JP2745680B2 - Alpha-olefin polymer and its composition - Google Patents

Description

The present invention relates to an α-olefin polymer and an α-olefin polymer composition, and more particularly to an α-olefin polymer and an α-olefin polymer having excellent vibration damping properties. It relates to an olefin polymer composition.

[Prior art] Conventionally, polymers of hexene-1 or octene-1 have been produced by using titanium tetrachloride-trialkylaluminum catalyst, titanium trichloride-diethylaluminum chloride catalyst, vanadium oxytrichloride-ethylaluminum sesquichloride catalyst. Polymers are known.

Polymers based on these catalyst systems have the disadvantage of low stereoregularity or low molecular weight.

[Problems to be Solved by the Invention] The present inventors have solved the problems of low steric regularity and low molecular weight, which are the drawbacks of conventional hexene-1 or octene-1 polymers, and have achieved high tacticity. To obtain a high molecular weight hexene-1 or octene-1 polymer.

[Means for Solving the Problems] In the first aspect of the present invention, a repeating unit is represented by a general formula: (N = 3 or 5), wherein the main chain is a linear α-olefin polymer, and a) the number average molecular weight in terms of polystyrene is 100,000 to 500,00.
0, preferably 200,000 to 400,000, and a weight average molecular weight in terms of polystyrene of 1,000,000 to 7,000,000, preferably
B) m according to triad level assignment by ¹³ C-NMR
An α-olefin polymer characterized in that the ratio of mm to the sum of m, mr and rr is in the range of 85 to 99%.

A second aspect of the present invention is that a) an organic peroxide compound is 0.5 to 5 parts by weight, and b) sulfur and / or a sulfur-containing compound is 0.1 to 3 parts by weight based on 100 parts by weight of the α-olefin polymer obtained by the first aspect of the present invention. The present invention provides a crosslinkable α-olefin polymer composition containing a part as an essential component.

 Hereinafter, the present invention will be described in detail.

Α-Olefin used in the first aspect of the present invention is hexene-
1, octene-1.

The α-olefin polymer of the present invention can be obtained, for example, by a catalyst comprising a combination of a so-called supported titanium catalyst in which a titanium compound is supported on a magnesium chloride carrier and a trialkylaluminum compound.

Examples of the supported titanium catalyst used in the polymerization of the present invention include, for example, JP-A-60-137910, JP-A-60-139706 and JP-A-60-139706.
158204, JP 60-161404, JP 60-184506, JP
60-243103, JP-A-61-23604, JP-A-61-23606, JP-A-61-91204, JP-A-61-106609, JP-A-61-108611,
JP-A-61-126109, JP-A-61-152707, JP-A-61-2280
04, JP-A-61-233005, JP-A-61-291602, JP-A-62
Magnesium compounds as described in 508 and the like,
A supported titanium catalyst containing a titanium compound, dicarboxylic acid mono- and diesters as essential components is exemplified. Examples of the trialkylaluminum compound used in the present invention include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum and the like.

The polymerization conditions of the polymer of the present invention are such that Ti / Al (molar ratio) is 5
~ 100, preferably 20-70, monomer / Ti (molar ratio) is 3,
000 or more. If Al / Ti (molar ratio) is less than 5, polymerization activity is not sufficient, and if Al / Ti (molar ratio) exceeds 100, the molecular weight of the obtained polymer may be low, which is not preferable.
On the other hand, if the ratio of monomer / Ti (molar ratio) is less than 3,000, the molecular weight of the obtained polymer is undesirably low. Other polymerization conditions are not particularly limited, but the polymerization temperature is 0 to 150.
° C, preferably 10 to 60 ° C, polymerization pressure 0 to 150 kg / cm ² (gauge pressure), preferably 0 to 50 kg / cm ² , polymerization time 3 to 120
It is desirable to carry out the process in the range of minutes.

As the polymerization solvent in the polymerization of the present invention, saturated aliphatic hydrocarbons, saturated alicyclic hydrocarbons, and aromatic hydrocarbons are preferable, and n-hexane, n-heptane, n-octane, cyclohexane, cyclooctane, benzene, and toluene are preferable. Are used. Hydrogen and an alkyl zinc compound can also be used as a molecular weight regulator.

