JPS6234924A - Crosslinking of cyclic olefin copolymer - Google Patents

Abstract

PURPOSE:To obtain the titled copolymer having excellent heat-resistance, solvent-resistance, chemical resistance and strength, etc., by crosslinking a specific cyclic olefin copolymer with sulfur, an organic peroxide, electron beam or radiation. CONSTITUTION:A cyclic olefin random copolymer containing a cyclic olefin of formula I (R<1>-R<12> are H, alkyl or halogen; R<9> or R<10> and R<11> or R<12> may together form a ring; n is 0 or >=1) and at least ethylene as comonomer components, wherein said cyclic olefin essentially takes the structure of formula II in the copolymer, is crosslinked with sulfur, an organic peroxide, electron beam or radiation. The molar ratio of ethylene to the monomer component of formula I in the cyclic olefin copolymer is preferably 40/60-90/10.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for crosslinking a cyclic olefin copolymer that can provide a cyclic olefin copolymer having excellent heat resistance, bath agent resistance, strength, etc.

[Conventional technology]

The applicant previously proposed a new substantially amorphous polymer having a cyclic olefin structure as shown in formula (2) in the polymer. Such polymers have excellent transparency, heat resistance, chemical resistance, solvent resistance, electrical properties, mechanical strength, moldability, and dimensional stability, and can be used in various fields.

However, depending on the application, further heat resistance, solvent resistance, or mechanical strength may be required, so if the above-mentioned cyclic olefin polymer is modified to improve these properties, its field of use will further expand. .

[Problem that the invention seeks to solve]

The problem to be solved by the present invention is to provide a method for modifying the above-mentioned cyclic olefin polymer to improve heat resistance, chemical resistance, bath agent resistance, mechanical properties, etc.

Means for Solving Problem C] That is, the present invention is a method of crosslinking a cyclic olefin copolymer with sulfur or M peroxide, an electron beam or radiation, the cyclic olefin copolymer having the formula A cyclic olefin is a random copolymer containing the cyclic olefin of (1) and at least ethylene as a comonomer component, and the cyclic olefin substantially has the structure of formula (2) in the copolymer. This is a method for crosslinking copolymers.

(+1(21) (In the formula, R1 to R11+ are hydrogen, an alkyl group, or a halogen, and may be the same or different, and R11 or RIG and Hp or RltJ may mutually form a ring. (n is 0 or a positive number of 1 or more, and when n is 2 or more, n R5-R8 may be the same or different.) [Operations and Effects] In the present invention, crosslinking The copolymer used contains the monomer of formula (1) and ethylene as essential components.

In the copolymer, the molar ratio of ethylene/monomer component of formula (11) is 5795 to 9515, particularly 40/60 to 90/1.
The range of 0 is preferable, and when an α-olefin other than ethylene is coexisting, the molar ratio of the total amount of these monomers/monomer component of formula (1) is 5795 to 9515,
Particularly preferred is a range of 30/70 to 90/10. Further, in the present invention, it goes without saying that the monomer component of formula (1) may be used not only as a single component but also as a mixture of a plurality of components represented by formula (1).

Specific examples of the monomer component represented by formula (1) include the following, but the examples shown here are extremely limited and are not those represented by formula (1). Any monomer component can be used as a monomer component of the present invention.

6 Among these, the formula (n=o or 1 in 11,
That is, monomer components represented by formulas (3), (4), and the like are preferable in terms of easy monomer availability or monomer synthesis.

Furthermore, those with n=1 are more preferable because they have better heat resistance etc. than those with n=o.

Other α-olefins that can be copolymerized with the monomer component of formula (1) and ethylene include α-olefins having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, such as propylene, 1-butene, 6-methyl-1-fun% 1
-Pentene, 6-methyl-1-pentene, 4-methyl-
Examples include 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-icosene.

Cyclic olefins other than formula (1) that can be copolymerized with the monomer component of formula (1) include non-crosslinked cycloolefins and styrenes, 7'C,! :
, tid'cyclopentene, cyclohexene, 3.4-
dimethylcyclopentene, 3-methylcyclohexene,
2-(2-Methylbutyl)-1-cyclohexene, styrene, α-methylstyrene, 3a.

