JPH0251512A - Unsaturated ethylene-alpha-olefin random copolymer and composition thereof - Google Patents

Abstract

PURPOSE:To increase vulcanizing rate, by copolymerizing ethylene, an alpha-olefin and a specific nonconjugated diene compd. CONSTITUTION:Ethylene, a 3-12C alpha-olefin (e.g., propylene) in a molar ratio of ethylene to said alpha-olefin of 5-90/95-10 and a nonconjugated diene compd. of the formula (wherein n is 2-10; R<1> is 1-8C alkyl; each of R<2> and R<3> is H or R<1>) having an iodine value >=3, pref. 20-40 (e.g., 7-methyl-1,6-octadiene) are copolymerized in the presence of a Ziegler-Natta catalyst at 0-150kg/cm<2> and 80-200 deg.C for 0.1-5hr to give an unsatd. ethylene-alpha-olefin random copolymer having a no.-average MW of 3,000-500,000, pref. 10,000-300,000, and a wt.-average MW of 6,000-5,000,000, pref. 20,000-3,000,000, in terms of PS.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to an unsaturated ethylene-α-olefin random copolymer and a composition thereof, and more particularly, to a conventional unsaturated ethylene-α-olefin random copolymer and a composition thereof. The present invention relates to an unsaturated ethylene-α-olefin random copolymer and a composition thereof, which have a faster vulcanization rate than random copolymers.

[Prior Art] Conventionally, unsaturated nyletine-α-olefin random copolymers have been produced using ethylidene norbornene (ENB) and dicyclopentadiene (DCP) as unsaturated components.
Copolymers using 1,4-hexadiene (1°4-HD) are known and are industrially produced as ethylene-propylene copolymers and ethylene-butene-1 copolymers.

Among these, copolymers using ethylidene norbornene have a fast vulcanization rate and are widely used in various industrial products. However, diene rubber (NRSSBRS IR
Even ethylidenenorbornene copolymers were not sufficient in terms of co-vulcanization with the vulcanizate, BRSNBRetc), and the vulcanization rate was not sufficient.

[Problems to be Solved by the Invention] The purpose of the present invention is to solve the problems of the prior art and to provide an unsaturated ethylene-α-olefin random copolymer and a composition thereof that have a higher degree of vulcanization than conventional products. It is about providing.

[Means for Solving the Problems] The present invention provides an ethylene-α-olefin random copolymer consisting of a) ethylene, b) an α-olefin having 3 to 12 carbon atoms, and C) a non-conjugated diene compound of formula 1. ① Polystyrene equivalent number average molecule ff13,000~5
00,000, ■ Polystyrene equivalent weight average molecular weight 6,000 to 5,
000,000, ■ The content of the non-conjugated diene compound is 3 or more in terms of iodine value, and ■ The bonding ratio of ethylene-α-olefin is 5 to 90/
95 to 10 (molar ratio) 3 R2 [-Formula I] (n is an integer of 2 to 10, R1 is an alkyl group having 1 to 8 carbon atoms, R2 and R3 are the same or different hydrogen atoms, or hydrogen atoms having 1 to 10 carbon atoms) It has been found that an unsaturated ethylene-α-olefin random copolymer characterized by having the following alkyl group (alkyl group of No. 8) solves the above-mentioned problems, and the present invention has been achieved.

The present invention will be explained in more detail below.

b) α-olefin having 3 to 12 carbon atoms used in the present invention includes propylene, butene-1, heptene-1,
hexene-1, heptene-1, octene-1, nonene-
1, decene-1, undecene-1, dodecene-1,3-
Examples include methyl-butene-1,4-methylpentene-1, and one or more of these may be used. Among these, preferred are propylene, butene-1, and hexene-1,
Particularly preferred is propylene. For example, in the case of propylene, the repeating unit in the copolymer of the present invention is -(C-C square).

C) Non-conjugated diene compounds of general formula I used in the present invention include combined methyl-1,5-hebutadiene, 6-methyl-1,5-hebutadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 7-
Methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene, 8-methyl-1,8-decadiene, 9-methyl-1°8-decadiene, 9-methyl-1,9-undecadiene, 10- Methyl-1,9-undecadiene, 1
0-methyl-1,10-dodecadiene, 11-methyl-
1,10-dodecadiene, 12-methyl-1,11-tridecadiene, 13-methyl-1゜11-tridecadiene, 12-methyl-1,2-tetradecadiene, 13-
Methyl-1,12-tetradecadiene, 13-methyl-
1,13-pentadecadiene, 14-methyl-1,13
-pentadecadiene, etc., and one or more of these may be used. Among these, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 8-
Methyl-1,7-nonadiene and 9-methyl-1,8-decadiene are preferred, particularly preferably 7-methyl-1,
6-octadiene.

