JPS63207839A - Vibration insulating rubber composition - Google Patents

Abstract

PURPOSE:To obtain a vibration insulating rubber composition having excellent vibration damping performance and heat-resistance, by compounding a hexene-1 polymer with a polymer obtained by grafting a hydroxyl-containing polysiloxane to a copolymer of 1-hexene and a specific silane compound. CONSTITUTION:The objective composition is produced by compounding (A) 100-5wt.% hexene-1 polymer and/or a copolymer of hexene-1 and a 3-20C alpha-olefin having hexene-1 content of >=30wt.% with (B) 0-95wt.% polymer obtained by grafting a hydroxyl-containing polysiloxane to a copolymer of hexene-1 and a compound of formula (n is >=1; m is 0-2; X is Cl or Br; R<1> is H or 1-5C alkyl) [preferably (5-hexenyl)dimethylchlorosilane] (including a polymer copolymerized further with a 3-20C alpha-olefin). The content of the compound of formula in the component B is 0.1-10wt.% and the content of polysiloxane in the graft polymer is preferably 0.5-50wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a vibration-proof rubber composition, and more particularly to a vibration-proof rubber composition with excellent vibration damping performance and heat resistance.

[Conventional technology]

Conventionally, butyl rubber has been used in anti-vibration rubber applications, particularly in fields where damping performance is required, because of its good vibration damping performance, but it has the drawback of poor heat resistance.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a vibration-insulating rubber composition that has superior vibration damping performance and heat resistance compared to rubber compositions using butyl rubber.

[Means for solving problems]

As a result of intensive research to achieve the above object, the present inventors found that (a) hexene-1 polymer and/or copolymer of hexene-1 and α-olefin having 3 to 20 carbon atoms excluding hexene-1; (b) a copolymer of hexene-1 and a specific silane compound grafted with polysiloxane having a hydroxyl group, and/or hexene-1 and hexene-1 1 (rubber composition mainly consisting of a polymer obtained by grafting polysiloxane having a hydroxyl group to a terpolymer consisting of an α-olefin having 3 to 20 carbon atoms and a specific silane compound (hereinafter referred to as a graft polymer) The inventors have discovered that the material exhibits excellent vibration absorption performance and heat resistance, and have arrived at the present invention.

That is, the present invention provides (a) a polymer of hexene-1 and/or a polymer of hexene-1 and hexene-1 (having 3 carbon atoms).
100-5% by weight of a copolymer of ~20 α-olefins,
(b) Hexene-1 and the general formula lCH2=CH-(CH2
) n-3i R1m X3-m (wherein, n is an integer of 1 or more, m is an integer of 0 to 2, X is a chlorine atom or a bromine atom,
A copolymer of a compound (R1 means a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) grafted with a polysiloxane having a hydroxyl group and/or hexene-1
It is characterized by containing 0 to 95% by weight of a copolymer of an α-olefin having 3 to 20 carbon atoms, excluding hexene-1, and a compound of general formula I, grafted with a polysiloxane having a hydroxyl group.

The anti-vibration rubber composition of the present invention has a blending ratio of graft polymer (along with al-hexene-1 polymer) of 100 to 5:0.
95 (weight ratio), preferably 75-5:30-95, it is possible to have excellent vibration damping properties and high heat resistance. The blending ratio of these is selected depending on the required heat resistance, and high heat resistance can be obtained by using a large amount of the (b) graft polymer.

The content of hexene-1 in the 31 hexene-1 compounds (a) in the present invention is preferably 30% by weight or more, particularly preferably 50 to 90% by weight. If the hexene-1 content is too low, the frequency dependence of the vibration damping properties of the rubber composition will become large, and if the hexene-1 content is too high, the vibration damping performance may be poor. Furthermore, the number average molecular weight (in terms of polystyrene) of the hexene-1 polymer in the present invention is 10.00.
It is preferably 0 or more, more preferably 30,000 or more. If the number average molecular weight is less than 10,000, the tackiness of the polymer may increase and handling may become extremely difficult, which is not preferable.