5,6.7a-tetrahuman 0-4.7-#'/-IH
- Examples include indene. Further, copolymerizable polyene components include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-hebutadiene, 7-methyl- Roux 1.6
-Octadiene, cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-impropylidene-2
-norbornene, 6-chloromethyl-5-(cyclobenyl-2-norbornene, divinylbenzene, 1,5-hexadiene.

Non-conjugated dienes such as norbornadiene, 2,3-diisopropyridene-5-norbornene, 2-ethyridane-
Representative examples include trienes such as 3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene, 1,3.7-octatriene, and 1,4.9-decatriene. Polyene components of particular interest are dicyclopentadiene, 5-vinylnorbornene, and 5-ethylidene-2-norbornene.

Furthermore, in addition to the monomer components described above, the copolymer may contain small amounts of other copolymerizable monomer components within a range that does not impair the object of the present invention.

The copolymer is produced by polymerizing the monomer component of formula (1) detailed above, ethylene, and, if necessary, other α-olefins and/or cyclic olefins using a well-known Ziegler catalyst, particularly a vanadium-based Ziegler catalyst. Manufactured by More details are disclosed in prior patent applications filed by the applicant (for example, Japanese Patent Application No. 50-110545 or 60-113074). The characteristic of the polymer is that the monomer component of formula (1) mainly takes the structure shown by formula (2) in the polymer, so that the iodine value of the copolymer does not include the polyene component. In the case of polyene components, the number is usually 5 or less, often 1 or less, and in the case of containing a polyene component, it is in the range of 2 to 50, and most of the numbers are in the range of 5 to 30. Furthermore, the fact that it has the structure of formula (2) is also supported by C-NMR.

By adopting this structure, the copolymer is chemically stable and has excellent water resistance and resistance to chemicals such as alkalis and acids, as well as excellent solvent resistance, heat resistance, and weather resistance. It also has an extremely low moisture content.

Furthermore, the copolymers of the raw materials of the present invention have low crystallinity, many of them are of poor quality, and many have no observed melting point.

Various known methods can be used to crosslink the above-mentioned copolymer, but particularly preferred are crosslinking by blending sulfur or organic peroxides, and crosslinking by irradiation with electron beams or radiation.

Sulfur crosslinking When the copolymer of the present invention is crosslinked with sulfur, a sulfur-based compound and, if necessary, a vulcanization accelerator and a vulcanization accelerator are added to the copolymer and heated to cause a crosslinking reaction. Close. Although there is no particular restriction on the amount of the sulfur-based compound, it is 0.1 parts by weight per 100 parts by weight of the copolymer in order to efficiently carry out the crosslinking reaction and improve the physical properties of the resulting crosslinked product, as well as from the economical point of view. ~10 parts by weight, preferably 0.3 to 5 parts by weight, and when used in combination with a vulcanization accelerator or vulcanization accelerator, 0.1 to 20 parts by weight, preferably 0.2 parts by weight. ~1
It is used in a range of 0 parts by weight.

Since the copolymer crosslinked by sulfur must have unsaturated bonds, it is preferable to use a copolymer containing a polyene component as a comonomer component and having an iodine value in the range of 5 to 50.

Various known sulfur compounds can be used to cause the crosslinking reaction, examples include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and dimethyldithiocarbamic acid. In addition, various vulcanization accelerators can be used, such as selenium, N-cyclohexyl-2-benzothiazole-sulfenami)-1N
-1su- Oxydiethylene-2-benzothiazole-sulfenamide %N, N-diisopropyl-2-benzothiazole-sulfenamide, 2-1 mercaftobenzothiazole, 2-(2,4-dinitrophenyl) Thiazoles such as mercaptobenzothiazole, 2-(2゜6-diethyl-4-morpholinothio)benzothiazole, benzothiazyl-disulfide; diphenylguanidine, triphenylguanidine, dioruntolylguanidine, oruntolyl biguanide, diphenylguanidine Guanidine series such as phthalate; acetaldehyde
Aniline reactant; butyraldehyde-aniline condensate;
Aldehyde amines or aldehyde-ammonia systems such as hexamethylenetetramine and acetaldehyde ammonia; imidacillin systems such as 2-mercaptoimidacillin; thiourea systems such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, and diorthotolylthiourea. ; Thiuram series such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethylthiocarbamate, di-n-butyldithiocarbamate Zinc, zinc ethyl phenyl dithiocarbamate, zinc butylphenyl dithiocarbamate,
Examples include dithioate salts such as sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, and tellurium diethyldithiocarbamate; xanthate salts such as zinc dibutylxanthate; and the like.