These repeating units in the copolymer of the present invention are, for example, in the case of 7-methyl-1,6-octadiene, CCY.The molecular weight of the unsaturated ethylene-α-olefin random copolymer of the present invention is From the balance between the mechanical strength of sulfur and roll workability, the number average molecular weight in terms of polystyrene is 3.
000-500,000, preferably 10,000-3
00,000, weight average molecular weight in terms of polystyrene: 6.
000-5゜ooo, ooo, preferably 20,000
~3°ooo, ooo.

Further, the content of the non-conjugated diene compound of general formula I in the unsaturated ethylene-α-olefin random copolymer is 3 or more in terms of iodine value, preferably 10 to 60, particularly preferably 20 to 40.

If the iodine value is less than 3, the desired vulcanization rate may not be obtained, which is not preferable.

The bonding ratio of ethylene and α-olefin in the unsaturated ethylene-α-olefin random copolymer of the present invention is ethylene/α-olefin = 5 to 90/95 to 10 (molar ratio), and the ratio is outside this range. This impairs the randomness of the random copolymer of the present invention, which is not preferable.

The unsaturated ethylene-α-olefin random copolymer of the present invention can be produced using a Ziegler-Natta type catalyst.

As the transition metal compound component of the Ziegler-Natta type catalyst, compounds of titanium, zirconium, and vanadium are preferred.

Examples of titanium compounds include titanium trichloride, titanium tetrachloride, ethoxytitanium trichloride, and tetrabutoxytitanium, and these compounds may also be used as organic acid esters, water, amines, amides, ethers, alcohols, etc. Magnesium compounds such as magnesium chloride, dialkoxymagnesium, fatty acid magnesium, silica, alumina,
Examples include supported titanium catalysts supported on metal oxides such as titania.

On the other hand, examples of the zirconium compound include biscyclopentadienyldichlorozirconium, biscyclopentagenyldimethylzirconium, and supported zirconium catalysts in which these compounds are supported on metal oxides such as silica, alumina, and titania.

Furthermore, vanadium compounds include vanadium tetrachloride, vanadium trichloride, tris(2,4-pentadionato)vanadium, tris(2-methyl-1°3-butanedionato)vanadium, and these compounds are combined with metal oxides such as silica, alumina, and titania. Examples include supported vanadium catalysts supported on etc.

On the other hand, as the organometallic compound which is another component of the Ziegler-Natta catalyst, an organoaluminum compound is preferable.

Examples of organoaluminum compounds include (a) trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminium, triisobutylaluminum, and tri-n-hexylaluminum; (b) dimethylaluminum monochloride, diethylaluminum monochloride, diisobutylaluminum monochloride; dialkylaluminum monochloride such as chloride, (c) alkylaluminum sesquichloride such as ethylaluminum sesquichloride and isobutylaluminum sesquichloride, (d) dialkylaluminum hydride such as diethylaluminum hydride and diisobutylaluminum hydride, (v) ethylaluminum dichloride, Alkylaluminum dichloride such as isopropylaluminum dichloride, (to)diethylaluminum ethoxide, diethylaluminium isopropoxide, di-n-propylaluminium-2,
Examples include dialkylaluminum alkoxides such as 6-di-t-butyl phenoxide, dialkylaluminum aryloxides, (t)dimethylaluminum trimethylsiloxide, diethylaluminum trimethylsiloxide, and aluminoxanes such as (th)methylaluminoxane and ethylaluminoxane.

These organoaluminum compounds can also be used as reaction products with water, secondary amines, or organic acid esters. Further, these organoaluminum compounds can be used alone or in combination of two or more.

The polymerization conditions for the unsaturated ethylene-α-olefin random copolymer of the present invention include a polymerization temperature of -80 to 200°C.
, preferably 0 to 150°C, polymerization pressure 0 to 150 kg/
CR! - G1 is preferably 0 to 50 kg/cJ-G, and the polymerization time is 0.1 to 5 hours, preferably 0.25 to 2 hours.

There are no particular restrictions on the polymerization mode, and (a) n-hexane, n-
A slurry method or a solution method using an inert solvent such as heptane or n-octane, (b) a bulk method in which the monomer acts as a solvent without substantially adding a solvent, a melt method, etc. are used.

Furthermore, hydrogen and/or dialkylzinc compounds can be used to adjust the molecular weight of the copolymer.