In the present invention, excluding hexene-1 which is a component of (a) hexene-1 based polymer (α-olefins having 3 to 20 carbon atoms include aliphatic linear α-olefins and aliphatic branched α-olefins). are preferably used.Specifically, propylene, butene-1, pentene-1,4-methylpentene-1,4゜4-dimethylpentene-1, heptene-1,4-methylhexene-1,5-methyl hexene-1,4-methylhebutene-1,5-methylhebutene-
1,6-methylhebutene-1,4,4-dimethyl-hexene-1, octene-1, nonene-1, decene-1,5
, 6,6-drimethylheptene, 5-methylnonene-1
, 5,5-dimethyloctene-1, undecene-1, dodecene-1, tetradecene-1, bexabcene-1, octadecene-1, and eicosene-1, among which butene-1,4-methylpentene-1 , octene
1, decene-1 is preferred, especially 4-methylpentene-1
1 is preferred. Two or more of these α-olefins can be used in combination.

In the present invention, (a) in the hexene-1 polymer)
In the copolymer of xene-1 and the α-olefin, the content of hexene-1 in the copolymer is preferably 30% by weight or more. In addition, (a) the weight ratio of the hexene-1 homopolymer and the copolymer of hexene-1 and α-olefin in the hexene-1 polymer (hexene-1 polymer/hexene-1 and α-olefin copolymer) is 100~
50150-0 is preferred.

In the present invention, the (al hexene-1 polymer) is, for example, hexene-1 and α-olefin having 3 to 20 carbon atoms excluding hexene-1 in the presence of a Ziegler-Natsuta catalyst at a polymerization temperature of 0 to 200°C, preferably is 20-150℃, polymerization pressure 0-150kg/cd・G (G: gauge pressure)
, preferably 0 to 50 kg/c/g, polymerization time 0.1
It is obtained by polymerizing for ~3 hours, preferably 0.5 to 2 hours.

The Ziegler-Natsuta catalyst used in the production of hexene-1 polymers has a transition metal component that is a titanium compound or its composition (
There are no particular restrictions as long as the titanium compound is of a supported type (including a supported type), and conventionally known titanium compounds can be used.

Examples of the titanium compound or its composition include (a) halogenated titanium compounds such as titanium tetrachloride, titanium trichloride and compositions thereof (e.g. T i Cl 3 .AlC13), titanium dichloride and compositions thereof; (B)
titanium tetrachloride, nidoxytitanium trichloride, titanium trichloride,
Examples include so-called supported catalyst components in which a titanium compound such as tetrabutoxytitanium is supported on various carriers, optionally together with an electron-donating compound such as an organic acid ester, water, amines, amides, ethers, or alcohols. be able to. Here, the carrier is not only a compound that simply functions as a carrier, but also a compound that forms a complex complex with the titanium compound and other components added as necessary.
It refers to compounds that have subtle effects on polymerization activity, stereoregularity, molecular weight distribution, etc., such as silica, alumina, silica/alumina, titania, magnesia, magnesium chloride, and their compositions (for example, magnesium chloride and Lewis acid). ), magnesium oxychloride, and reaction products with alkylaluminum dichlorides.

The composition of the titanium compound mainly consists of the titanium compound, and usually contains 30% by weight or less of an alkyl aluminum monohalide and/or an alkyl aluminum monohalide based on the titanium compound.
or Lewis acids (e.g., aluminum chloride, antimony trichloride, phosphorous halide compounds, etc.) and/or electron donors (e.g., ethers, organic acid esters, organic acid amides, phosphoric acid amides, amines, phosphines, etc.) ) and the above-mentioned supporting components.

Preferred titanium compounds or compositions thereof used in the present invention include titanium tetrachloride and titanium trichloride obtained by reducing titanium tetrachloride with various reducing agents (e.g., hydrogen, aluminum, titanium, organic aluminum, etc.). or titanium trichloride compositions (e.g., TiCj!3 ・n
Ajlc/3), a titanium trichloride composition obtained by pulverizing this titanium trichloride (composition) with an electron donor such as an organic acid ester, ether, phosphoric acid amide, etc., a titanium trichloride composition obtained by grinding titanium tetrachloride with an organic aluminum After reduction, titanium trichloride composition obtained by ether treatment and Lewis acid treatment, reaction product of magnesium oxychloride and alkyl aluminum dichloride, compound obtained by further reacting these with a siloxane compound, magnesium chloride as a carrier. , electron donors (e.g., organic acid esters, alcohols, amines, organic acid amides, ethers,
water) and halogen-containing titanium compounds (e.g., titanium tetrachloride, titanium trichloride, alkoxytitanium trichloride, etc.)
Examples include supported catalyst components in which the essential component is supported.