A) The organic peroxide compound used in the second embodiment of the present invention includes dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxyhexane), 2 , 5-Dimethyl-2,5-di (t-butylperoxy) hexyne-3, 1,3-bis (t-butylperoxyisopropyl) benzene, t-butylcumyl peroxide, 1,1-bis (t -Butylperoxy) -3,3,5-trimethylcyclohexane and the like. The amount of these used is the α-olefin polymer 100
It is 0.5 to 5 parts by weight, preferably 1 to 4 parts by weight with respect to parts by weight. If the amount is less than 0.5 part by weight, the crosslinking does not proceed sufficiently and the mechanical strength of the crosslinked product may be low, which is not preferable. B) As sulfur and / or the sulfur-containing compound, sulfur, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram tetrasulfide, dipentamethylenethiuram hexasulfide, Examples thereof include 4,4'-dithiobisdimorpholine, and among them, sulfur is particularly preferred. These are used in an amount of 0.1 to 3 polymerization parts, preferably in the case of sulfur.
0.2 to 0.5 part by weight, and in the case of another sulfur-containing compound, 1 to 2 parts by weight. If the amount used is less than 0.1 part by weight, the crosslinking does not proceed sufficiently and the mechanical strength of the cross-linked product tends to decrease. Even if the amount used exceeds 3 parts by weight, the cross-linking does not proceed sufficiently and the Unfavorably, the mechanical strength is reduced.

In the production of the composition of the present invention, a reinforcing agent, a filler, a softener, an activator, an antioxidant, a lubricant, and the like described in Rubber and Plastic Compounding Chemical Handbook, edited by Rubber Digest Co., Ltd., can also be blended. The composition of the present invention can be compounded using a Banbury mixer, a kneader blender, an intermixer, a roll, a continuous kneader, or the like, which is used in general rubber compounding.

EXAMPLES Hereinafter, the present invention will be described in detail based on examples. In the examples, parts and% indicate parts by weight and% by weight, respectively, unless otherwise specified.

In this example, the polystyrene-equivalent number average molecular weight and polystyrene-equivalent weight average molecular weight of the polymer were measured at 135 ° C. using trichlorobenzene as a solvent, using GPC150 type manufactured by Waters, USA. In addition, the ratio of each component of mm (meso meso), mr (meso racemate), and rr (racemic racem) according to triad level assignment indicating the stereoregularity of the polymer in the present example is JNM-FX100 type carbon manufactured by JEOL Ltd. Using 13 NMR, 1 in ortho-dichlorobenzene solvent
Measured at 20 ℃, Polymer Preprint Japan (Poly
mer Preprints, Japan) VOL. 36, No. 8, 2408 (1987).

Further, regarding the cross-linking properties of the polymer composition, JIS K6
It was measured according to 301.

Example-1 A. Preparation of catalyst A stainless steel ball mill previously substituted with nitrogen was charged with 100 mmol of magnesium chloride, 7.5 mmol of ethyl benzoate, 15 mmol of titanium tetrachloride, and 64 ml of n-hexane, and was shaken at room temperature for 7 hours and pulverized. After pulverization, the entire content was taken out, washed five times with 500 ml of n-hexane, and then washed with n-hexane.
Hexane (700 ml) was charged to obtain a titanium catalyst slurry.
The titanium concentration of this supported titanium catalyst slurry is 0.02 mol / l
Met.

B. Polymerization Into a 5 l flask previously purged with nitrogen, 3 l of dehydrated and purified n-hexane and 300 ml of dehydrated and purified hexene-1 (Dialen-6, manufactured by Mitsubishi Kasei Co., Ltd.) were charged, and then prepared with 7.125 mmol of triisobutylaluminum, A 0.15 mmol of a supported titanium catalyst was charged (Al / Ti = 47.5, monomer / Ti = 16,400), and the mixture was stirred at 20 ° C. for 60 minutes for polymerization. 60
After one minute, 5 ml of isopropyl alcohol was added to the reaction solution to terminate the polymerization reaction, followed by coagulation with methanol and drying with a roll at 100 ° C. The yield of the produced polymer was 46.1 g, the number average molecular weight and the weight average molecular weight in terms of polystyrene of the produced polymer were 190,000 and 1,577,000, respectively.
The value of / Mn was 8.3, and the ratio of mm by ¹³ C-NMR was 87%.

Example-2 B. Polymerization In Example-1, triisobutylaluminum was replaced with 9
Polymerization was carried out in the same manner as in Example 1 except that mmol (Al / Ti = 60, monomer / Ti = 16,400) was used. Polymer yield is
132 g, polystyrene reduced number average molecular weight and weight average molecular weight are 160,000 and 1,056,000, respectively, Mw / M
n = 6.6, The ratio of mm by ¹³ C-NMR was 87%.

Comparative Example-1 B. Polymerization A 500 ml flask previously purged with nitrogen was charged with 300 ml of dehydrated and purified n-hexane and 30 ml of hexene-1, 10 mmol of triisobutylaluminum and 0.5 mmol of titanium tetrachloride (Al / Ti = 20). , Monomer / T
i = 490) The polymerization was carried out at 30 ° C. for 60 minutes. 0.9 polymer yield
g, the number average molecular weight and the weight average molecular weight in terms of polystyrene were 45,000 and 1,615,000, respectively, and Mw / Mn =
The ratio of mm by 35.9 and ¹³ C-NMR was 79%.