The unsaturated ethylene-α-olefin random copolymer of the present invention can be made into an oil-extended product by adding a paraffinic oil, a naphthenic oil, or the like, if necessary.

The second aspect of the present invention is a) reinforcing agent 0 to 30 parts by weight per 100 parts by weight of the unsaturated ethylene-α-olefin random copolymer.
0 parts by weight, preferably 5 to 150 parts by weight b) 0 to 150 parts by weight, preferably 5 to 100 parts by weight C) 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight of a crosslinking agent. Possibly a vulcanizable composition.

a) As reinforcing agents, carbon black, white carbon, basic magnesium carbonate, activated calcium carbonate,
Ultrafine magnesium silicate powder, hard clay, etc. can be used, and among these, carbon black and white carbon are preferred.

b) Paraffinic oil, naphthenic oil, aromatic oil, silicone oil, etc. can be used as the softening agent, and among these, paraffinic oil is preferred.

C) Sulfur, organic peroxide, etc. are used as the crosslinking agent. Powdered sulfur, flower sulfur, colloidal sulfur, insoluble sulfur, etc. are used as the sulfur, and di-t-butyl peroxide, t-butyl peroxide, etc. are used as the organic peroxide. −
Butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5(di-t-
butylperoxy)hexyne-3,1,3-bis(t-
butylperoxyisopropyl)benzene, 1,1-bis(t-butylperoxy')-3,3°5-trimethylcyclohexane, and the like are used.

When sulfur is used as a crosslinking agent, thiazole-based vulcanization accelerators, dithiocarbamate-based vulcanization accelerators, thiuram-based vulcanization accelerators, thiourea-based vulcanization accelerators, etc. are used as vulcanization accelerators. On the other hand, when organic peroxide is used as a crosslinking agent, crosslinking aids such as sulfur, dibenzoquinone dioxime, benzoquinone dioxime, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, divinylbenzene, triallylisocyanurate, maleic anhydride, etc. is used.

In producing the composition of the present invention, an activator such as zinc white is usually used. In addition, anti-aging agents, lubricants,
Slip agents, adhesives, etc. can be added.

The unsaturated ethylene-α-olefin random copolymer of the present invention has a fast vulcanization rate, excellent co-vulcanization with diene rubber,
A blend of diene synthetic rubber such as SNBR can also be used.

The composition can be produced using a kneader such as a Banbury mixer, a kneader-intermixer, a continuous kneader, or a roll.

[Example] Hereinafter, the present invention will be explained in detail with reference to Examples.

Parts and % in the examples refer to parts by weight and % by weight unless otherwise specified.

In this example, the molecular weight of the copolymer was measured using a trichlorobenzene solvent using a 150 type GPC manufactured by Waters, USA.
Measured at 135°C.

Further, the content of the non-conjugated diene compound of general formula 1 in the copolymer was determined as an iodine value by a known iodine titration method.

Furthermore, the vulcanization rate was measured using a JSRnB type curelastometer. t' c (10) is 10 for optimal vulcanization.
The time (minutes) required to reach %t'e (90) is 9 as above.
Indicates the time (minutes) required to reach 0%.

Example-1 A. Catalyst Preparation In a stainless steel ball mill that had been purged with nitrogen in advance, 100 mmol of magnesium chloride, 7.5 mmol of ethyl benzoate, 15 mmol of titanium tetrachloride, and 64 m of n-hexane were added.
1 was charged and ground in a vibrating mill at room temperature for 7 hours. After pulverization, the entire content was taken out and washed five times with 400 ml of n-hexane, and the n-hexane concentration was 0.02 mol/Il.

80 Polymerization 200 ml of dehydrated n-hexane was placed in 13 500 ml flasks that had been purged with nitrogen. 5 ml of dehydrated and purified 7-methyl-1,6-octadiene was charged, and a mixed gas of ethylene/propylene = 1/1 (molar ratio) was supplied for 5 minutes at a rate of 41 twp in a water bath at 30°C. After dissolving the mixed gas, 0.03 mmol of a catalyst prepared with 3 mmol of triisobutylaluminum A was sequentially charged, and polymerization was carried out at 30° C. for 30 minutes while supplying the mixed gas.

After polymerization for 30 minutes, 10 ml of a methanol-hydrochloric acid mixture was added to stop the polymerization reaction, followed by methanol coagulation and vacuum drying.

The yield of the produced polymer was 10.5 g (polymerization activity 14,6k
g/g-T L-h), the number average molecular weight in terms of polystyrene is 47,000, the weight average molecular weight in terms of polystyrene is 359,000, and ethylene/propylene in the copolymer = 29/71 (mol). The content of 7-methyl-1,6-octadiene was 14 in terms of iodine value.

