of hydrogen was 80 n/hr instead of nitrogen.
01/hr, except that the polymerization temperature was 30°C, the copolymerization reaction was carried out in the same manner, and a copolymer of 3.81% was obtained. 20
Mol%, intrinsic viscosity measured in decalin at 135°C [η]
is 0.10. =1 Prime value was 0.6 Emiller rotational viscometer (manufactured by Yagami), 75 Grpm, 28
It was measured at 0'C and was found to be 1 osocp.

Holimar at 200℃ 11! A measurement test piece was prepared by press molding to a thickness of Lm. The sheet was fairly brittle in nature. The crystallinity by X-ray diffraction is 0%,
5℃/DuPont Differential Scanning Calorimeter 990 (DSC)
When measured at a heating rate of min., no melting peak was observed, and the glass transition temperature was 123°C. Penetration measuring device manufactured by DuPont (TMA: Therm)
omechanical anelys, er, load 4
10°C/min with 92.0.025 inch quartz needle)
The softening temperature of the heating rate was 120°C. ASTM
Haze according to D'1003-52 is 1
It was 2 chi. Furthermore, in order to check the solvent resistance, the test pieces were immersed in 97% sulfuric acid, 2fM aqueous ammonia, acetone, methyl acetate, etc. for 20 hours, and then the appearance was observed. It did not fit.

Table 1 〔Effect of the invention〕

Claims (4)

[Claims] (1) (A) 1, 4, 5, 8 represented by the following formula (I)
-Dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalenes (hereinafter abbreviated as DMONs)
A random multicomponent copolymer consisting of ethylene and an α-olefin and/or a cycloolefin having 3 or more carbon atoms, ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) (where R^1, R ^2 is hydrogen, an alkyl group, or a halogen, and each may be the same or different.) (B) Ethylene/DMON (molar ratio) is 95/5 to 5
/95, (C) [α-olefin and/or cycloolefin having 3 or more carbon atoms]/DMONs (molar ratio) is 95/5 to 20/80, (D) DMON units are mainly composed of the following formula (II ) has the structure shown in ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) (E) Intrinsic viscosity measured in decalin at 135℃ [η]
A novel random multicomponent copolymer defined by 0.005 to 20 dl/g. (2) A novel random multicomponent copolymer according to claim 1, comprising DMONs, ethylene, and an α-olefin having 3 or more carbon atoms. (3) A novel random multicomponent copolymer according to claim 1, comprising DMONs, ethylene, and cycloolefin. (4) A novel random multicomponent copolymer according to claim 1, comprising DMONs, ethylene, an α-olefin having 3 or more carbon atoms, and a cycloolefin.