Example-3 B. Polymerization A 3 l flask previously purged with nitrogen was charged with 2 l of dehydrated and purified n-hexane and 270 ml of dehydrated and purified octene-1 (Dialen-8, manufactured by Mitsubishi Kasei Co., Ltd.), and 15 mmol of triisobutylaluminum was supported. Ti catalyst (JP-A-63-22
3010) (prepared according to Example 1 of 3010)
l / Ti = 50, monomer / Ti = 5,700) and stirred at 30 ° C. for 60 minutes. After adding 10 ml of isopropyl alcohol to the reaction solution to terminate the polymerization reaction, the solution was coagulated with methanol and dried under vacuum. The polymer yield was 166 g, the number average molecular weight and weight average molecular weight in terms of polystyrene were 140,000 and 3,300,000, respectively, and Mw / Mn = 23.5, mm by ¹³ C-NMR.
Was 91%.

Example-4 C. Evaluation of physical properties The polymer of Example-2 was kneaded by a 6-inch roll with the compounding recipe shown in Table 1, and press-vulcanized at 160 ° C for 20 minutes. Table 2 shows the physical property test results. A crosslinked rubber was obtained with the organic peroxide and sulfur.

Example-5 B. Polymerization 18.8 l of dehydrated and purified cyclohexane and 1.2 l of hexene-1 were charged into a 30 l reactor previously substituted with nitrogen, then 90 mmol of triisobutylaluminum and 1.98 mmol of the supported Ti catalyst of Example 3 (Al / Ti = 45.
5, monomer / Ti = 5,000) and polymerized at 30 ° C. for 60 minutes. After 60 minutes, the reaction solution was placed in a nitrogen-sealed polyvinyl bottle containing isonpropyl alcohol and stirred to terminate the polymerization reaction.

After the polymer solution was dissolved by steam stripping, it was dried with a roll at 100 ° C. 5 polymer yield
22 g, polystyrene reduced number average molecular weight and weight average molecular weight are 271,000 and 1,626,000, respectively, Mw / M
n = 6.0, and the ratio of mm according to ¹³ C-NMR was 94%.

Examples -6 to 8, Comparative Examples -2-3 C. Evaluation of physical properties The polymer of Example -5 was used in the formulation shown in Table-3.
Use a 250cc Labo Plast Mill (Toyo Seiki Co., Ltd.)
After kneading at 4 ° C. for 4 minutes, press vulcanization was performed under the vulcanization conditions shown in Table 4, and a physical property test was performed. The results are shown in Table-4.

Example-9, Comparative Example-4 C. Evaluation of physical properties Using the polymer of Example-5 and the compounding formulation shown in Table-5, physical properties were evaluated in the same manner as in Example-6.
The results are shown in Table-6.

In Examples -6 to 9, good crosslinked products were obtained.
Comparative Examples 2, 3, and 4 could not be crosslinked.

Example-10 60 mmol of triisobutylaluminum, 12 mmol of phenyltriethoxysilane, supported Ti catalyst of Example-3
Using 1.98 mmol, polymerization was carried out at 20 ° C. in the same manner as in Example-5. The polymer yield was 263 g, and the polystyrene reduced number average molecular weight and weight average molecular weight were 446,000 each.
And 5,800,000, Mw / Mn = 13.0, and the ratio of mm by ¹³ C-NMR was 96%.

[Effects of the Invention] According to the present invention, a high stereoregular hexene-1 or octene-1 linear polymer is obtained, and a high molecular weight polymer is obtained with high activity.

In addition, the composition of the present invention can provide a novel cross-linked product of a hexene-1 or octene-1 linear polymer, and can be used in various industrial products such as packings, hoses, belts, etc. because of the low compression set of the cross-linked product. Useful.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // (C08K 5/00 5:14 5:36) (C08K 13/02 3:06 5:14)

Claims (2)

(57) [Claims] (1) a repeating unit represented by the general formula: (N = 3 or 5) a polymer of α-olefin having a straight-chain main chain, a) having a polystyrene equivalent number average molecular weight of 100,000 to 500,00
0, and the weight average molecular weight in terms of polystyrene is 1,000,000-
B) m by triad level assignment by ¹³ C-NMR.
An α-olefin polymer, wherein the ratio of mm to the sum of m, mr, and rr is in the range of 85 to 99%. 2. An organic peroxide compound of 0.5 to 5 parts by weight, b) sulfur and / or a sulfur-containing compound of 0.1 to 3 parts by weight, based on 100 parts by weight of the α-olefin polymer of claim 1. Crosslinkable α-olefin polymer composition.