Example-2, Comparative Example-1 JS, which is an EPDM using ethylidene norbornene as the polymer and diene component obtained in Example-1
Using REP24 (manufactured by Japan Synthetic Rubber Co., Ltd., iodine value: 15), the mixtures were kneaded according to the formulation shown in Table 1, and the vulcanization speeds were compared. The results are shown in Table-2.

Table-1 Table-2 The polymer of Example-1 shows almost the same iodine value as EP24, but Example-2 using the polymer of Example-1 has a faster acceleration rate than Comparative Example-1 using EP24. Indicates sulfur rate.

Example 3 88 Polymerization In Example IB, the amount of 7-methyl-1,6-octadiene was changed to 3 ml, 1 mmol of ethyl sesquichloride was added instead of triisobutylaluminum, and tris(2-methyl Using 0.1 mmol of vanadium (1,3-butanedionato), the polymerization temperature was set to 20
Polymerization was carried out in the same manner as in Example-IB except that the temperature was changed to °C. The yield of the produced polymer was 0.44 g (polymerization activity 0.1
7 kg/g-V-h), the number average molecular weight in terms of polystyrene is 89,000, the weight average molecular weight in terms of polystyrene is 189,000, and the ethylene/propylene in the copolymer is 48/22 (molar ratio ), 7
-Methyl-1,6-octadiene content was 9 in terms of iodine value.

Example-4 80 Polymerization In a 500 ml flask that had been purged with nitrogen in advance, 100 ml of dehydrated n-hexane and dehydrated hexene-11 were added.
00m1. 10 ml of dehydrated and purified 7-methyl-1,6-octadiene was charged, then 3 mmol of triisobutylaluminum and 0.03 mmol of the supported titanium catalyst prepared in Example-IA were charged, and at the same time, 0.2 g/ml of ethylene gas was charged. Polymerization was carried out at 30°C for 30 minutes while charging at a rate of 1 minute. The yield of the produced polymer was 6.0 g (polymerization activity 8.35 kg/g-Ti・h), the number average molecular weight in terms of polystyrene was 133,000, the weight average molecular weight in terms of polystyrene was 1,513,000, and the Ethylene/hexene-1= (by C13-NMR) in the polymer
7/93 (molar ratio), the 7-methyl-1,6-octadiene content was 36 in terms of iodine value.

Example-5 89 Polymerization In Example-IB, polymerization was carried out in the same manner as in Example-IB, except that the amount of 7-methyl-1,6-octadiene was changed to 10 ml. The yield of the produced polymer was 11.3 g (polymerization activity 15.7 kg/gφT1 h), the number average molecular weight in terms of polystyrene was 27,000, and the number average molecular weight in terms of polystyrene was 199,000. /propylene=43157 (molar ratio), 7-
The methyl-1,6-octadiene content was 32 in terms of iodine value.

[Effects of the Invention] According to the present invention, an unsaturated ethylene-α-olefin random copolymer having a faster vulcanization rate than ever before can be obtained, and the composition can be prepared by replacing EPDM etc. with the present copolymer. This can improve production efficiency. In addition, blends with diene rubber have improved co-crosslinking properties and exhibit excellent physical properties.

The copolymer of the present invention is useful for manufacturing various industrial products such as tires, belts, hoses, sponges, and packing.

Patent applicant: Japan Synthetic Rubber Co., Ltd.

Claims (2)

[Claims] (1) A random copolymer consisting of a) ethylene, b) an α-olefin having 3 to 12 carbon atoms, and c) a non-conjugated diene compound of general formula I, [1] polystyrene equivalent number average molecular weight 3, 000-50
0,000, [2] Polystyrene equivalent weight average molecular weight 6,000 to 5
,000,000, [3] The content of the non-conjugated diene compound is 3 or more in terms of iodine value,
and [4] The bonding ratio between ethylene and α-olefin is 5 to 9
Unsaturated ethylene-α-olefin random copolymer characterized by a molar ratio of 0/95 to 10 (Integer, R^1 is an alkyl group having 1 to 8 carbon atoms, R^2 and R^3 are the same or different hydrogen atoms, or an alkyl group having 1 to 8 carbon atoms) (2) With respect to 100 parts by weight of the copolymer according to claim 1,
A composition comprising a) 0 to 300 parts by weight of a reinforcing agent, b) 0 to 150 parts by weight of a softener, and c) 0.1 to 10 parts by weight of a crosslinking agent.