On the other hand, as the organometallic compound component, which is the other component of the Ziegler-Natsuta catalyst, organometallic compounds of groups rm to m of the periodic table are suitable, and among them, organometallic compounds of group Ⅰ metals, especially aluminum, are suitable. Preferably used. Examples of organoaluminum compounds that are usually preferably used include (a) trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and tolyl n-hexylaluminum; (b) diethylaluminum chloride and di-n-propylaluminum chloride. , dialkyl aluminum halide such as diisobutyl aluminum chloride, (c) dialkyl aluminum hydride such as diethyl aluminum hydride, diisobutyl aluminum hydride, (
d) Alkylaluminum sesquichloride such as methylaluminum sesquichloride, ethylaluminum sesquichloride, n-propylaluminum chloride, isobutylaluminum sesquichloride, (e) methylaluminum dichloride, ethylaluminum dichloride,
Alkylaluminum cybarides such as isopropylaluminum dichloride, dialkylaluminum alkoxides such as diethylaluminum ethoxide, diethylaluminum isopropoxide, di-n-propylaluminum-2,6-di-t-butyl phenoxide, or nitroxides. , (t)dimethylaluminum trimethylsiloxide, diethylaluminum trimethylsiloxide, and the like. It may also be a reaction product of these organoaluminiums and water, a secondary amine, or an organic acid ester.

These organoaluminum compounds can be used alone or in combination of two or more.

There is no particular restriction on the composition ratio of this catalyst, but it is usually titanium 1
The organometallic compound is used in an amount of 0.1 to 2,000 mol, preferably 0.5 to i,00 mol, and more preferably 1 to 500 mol, per atom.

The amount of the electron-donating compound that is optionally used as the third component of the catalyst is generally about 0.01 to 1 mol per 1 mol of the organometallic compound.

The amount of the catalyst to be used is usually about o, ooa mmol to 0.5 mmol, preferably about 0.005 mmol to 0.002 mmol, per 1 mole of all monomers.

On the other hand, in the present invention, the α-olefin having hexene-1 II<U prime number of 3 to 20 in the (bl graft polymer) is the same as the α-olefin used in the hexene-1 polymer (a) above. be able to.

Also, hexene-1 and the compound of general formula I or hexene-1
(a) Polymerization conditions and polymerization catalyst for hexene-1 based polymer It can be done similarly.

The graft polymer (b) in the present invention is hexene-1
and a copolymer of a compound of general formula I and/or a copolymer of hexene-1 and an α-olefin having 3 to 20 carbon atoms excluding hexene-1 and a compound of general formula I, a copolymerization reaction When the reaction rate has increased sufficiently, for example, at a polymerization addition rate of 30 to 100%, polysiloxane having a hydroxyl group is added, and the grafting reaction is advanced by stirring for one hour at room temperature, and then the catalyst is catalyzed with a polymerization reaction terminator. It can be obtained in a dry state by deactivating the polymer and stopping the polymerization reaction, for example, by methanol coagulation, roll drying, or the like.

As the polymerization reaction terminator, alcohols having 1 to 10 carbon atoms, such as methanol, ethanol, isopropyl alcohol, butanol, hexanol, octatool, etc., are used, and those obtained by dehydration and purification are preferred.

The content of hexene-1 in the graft polymer (b) of the present invention is preferably 30% by weight or more, particularly 50% by weight or more.