Examples of vulcanization accelerators include zinc oxide, activated zinc white, zinc carbonate, composite zinc white, magnesium oxide, metal oxides such as lithium, red lead, and basic lead carbonate, stearic acid, oleic acid, and lauric. acids, fatty acids such as lead stearate,
Examples include organic amines and glycols such as triethanolamine and diethylene glycol.

Organic peroxide bridge Crosslinking with an organic peroxide is suitable when the copolymer is in the form of a saturated polymer, that is, it does not contain a polyene component as a comonomer and therefore has an iodine number of 5 or less.

For crosslinking using an organic peroxide, the usual crosslinking method using an organic peroxide applied to polyolefins can be applied as is. That is, an organic peroxide such as dicumyl peroxide is blended into the copolymer of the present invention, a crosslinking aid such as triallyl cyanurate is blended as needed, and the copolymer is heated and crosslinked.

Although there is no particular restriction on the blending ratio of the organic peroxide, it is about 0.02 to 10 parts by weight per 100 parts by weight of the copolymer, preferably 0.0605 to 100 parts by weight, for the same reason as the above-mentioned blending ratio of sulfur.
-5 parts by weight, and when a crosslinking auxiliary agent is used in combination, the amount of the auxiliary agent is 0.02 to 8 parts by weight, preferably 0.03 to 3 parts by weight.

Examples of organic peroxides include 2,4-dichloropenzoylheroxide, benzoylperoxide, 1゜1-di(t
-butylperoxy) 3.3.5-) Limethylcyclohexane, n-butyl-4,4-di(t-butylperoxy)valerate, dicumylperoxide, α, α'-
Bis(t-butylperoxydiisopropyl)benzene, 2,5-dimethyl-2゜5-di(t-butylperoxy)hexane, -butylperoxycumene, di-t-
Butyl peroxide, 2,5-dimethyl-2,5-di(
t-Butylperoxy)hexyne-3 can be mentioned as an example, but these are extremely limited examples, and more detailed examples of organic peroxides are given in "Crosslinking Agent Handbook JP520-535" published by Taiseisha. Crosslinking aids are used to increase the crosslinking efficiency of organic peroxides, and compounds with sulfur and polyfunctional double bonds are used.More specifically, in addition to sulfur, metaphenylene bismaleimide and quinone are used. dioxime, 1,2-polybutadiene,
Examples include triallyl cyanurate, diallyl phthalate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, triethylene glycol dimethacrylate, and triallyl in cyanurate.

The above-mentioned sulfur crosslinking is similar, but the crosslinking is usually 100 to 2
The crosslinking is carried out at a temperature of 50°C, preferably 120 to 200°C, and a crosslinking time of usually 10 to 60 minutes, preferably 20 to 40 minutes. In particular, when crosslinking with organic peroxides,
The crosslinking time is preferably about four times the half-life of the organic peroxide.

Crosslinking by electron beam or radiation The copolymers of the present invention are also crosslinked by electron beam or radiation. When carrying out electron beam or radiation crosslinking, shea lyl sepacate, triallyl cyanurate, or N is used to increase the crosslinking efficiency.

N'-hexamethylene bismethacrylamide or the like may also be blended. The amount of electron beam irradiation is about 10 to 50 Mrad, but there is no particular problem even if the amount is outside this range as long as the properties of the crosslinked product obtained do not fall outside the intended range.

Radiation fm or electron beams include α-rays, β-rays, and r-rays from radioactive isotopes. Examples of electron beam accelerators include Van de Graag type electron beam accelerator, Kotku-Kurotto, Walton type electron beam accelerator, and isolation transformer. Ionizing radiation such as an electron beam from a type electron beam accelerator, a transformer type gas (oil) insulated type electron beam accelerator, a cold cathode shock voltage type electron beam accelerator, a linear filament type electron beam accelerator, etc. is preferable. But X
Lines can also be used.

