JP3274197B2 - Isobutylene polymer having functional group and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an isobutylene polymer having a functional group and a method for producing the same.

[0002]

2. Description of the Related Art Polymers having a functional group at a molecular chain terminal or in a graft chain are useful as raw materials for adhesives, modifiers, coating agents, sealing agents and the like. One of such polymers, for example, a method for producing a terminal-functional isobutylene-based polymer includes 1,4-bis (α-chloroisopropyl).
Benzene (hereinafter "p-DCC" hereinafter) as an initiator and a chain transfer agent, and the inifer method for cationic polymerization of isobutylene BCl ₃ as a catalyst (U.S. Pat. No. 4276
394) are known. Further, the isobutylene-based polymer having chlorine atoms at both ends immediately after polymerization or after purification obtained by the inifer method is added with B as a polymerization catalyst.
It is known that, in addition to Cl ₃ , TiCl ₄ is further added and then reacted with allyltrimethylsilane to be converted into a polymer having allyl groups at both ends (JP-A-63-105005).

However, according to the above-mentioned method, a functional group can be introduced only at the terminal of a molecular chain. Therefore, in order to introduce a plurality of functional groups into one polymer molecule, it is necessary to use a compound having two or more polymerization initiation points (such as p-DCC). An object of the present invention is to provide a novel polymer having a plurality of functional groups in one molecule and to provide p-DC
An object of the present invention is to provide a method for producing an isobutylene-based polymer having a plurality of functional groups in a molecule without using an expensive compound such as C.

[0004]

That is, the present invention provides (1)
At least one compound of formula (I) per molecule

[0005]

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[Wherein, R represents a hydrogen atom, a methyl group or an ethyl group. Q is

Embedded image And n represents an integer of 1 to 3. Y is -NO ₂ ,-
Indicates OCH ₃ or a hydrogen atom . A number-average molecular weight of 500 to 500,0
No. 00, having a unit represented by an isobutylene polymer having a functional group, having a number average molecular weight of 500
To 500,000 isobutylene-based polymers having a functional group, (2) a cationically polymerizable monomer containing isobutylene, and a compound represented by the general formula (II):

[0007]

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[ Wherein , R and Q are as defined above.
You. The method for producing an isobutylene-based polymer according to the above (1), wherein the styrene-based compound is polymerized in the presence of a Lewis acid .

[0009]

[0010]

The isobutylene-based polymer having a functional group of the present invention has at least one of the above-mentioned general formula (I) in one molecule.
It is a polymer characterized by having the unit represented by these. In the general formula (I), R represents a hydrogen atom, a methyl group or an ethyl group, and is preferably a hydrogen atom or a methyl group. Q represents a monovalent organic group having the above specific functional group. The number average molecular weight of the isobutylene-based polymer of the present invention mainly containing isobutylene monomer units is usually 500 to
500,000, preferably 1,000 to 50,000
And having at least one, preferably 1.05 or more units represented by the general formula (I) per molecule. If the number average molecular weight is less than 500, the content of the isobutylene unit is small and the properties as an isobutylene-based polymer cannot be exhibited. If the number average molecular weight exceeds 500,000, the polymer becomes resinous and handling becomes difficult.

In the present specification, the cationically polymerizable monomer containing isobutylene is not limited to a monomer comprising only isobutylene, but 50% by weight of isobutylene (hereinafter simply referred to as "%") or less. It also means a monomer substituted with a cationically polymerizable monomer capable of copolymerizing with the above. Cationic polymerizable monomers copolymerizable with isobutylene include, for example, those having 3 to 1 carbon atoms.
2, olefins, conjugated dienes, vinyl ethers,
Examples thereof include aromatic vinyl compounds and vinyl silanes. Among them, olefins having 3 to 12 carbon atoms and conjugated dienes are preferable.

Specific examples of the cationically polymerizable monomer copolymerizable with isobutylene include, for example, propylene,
1-butene, 2-butene, 2-methyl-1-butene, 3
-Methyl-2-butene, pentene, 4-methyl-1-pentene, hexene, vinylcyclohexane, butadiene, isoprene, cyclopentadiene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene , Dichlorostyrene, β-pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl- 1,1,
3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, p-hydroxystyrene and the like. These cationically polymerizable monomers copolymerizable with isobutylene may be used alone or in combination of two or more with isobutylene.
The styrene compound used in the present invention is represented by the general formula (II)

[0014]

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Wherein R and Q are as defined above.
You. ] Are shown below. In the present invention, as long as the compound falls under the general formula (II), a conventionally known compound or a novel compound which has not been known can be widely used.