Compounds of general formula I used in the present invention include, for example, (2-propenyl)dimethylchlorosilane, (3-butenyl)dimethylchlorosilane, (4-pentenyl)dimethylchlorosilane, (5-hexenyl)dimethyl Chlorsilane, (6-hebutenyl)dimethyl-chlorosilane,
(7-octenyl)dimethylchlorosilane, (2-propenyl)-methyldichlorosilane, (3-butenyl)methyldichlorosilane, (4-pentenyl)methyldichlorosilane, (5-hexenyl)methyldichlorosilane ,
(6-pentenyl)dimethylchlorosilane, (7-octenyl)-methyldichlorosilane, (2-propenyl)
Trichlorosilane, (3-7'tenyl)trichlorosilane, (4-pentenyl)trichlorosilane, (5-hexenyl)trichlorosilane, (6-hebutenyl)-trichlorosilane, (7-octenyl)trichlorosilane, etc. It will be done. Among these, (5-hexenyl)dimethylchlorosilane and (7-octenyl)dimethylchlorosilane are preferred.

These silane compounds represented by the general formula I are made from hexene-1 and/or hexene-1 and an α-olefin having 3 to 20 carbon atoms excluding hexene-1 and the compound of the general formula I. It is preferable to contain 0.1 to 10% by weight in the copolymer.

In addition, as the polysiloxane having a hydroxyl group used in the present invention, commercially available silicone oil modified with hydroxyl groups at both ends,
Can use silicone oil modified with carbinol at both ends.
For example, polydiphenylsiloxane-terminated silanol, polydimethylsiloxane-terminated silanol, polydimethyldiphenylpolysiloxane-terminated silanol, polydimethylmethylvinylsiloxane-terminated silanol, polydimethylsiloxane-terminated carbinol, etc. are used.

From the viewpoint of heat resistance and mechanical strength of vulcanized rubber, these polysiloxanes having hydroxyl groups are preferably contained in the BL graft polymer in an amount of 0.5 to 50% by weight, particularly 0.3 to 10% by weight. Preferable.Also, the amount of polysiloxane having these hydroxyl groups to be added is determined relative to the content of the compound of general formula I in the copolymer, but from the viewpoint of heat resistance and processability, the content of the compound of general formula The number average molecular weight (in terms of polystyrene) of the graft polymer (b) in the present invention is preferably 10.000 or more, and more preferably is 30,000 or more.The number average molecular weight is 1
If it is less than 0,000, the tackiness of the graft polymer may increase and handling may become extremely difficult.
Undesirable.

In the present invention, the graft polymer (b) is a polymer obtained by grafting polysiloxane having a hydroxyl group onto a copolymer of hexene-1 and a compound of general formula (1)/hexene-1, α-olefin and a compound of general formula (1). The weight ratio of the copolymer obtained by grafting a polysiloxane having a hydroxyl group to the copolymer with the compound is preferably 100 to 50,150 to 0.

The rubber composition of the present invention can be prepared using common rubber compounding agents, such as
reinforcing agents, fillers, softeners, activators, fire retardants, lubricants,
A crosslinking agent, a crosslinking aid, etc. can be added as necessary. Specifically, reinforcing agents include carbon black, white carbon, basic carbon magnesium, activated carbon calcium, etc. fillers include calcium carbonate, clay, talc fiber, etc., and softeners include paraffin. Examples include naphthenic oils, naphthenic oils, aroma oils, and the like. In addition, anti-aging agents include phenolic, imidazole, and amino-based agents; crosslinking agents include organic peroxide; crosslinking aids include sulfur,
p-Benzoquinone dioxime, p,p'dibenzoyl-
Examples include quinone dioxime, dinitrosobenzene, ethylene glycol dimethacrylate, triallylisocyanurate, trimethylpropane trimethacrylate, liquid polybutadiene, polybutene, and polybutadiene resin.

The rubber composition of the present invention can be obtained by kneading with a common rubber mixing machine such as a Banbury mixer, a kneader blender, an intermixer, a roll, or the like.

〔Example〕

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

In the examples, parts and % mean parts by weight and % by weight unless otherwise specified. In addition, the polystyrene equivalent number average molecular weight in the Examples was measured as follows according to the method described in "Gel Permeation Chromatograph" (written by Takeuchi, published by Maruzen Co., Ltd.).