When crosslinking the copolymer of the present invention with an electron beam or radiation, it may be given a predetermined shape in advance by a method such as injection molding, extrusion molding, vacuum forming, or compression molding, and then irradiated, or if possible, at the same time as molding. An in-line method of irradiation can also be adopted.

The cyclic olein copolymer crosslinked product obtained as described above may contain an activator, a dispersant, a filler, a plasticizer, a tackifier, a coloring agent, a foaming agent, a foaming aid, a lubricant, and an aging agent, if necessary. Inhibitors and other additives can be used together.

Fillers include inorganic fillers such as carbon black, white carbon (silicic acid compound), calcium carbonate, talc, and clay; high styrene resin, coumaron indene resin, phenol resin, lignin, modified melamine resin 1
Organic fillers such as oleoresin may be mentioned. Among these, inorganic fillers are particularly preferably used.

Softeners include process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, petroleum softeners such as petrolatum; coal tar softeners such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil,
Fatty oil-based softeners such as coconut oil; tall oil; sub; waxes such as beeswax, carnauba wax, and lanolin hiko; fatty acids and fatty acid salts such as ricinoleic acid, valmitic acid, barium stearate, calcium stearate, and zinc laurate; petroleum Examples include synthetic polymeric substances such as resins.

Plasticizers include phthalic acid esters, adipic acid esters, sebacic acid esters, and nitric acid. Tackifiers include coumaron indene, terpene, phenolic resin, xylene, formalin resin, etc. , colorants such as inorganic and organic pigments, blowing agents such as sodium bicarbonate, ammonium carbonate, N, N
'-Dinitrosopentamethylenetetramine, azocarbonamide.

For the foaming aid layer, salicylic acid, phthalic acid, urea, etc. can be used, such as azobisisobutyronitrile, benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, calcium amide, and para-toluenesulfonyl azide.

Further, the compound can be manufactured by a known method using an open roll mill, a Banbury mixer, a Nigu, a screw extruder, a twin screw extruder, or the like.

Further, depending on the case, the copolymer may be dissolved in a solvent and necessary additives may be mixed therein.

The crosslinked product obtained by the method of the present invention has excellent solvent resistance, heat resistance, mechanical strength, etc., and can be applied to electric circuit boards (for high frequency), electric wire coatings, vibration isolating materials, tableware for microwave ovens, etc.

〔Example〕

Example 1 Using a 21 glass polymerization vessel equipped with a stirring blade.

Continuously ethylene and 2-methyl-1,4,5,8-dimethano-'I, 2.3.4.4a, 5.8.8a, -
A copolymerization reaction of octahydronaphthalene (hereinafter abbreviated as M-DMON) was carried out. That is, the M-DMON concentration in the polymerization vessel from the top of the polymerization vessel is 60. ! i'# Tonal, 1:
UKM-DMON notluene solution at 0.91% per hour. A toluene solution of vO(OC2H,)C1 was added at 0.7 A per hour so that the vanadium concentration in the polymerization vessel was 0.5 mm01/4, and the aluminum concentration in the polymerization vessel was 3 mmo.
A toluene solution of ethylaluminum sesquichloride (AJt (C! Hs) t5C115) was continuously fed into each polymerization vessel at a rate of 0.41/hour so that the ratio was 1/13. On the other hand, the polymer solution is continuously drawn out from the lower part of the polymerization vessel so that the volume of polymerization liquid in the polymerization vessel is always 11. In addition, ethylene was supplied from the top of the polymerization vessel at 401.0% per hour. Nitrogen is fed at a rate of 801 per hour.

The copolymerization reaction was carried out at a controlled temperature of 10° C. using a refrigerant. A small amount of methanol was added to the polymer polymerization liquid extracted from the lower part of the polymerization vessel to stop the polymerization reaction, and the resultant copolymer was poured into a large amount of isopropyl alcohol to precipitate the resulting copolymer, which was then washed with isopropyl alcohol. At this time, the copolymer was obtained at a rate of 30 g/hour.