[0016]

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And the like.

[0018]

[0019]

[0020]

The Lewis acid used in the present invention is a component used as a polymerization catalyst, and MX'p (M is a metal atom, X '
Is a halogen atom, p is an integer of 2 or more), for example, AlCl ₃ , SnCl ₄ , TiCl ₄ , VC
l ₅ , FeCl ₃ , BF _3, Et ₂ AlCl, EtAl
Organic aluminum compounds such as Cl _{2 and the} like,
It is not limited to these. Among these Lewis acids, SnCl ₄ , TiCl ₄ , Et ₂ AlCl, EtAl
Cl _{2 and the} like are preferred.

The amount of the Lewis acid used is usually preferably 0.1 to 50 times the styrene compound to be copolymerized with the cationically polymerizable monomer containing isobutylene.
More preferably, it should be 0.2 to 10 times. If the amount of the Lewis acid is less than 0.1 times, the yield of the polymerization reaction may be low, and if it is more than 50 times, particularly good results cannot be obtained.

In the present invention, as the polymerization solvent, for example, a hydrocarbon solvent such as an aliphatic hydrocarbon and a halogenated hydrocarbon is used. Of these, halogenated hydrocarbons are preferred, and chlorinated hydrocarbons having a chlorine atom are more preferred. Specific examples of such aliphatic hydrocarbons include pentane and hexane, and specific examples of halogenated hydrocarbons include chloromethane, chloroethane, methylene chloride,
Examples thereof include 1,1-dichloroethane, chloroform, and 1,2-dichloroethane. These may be used alone or in combination of two or more. And even small amounts of other solvents,
For example, an acetate such as ethyl acetate or an organic compound having a nitro group such as nitroethane may be used in combination.

In carrying out the production method of the present invention, there is no particular limitation, and conventional polymerization methods can be widely applied. In one container, a polymerization solvent, a cationic polymerizable monomer containing isobutylene, a styrene compound, a batch method of sequentially charging a polymerization catalyst, or the like may be used, or a polymerization solvent, a cationic polymerizable monomer containing isobutylene, a styrene compound, A continuous method may be employed in which a polymerization catalyst or the like is continuously charged into a certain system while reacting and then further taken out.

In the production method of the present invention, the polymerization temperature is preferably about +10 to -80 ° C, more preferably about 0 to -40 ° C, and the polymerization time is usually 0.5 to 120 minutes. Degree, preferably about 1 to 60 minutes. Further, the monomer concentration of the cationically polymerizable monomer containing isobutylene during polymerization is usually preferably about 0.1 to 8 mol / l, more preferably about 0.5 to 5 mol / l. Further, in the production method of the present invention, the styrenic compound to be added to the polymerization system is usually 0.002 to 1 times mol, preferably 0.01 mol, per mol of the cationically polymerizable monomer containing isobutylene to be used.
It is desirable to add about 0.1 times mol. If the amount of the styrene-based compound is less than 0.002 mole, it is difficult to introduce one or more units represented by the general formula (I) into one molecule of the polymer. If the amount is too large, it becomes difficult to exhibit characteristics as an isobutylene-based polymer.

In the production method of the present invention, it is preferable to terminate the polymerization reaction by adding an alcohol such as methanol from the viewpoint of ease of handling later. However, the present invention is not particularly limited to this, and any conventional conventional means may be used. Can be applied, and it is not particularly necessary to perform the termination reaction again. By such a production method, a polymer mainly composed of isobutylene monomer units and having a number average molecular weight of 500 to 500,000, wherein at least one unit represented by the general formula (I) per molecule is a polymer The isobutylene polymer contained therein is produced.

[0027]

EXAMPLES then set a reference example, clarify the invention further, but the invention is not intended to be limited by the embodiment.