First, using standard polystyrene with a known molecular weight (manufactured by Toyo Soda Co., Ltd., monodispersed polystyrene), the molecular weight M and its GP are determined.
The C (gel permeation chromatography) count was measured, and the molecular weight M and EV (Elution Vo) were determined.
lume, eluent volume) was drawn, the GPC pattern of the sample was then measured by the GPC measurement method, and the molecular weight M was determined using the calibration curve. The sample preparation conditions and GPC measurement conditions at that time are as follows.

A) Sample preparation 0-Dichlorobenzene solution with 2.6-
Adding 0.08% di-t-butyl-p-cresol,
Dissolve the solution and separate the sample into an Erlenmeyer flask together with the solution to a concentration of 0.1%. The Erlenmeyer flask is heated to 120° C., stirred for about 60 minutes to dissolve, and subjected to GPC. Note that in the GPC device, filtration is automatically performed using a 0.5 μm sintered filter.

B) GPC measurement conditions Equipment: Manufactured by Waters, USA, 150 type column: Manufactured by Toyo Soda, H type Sample amount = 500 μl Temperature = 120°C Flow rate: 1 m 11 minutes Total number of theoretical plates: 1X10-2X10' (measured value with acetone) ) Furthermore, the hexene-1 content of the hexene-1 polymer used in the present invention was determined by infrared spectroscopic analysis.

That is, the ratio of the absorption spectrum near 730 cm-1 of the hexene-1 polymer to the characteristic absorption spectrum of the α-olefin is determined, and in advance, polyhexene-1 and poly-
The hexene-1 content was determined from a calibration curve prepared using samples with a known mixing ratio with α-olefin.

Vulcanized physical properties were measured according to JISK6301.

Example 1 Catalyst Preparation In a stainless steel ball mill that had been purged with nitrogen in advance, 210 mmol of magnesium chloride and 1 mol of tetrabutoxytitanium were added.
05 mmol and 64 ml of n-hexane were charged, and the mixture was ground in a vibration mill at room temperature for 7 hours.

After crushing, take out the entire contents and add n-hexane 4Q Q
mj! After washing with water five times, 400 ml of n-hexane was charged, and 105 mmol of a 1 mol/1 solution of diethylaluminium chloride was added dropwise with stirring at room temperature, followed by reaction at room temperature for 5 hours.

The reaction solution thus obtained was mixed with 400ml of n-hexane.
After washing with water five times, 40 Qmffi of n-hexane was added to prepare a titanium catalyst solution. The titanium concentration of this titanium catalyst solution was 0.04 mol/1.

■Polymerization In a flask with an internal volume of 5β that was purged with nitrogen in advance, 31 n-hexane dehydrated and purified with a molecular sieve, 180 ml of hexene-1 purified in the same way (special grade reagent),
Add 20mf of 4-methylpentene-1 (special grade reagent) and add triisobutylaluminum 2 with sufficient stirring.
5 mmol, the titanium catalyst solution is 0 in terms of titanium atoms.
．． Copolymerization was started by charging 5 mmol.

After copolymerization was carried out at 30° C. for 120 minutes, the polymerization reaction was stopped by adding 5 m6 of isopropyl alcohol to the polymerization solution I. Then, the polymerization reaction solution was poured into a large amount of methanol to solidify, and then vacuum-dried.

The yield of the produced polymer was 112 g, containing i81 hexene-1.
%, and the number average molecular weight (in terms of polystyrene) was 49.000.

■ Physical property evaluation Using the obtained polymer, kneading it for 4 minutes at 70°C using a 250 CC Labo Plastomill according to the formulation shown in Table 1, then kneading the crosslinking agent and crosslinking aid using a roll machine to form a rubber compound. I got something.

Below are the margins in Table 1 *1: Diablack G, manufactured by Mitsubishi Kasei *2 = Fukol P400, manufactured by Fuji Kosan *3: Bark Mill D, manufactured by NOF Corporation Press the obtained rubber composition at 160°C for 35 minutes After vulcanization and molding into a sheet, physical property tests were conducted. The results are shown in Table 2.

The rubber composition of this example had a large tan δ, exhibited excellent vibration damping performance, and had a relatively small static-dynamic ratio (frequency dependence).