This copolymer was vacuum dried at 160° C. day and night.

"The ethylene composition of the copolymer according to C-NMR analysis is 66
Mol%, intrinsic viscosity measured in decalin at 135°C [η]
is 1.2061/g, DuPont JCI! Dynam
icMechanical Analyzer (DM
The glass transition temperature according to A) was 121° C., and the iodine value measured as the consumption amount (g) of iodine monochloride per 100 g of copolymer was 0.5.

For every 100 I of this polymer, 5 l of zinc oxide and 1 l of stearic acid. 3.0 I of y, p, p'-dibenzoylquinone dioxime were mixed and mixed in a kneader at 200°C.

After pulverizing the mixture, dicumyl peroxide 1. OI
was made into a benzene solution and impregnated into the mixture. After removing benzene with a vacuum dryer, 16
Crosslinking molding was carried out by heating at 0° C. for 20 minutes. The obtained sheet is AS
The flexural modulus measured in accordance with TM D 790 is 2.
OX 10' kg/cJ, ASTM D 64B (
The heat distortion temperature based on a load of 4.6 kg was 120°C.

Furthermore, the solvent resistance was extremely good as determined from the change in the groove shape when a molded plate with grooves 2 mm wide and 0.5 mm deep was immersed in a cyclohexane solution for 10 hours.

In fact, on the downstream side 2 In Example 1, 5-ethylidene-2-norbornene (ENB
) was carried out in the same manner except that polymerization was carried out by adding . The result is 5
It is shown in Table 1.

Example 3 In Example 1, i instead of f-DMON, 4.5.
8-dimethano-1,2,3,4,4a, 5.8.8a
+ −, t The same procedure was performed except that phtahydronaphthalene (DMON) was used. The results are shown in Table 1.

Example 4 The same procedure as in Example 3 was carried out except that dicyclopentadiene (DCPD) was added and polymerized. The results are shown in Table 1.

Examples 5 and 6 In Example 1, 6-nitylbicyclo(221)hep)-2ene was used in place of M-DMON, and 1°4 hexadiene (1,4HD) or 5-ethylidene-2-norbornene was used. I did the same thing except that.

The results are shown in Table 1.

Comparative Examples 1 to 6 The polymers of Examples 1 to B were press-molded as they were, and measured in the same manner as in the Examples.

-9A- Example 7 To 100 g of Example 20 polymer, 5 g of zinc white 511 stearic acid, 2-mercaptobenzothiazole O, Sg,
Tetramethylthiamine monosulfide 1.5. ! i'
, sulfur 1. DI was added and mixed with a mixer. This mixture was press-molded at 180° C. for 10 minutes to effect crosslinking.

As a result, the bending elastic modulus was 2. I x 10' kg/c
L#, heat distortion temperature was 123°C, and solvent resistance was good.

Example 8 The polymer of Example B was crosslinked in the same manner as in Example 7. As a result, the flexural modulus is 1.7 x 10' kVarl,
The heat distortion temperature was 75°C, and the solvent resistance was good6.
Example 9 0.1 w of triallyl cyanurate was added to the polymer of Example 1.
t% and molded into a 0.5 inch thick sheet.

γ-rays of 15 Mrad were irradiated. As a result, the bending elastic modulus of the sheet after irradiation was 1.8 x 10' kg/cd, and the thermal deformation source was 20.

Claims (1)

[Scope of Claims] A method of crosslinking a cyclic olefin copolymer with sulfur or an organic peroxide, an electron beam, or radiation, wherein the cyclic olefin copolymer is crosslinked with a cyclic olefin of formula (1) at least 1. A method for crosslinking a cyclic olefin copolymer, which is a random copolymer containing ethylene as a comonomer component, wherein the cyclic olefin has substantially the structure of formula (2) in the copolymer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) (In the formula, R^1 to R^1^2 are hydrogen, alkyl groups, or halogens, and each is the same or may be different, and further R^
9 or R^1^0 and R^1^1 or R^1^2 may mutually form a ring. n is a positive number of 0 or 1 or more, and n
is 2 or more, n R^5 to R^6 may be the same or different. )