Synthesis of non-conjugated diene A 4-hydroxybenzaldehyde (100 mm) was placed in a 500 ml eggplant-shaped flask.
ol) 12.2 g, 18.5 ml of a 28% methanol solution of sodium methylate (130 mmol), 60 ml of methanol
And 6-bromo-1-hexene (150 mmol)
0 ml was added and the mixture was heated under reflux for 18 hours. After distilling off volatile components, the solution was concentrated to about 1/2 of the liquid volume, 200 ml of toluene and 100 ml of water were added, and the mixture was shaken, and then the aqueous phase was removed. The organic phase was washed three more times with 150 ml of water, dried over 10 g of anhydrous magnesium sulfate, filtered to remove solids and evaporated to remove volatiles to give 18.9 g of 4- (1-hexenyloxy) benzaldehyde. Was.

Under a nitrogen atmosphere, 150 ml of dry diethyl ether, 7.5 g of methyltriphenylphosphonium bromide (21 mmol), 1.6 N hexane solution of n-butyllithium (21 mmol) in a 200 ml three-necked flask 13.
1 ml was added, and the mixture was stirred at room temperature for 5 hours to prepare methylenephosphorane. A solution of 4.08 g of 4- (1-hexenyloxy) benzaldehyde (20 mmol) in dry diethyl ether (20 ml) was added dropwise thereto over 3 minutes. The reaction solution was further heated to reflux for 1 hour, the solid content was filtered off, 150 ml of hexane was added, and the organic phase was washed three times with 150 ml of water. [Non-conjugated diene A] 3.0 g was obtained.

[0030]

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The structure of the obtained conjugated diene A was analyzed by ¹ H NMR.
The spectrum and IR spectrum were examined. The results are shown below. ¹ H NMR spectrum (300 MHz, CDCl ₃ ) δ =
6.8-7.4 (4H), δ = 6.7 (1H), δ =
5.8 (1H), δ = 5.6 (1H), δ = 5.2 (1
H), δ = 4.9-5.1 (2H), δ = 4.0 (2H)
H), δ = 2.1 (2H), δ = 1.8 (2H), δ =
1.6 (2H) IR spectrum (cm ^-1 ) 1640 (medium), 1630 (medium), 1610 (large), 1
510 (large), 1250 (large), 1175 (medium), 99
0 (medium), 850 (medium), 780 (large)

Reference Example 1 A stirring blade was placed in a 100 ml pressure-resistant glass autoclave.
The polymerization vessel was dried by heating the polymerization vessel at 100 ° C. for 1 hour while attaching a three-way cock and a vacuum line and applying a vacuum to the vacuum line, and after cooling to room temperature, the pressure was returned to normal pressure with nitrogen using the three-way cock. Then, while flowing nitrogen from one of the three-way cocks, 40 ml of the main solvent methylene chloride dried by calcium hydride treatment was introduced into the autoclave using a syringe. Then, the non-conjugated diene A [4-
(1-hexenyloxy) styrene] was added in an amount of 1 mmol.

Next, a liquefied gas sampling tube made of pressure-resistant glass with a needle valve containing 5 g of isobutylene dehydrated by passing through a column filled with barium oxide was connected to a three-way cock. It was immersed in a dry ice-acetone bath and cooled for 1 hour while stirring the inside of the polymerization vessel. After cooling, the pressure inside was reduced by a vacuum line, then the needle valve was opened, and isobutylene was introduced into the polymerization vessel from a pressure-resistant glass liquefied gas sampling tube.
Thereafter, the pressure was returned to normal pressure by flowing nitrogen from one of the three-way cocks, then immersed in a -30 ° C dry ice-acetone bath, and further stirred for 1 hour to raise the temperature of the polymerization vessel to -30 ° C. Next, 1.1 ml (10 mmol) of TiCl ₄ was added from a three-way cock using a syringe to start polymerization, and after 20 minutes, methanol which had been cooled to 0 ° C. or less in advance was added. The reaction was completed.