Comparative Example 1 Using Butyl rubber (JSR Butyl 268, manufactured by Butyl Co., Ltd., Japan), a test was conducted in the same manner as in Example 1 to evaluate the physical properties according to the formulation shown in Table 3. Second result
As shown in the table, the tan δ was small and the vibration damping performance was poor.

Table 3 *4 = Tsukuseramon, Mercaptobenzothiazole book manufactured by Nyuuchi Shinkosha! I Nickcellar TT, 〃 Tetramethylthiuram disulfide Example 2 In the polymerization of Example 1, hexene-1 was used as a monomer.
200mj! Polymerization was carried out in the same manner except that 4-methylpentene-1 was not used. The polymer yield was 115 g, and the number average molecular weight was 65,000.

Further, in the physical property evaluation of Example 1, the test was conducted in the same manner except that the polymer of this example was used as the polymer. The results are shown in Table 2, and showed excellent vibration damping performance.

Example 3 In the polymerization of Example 1, hexene-1 was used as a monomer.
Polymerization was carried out in the same manner except that 100 mA of 14-methylpentene-1 was changed to 100 mA. The polymer yield was 116 g, the hexene-1 content was 47%, and the number average molecular weight (in terms of polystyrene) was 82,000.

Further, in the physical property evaluation of Example 1, the test was conducted in the same manner except that the copolymer of this example was used as the polymer. The results are shown in Table 2, and the tan δ was very large, indicating excellent vibration damping performance, and the frequency dependence was also large.

Example 4 In the polymerization of Example 1, the monomers were hexene-1 and 1
Polymerization was carried out in the same manner except that 80 ml and butene-1 was changed to 20 ml. Polymer yield is 121
g, hexene-1 content was 76%, and number average molecular weight (polystyrene equivalent) was 53,000.

Further, in the physical property evaluation of Example 1, the test was conducted in the same manner except that the copolymer of this example was used as the polymer. The results are shown in Table 2, and showed excellent vibration damping performance.

Example 5 In the polymerization of Example 1, hexene-1 was used as a monomer.
200mf and 7-octynyldimethylchlorosilane 1
Copolymerization was carried out in the same manner as in Example 1 except that ml of silicone oil modified with silanol at both ends (
XF40-518 (manufactured by Toshiba Silicone Co., Ltd.) 2.5 m/ml was charged and stirred for 1 hour. Next, 5 ml of dehydrated methanol was added to deactivate the catalyst, and the methanol was coagulated.
It was dried on a roll at 00°C. Polymer yield is 121g
, the silicone oil content was 1.3%.

The physical properties were evaluated in the same manner as in Example 1 using 50 parts of the copolymer obtained in Example 1 and 50 parts of the graft polymer obtained in this example as polymers. The results are shown in Table 2, and the obtained rubber composition showed excellent vibration damping performance.

(Effects of the Invention) The anti-vibration rubber composition of the present invention has excellent vibration damping performance and heat resistance, and is useful for various automobile anti-vibration rubbers, track butts, fenders, various mechanical parts, and the like.

Claims (3)

[Claims] (1) (a) 100 to 5% by weight of a polymer of hexene-1 and/or a copolymer of hexene-1 and an α-olefin having 3 to 20 carbon atoms excluding hexene-1, (b) hexene-1 and General formula I CH_2=CH-(CH_2)_n-SiR^1mX_
3_-_m (in the formula, n is an integer of 1 or more, m is an integer of 0 to 2, X is a chlorine atom or a bromine atom, R^1 means a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) A copolymer of a compound grafted with polysiloxane having a hydroxyl group and/or a copolymer of hexene-1 and an α-olefin having 3 to 20 carbon atoms excluding hexene-1 and a compound of general formula I. An anti-vibration rubber composition comprising 0 to 95% by weight of a polymer grafted with a polysiloxane. (2) The anti-vibration rubber composition according to claim 1, wherein the content of hexene-1 in (a) is 30% by weight or more. (3) The vibration isolation according to claim 1, wherein (b) is a polymer obtained by grafting polysiloxane having a hydroxyl group to a copolymer of hexene-1 and the compound of general formula I. Rubber composition.