Thereafter, the reaction mixture was taken out into an eggplant type flask, unreacted isobutylene, methylene chloride and methanol were distilled off. The remaining polymer was dissolved in 100 ml of n-hexane, and the solution was washed with water until neutral. Was repeated. Thereafter, the n-hexane solution was concentrated to 20 ml, and the concentrated solution was poured into 300 ml of acetone to precipitate and separate the polymer. The polymer thus obtained was again dissolved in 100 ml of n-hexane, dried over anhydrous magnesium sulfate, filtered, and n-hexane was distilled off under reduced pressure to obtain an isobutylene-based polymer. The yield is calculated from the yield of the obtained polymer, and the number average molecular weight (Mn) and the molecular weight distribution (Mw) are calculated.
/ Mn) by the GPC method (based on polystyrene), and the amount of the copolymer component contained in the polymer was measured by ¹ H-NMR.
The intensity was determined by measuring and comparing the intensity of the resonance signal of the proton belonging to each structure by the (300 MHz) method. The GPC measuring apparatus used was a Waters system (pump 600E, differential refractometer 401, etc.), the column was Shodex K-804 manufactured by Showa Denko KK, and the mobile phase was chloroform.

Reference Examples 2 to 7 Polymers were prepared and evaluated in the same manner as in Reference Example 1 except that the types (A to D) of non-conjugated dienes, the amounts used, and the polymerization catalysts were changed as shown in Table 1. .

[0036]

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[0037]

[Table 1]

Reference Example 8 A polymer was produced and evaluated in the same manner as in Reference Example 1, except that the polymerization reaction was carried out at -10 ° C. Comparative Example 1 A polymer was produced and evaluated in the same manner as in Reference Example 1, except that a non-conjugated diene was not used. Table 2 also shows the results of Reference Examples 1 to 8 and Comparative Example 1.

[0039]

[Table 2]

Reference Example 9 Based on Example 9 described in JP-A-3-95266, 1,9-decadiene and polyhydrodienesiloxane (LS8600, manufactured by Shin-Etsu Chemical Co., Ltd.) were used as raw materials to obtain a hydrocarbon-based addition type. A curing agent was synthesized. A cured product of the isobutylene-based polymer produced in Reference Example 1 of the present invention was prepared in the same manner as in Example 11 described in JP-A-3-95266 using the above-mentioned hydrocarbon-based addition-type curing agent. A No. 3 dumbbell according to JIS K6301 was punched out of the sheet of the cured product, and a tensile test was performed at a tensile speed of 200 mm / min. Table 3 shows the results. In addition, EB (%) refers to deformation when a test piece is broken by being subjected to tension, and represents a ratio of an elongated length to an original length as a percentage. Also,
TB (Kgf / cm ² ) indicates the maximum stress until the test piece is broken by being pulled.

[0041]

[Table 3]

Reference Example 10 The viscosity at 23 ° C. of the isobutylene polymer produced in Reference Example 1 was measured using an E-type viscometer. Table 4 shows the results. At the same time, an attempt was made to measure the viscosity of the isobutylene polymer produced in Comparative Example 1. However, the measurement was impossible because the polymer was rubbery. Table 4 also shows the results.

[0043]

[Table 4]

From the results shown in Table 4, it was clarified that the viscosity of the isobutylene-based polymer decreased due to the effect of the non-conjugated diene as a copolymer component. Considering the processability at the time of preparing a cured product of the isobutylene polymer, the lower the viscosity,
Mixing with various compounding components is easy and preferable. Therefore, a preferable effect specific to the present invention is a decrease in the viscosity of the polymer.

[0045]

According to the preparation of the present invention, by controlling the type and amount of functional groups, it is possible to obtain polymers having different functional group content of conveniently. Further, unlike the case where a conjugated diene is used, since there is no olefin group remaining in the main chain due to 1,4-addition, high weather resistance and the like can be expected. The polymer thus obtained is used as it is as a raw material for a crosslinked cured product, and its functional group is a hydroxyl group,
It can be converted into an amino group, an alkoxysilyl group, a hydrogensilyl group and the like .

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 210/10 C08F 212/14

Claims (2)

(57) [Claims] (1) at least one compound represented by the general formula (I) per molecule: [Wherein, R represents a hydrogen atom, a methyl group or an ethyl group.
Q is And n represents an integer of 1 to 3. Y is -NO ₂ ,-
Indicates OCH ₃ or a hydrogen atom . A number-average molecular weight of 500 to 500,0
No. 00, an isobutylene-based polymer having a functional group. 2. A cationically polymerizable monomer containing isobutylene and a compound represented by the general formula (II): Wherein R and Q are as defined above. The method for producing an isobutylene-based polymer according to claim 1, wherein the styrene-based compound is polymerized in the presence of a Lewis acid.