JPS61271307A - Living polymer of substituted 1,3-butadiene derivative - Google Patents

Abstract

PURPOSE:A reactive silyl group-containing living diene polymer which can be used as an anionic polymerization initiator and forms a polymer having an affinity for inorganic substances, obtained by anion-polymerizing a specified substituted 1,3-butadiene derivative. CONSTITUTION:A living polymer obtained by anion-polymerizing a substituted 1,3-butadiene of the formula (wherein X is H or SiR1R2R3 and at least one X must be SiR1R2R3, and R1, R2 and R3 are each a lower alkoxy group, lower alkyl group or tri-lower-alkylsilyloxy group, provided that the case where R1, R2 and R3 are simultaneously lower alkyl groups is excluded). An example of the compound of the above formula is 1-(trimethoxy)-silyl-1,3-butadiene. Examples of the anionic polymerization initiators include napthalene lithium salt and naphthalene sodium salt. The anionic polymerization is carried out at room temperature--100 deg.C in the presence of, preferably, a solvent (e.g., dioxane).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel flexible polymer obtained by anionic polymerization of a substituted-1,3-butadiene derivative, and more particularly, to a diene-based living polymer having a reactive silyl group. It is something.

Conventional reactive silane compounds are often used for the purpose of surface treatment of inorganic materials, and most of them are low-molecular compounds. There are also polymerizable silane compounds such as vinyl compounds and methacrylic acid compounds that have reactive silyl groups, but these are rarely polymerized alone and are copolymerized in small amounts for the purpose of modifying other plastics. It was the extent that it was done.

The present inventors have discovered that living polymers having a reactive silyl group and a diene structure, which are not found in conventional silane compounds, can be used for various purposes, and have completed the present invention.

That is, the slipping polymer of the present invention can also be used as an anionic polymerization initiator to produce a polymer that has an affinity for inorganic substances.

In addition, the polymer obtained from the pasting polymer of the present invention can be used in the same way as conventional silane coupling agents, as well as in UV
Using photoresists, reactive silyl groups and diene structures, rubber elasticity is added to the surface of inorganic fillers to improve the impact resistance of plastics, production of highly dispersible magnetic materials by coating on the surface of magnetic materials, and combinations with rubber. The co-vulcanization process after blending includes crosslinking using reactive silyl groups, improving the hydrolysis resistance of FRP etc. by treating the surface of inorganic fillers, glass,
It can be used as an adhesive and coupling agent for ceramics and rubber products, and can be used in a variety of other applications.

Furthermore, the slipping polymer of the present invention is a (living) block copolymer with other monomers such as styrene, α-methylstyrene, 1°3-butadiene, isoprene, methyl acrylate, methyl methacrylate, acrylonitrile and methacrylonitrile. They are useful as synthetic raw materials for polymers, and are used as compatible agents in polymer blends, medical applications that take advantage of their microphase-separated structure, and impact modifiers.

The novel diene polymer having a reactive silyl group of the present invention can be obtained by anionically polymerizing a substituted-1,3-butadiene derivative represented by the structural formula [I].

HC=CCH=CH2 Support 1"9 (X represents hydrogen or siR, R2R, and one of the X's is always SiR+92ft:l. Also, R1, R2
, R3 represents a halogen, a lower alkoxy group or a tri-lower alkylsilyloxy group, except when R1, R2 and R3 are all lower alkyl groups. ) Substitution-1 of the present invention
,3-butadiene derivatives include 1-(trimethoxy)silyl-1,3-butadiene, 1-(triisopropoxy)silyl-1,3-butadiene, 1-(,methoxydimethyl)silyl-1,3-butadiene. and 1-(dimethoxymethyl)silyl-1,3-butadiene.

Also, 2-(trimethoxy)silyl-1,3-butadiene, 2-(triisopropoxy)silyl-1,3-butadiene, 2-(methoxydimethyl)silyl-1,3-butadiene and 2-(dimethoxymethyl) Silyl-1,3-
The glueing polymers of the invention, which also include butadiene, are produced by anionic polymerization.

As the anionic polymerization initiator, naphthalene lithium salt,
Naphthalene sodium salt, naphthalene potassium salt, (α
-methylstyrene oligomer) lithium salt, (α-methylstyrene oligomer) sodium salt, (α-methylstyrene oligomer) potassium salt, cumyl potassium salt, and n-butyllithium.

Anionic polymerization is carried out at a low temperature of room temperature to -100°C, with a
It is carried out for 20 hours, preferably in the presence of a solvent.

Such solvents include benzene, toluene, hexane,
One or more ethereal solvents such as cyclohexane, preferably tetrahydrofuran and dioxane are used.

Further, the anionic polymerization reaction is carried out in an inert gas atmosphere or the like free of moisture and oxygen that would interfere with the polymerization reaction.

The molecular weight of the living polymer can be controlled by changing the ratio of substituted-1,3-butadiene derivative/anionic polymerization initiator, and by increasing the ratio, the molecular weight can be increased.

The polymer thus obtained usually has a physical property of about 500% based on the physical properties of the polymer obtained from this living polymer.
~about 500,000, preferably from about 2,000 to about 20
0,000, more preferably about 5,000 to about 100,
It has a number average molecular weight of 0.000.

Furthermore, a living polymer with an extremely narrow molecular weight distribution in which the ratio of it average molecular weight/number average molecular weight is close to 1 can be easily produced.

Hereinafter, the present invention will be explained in more detail using actual road examples, but the present invention is not limited thereto.

Example 1 A mixed solution of 3.88 mmol of 2-(triisopropoxy)silyl-1,3-butadiene and 5 ml of tetrahydrofuran, 0.119 mmol of naphthalene potassium salt, and 0.238 mmol of α-methylstyrene connected to a high vacuum line. and 5 ml of tetrahydrofuran! Anionic polymerization was carried out in the following manner using an apparatus consisting of an ampoule with a breaker pull seal and a reaction flask containing a frozen and degassed mixed solution.

That is, ],] After being kept at 0-61■H for 5 hours and degassed -
A solution of naphthalene potassium salt, α-methylstyrene and tetrahydrofuran cooled to -78°C was introduced into the reaction flask by breaking the seal of the ampoule and introducing the solution into the reaction flask. Similarly, a tetrahydrofuran solution of 2-(triisopropoxy)silyl-1,3-butadiene was introduced into the reaction flask from an ampoule containing a tetrahydrofuran solution of propoxy)silyl-1,3-butadiene at -78°C.
The reaction was carried out for 0.5 hours at 0°C, for 1.5 hours at 0°C, and further for 1 hour at 20°C.

It had a yellow-brown color characteristic of polymerized apex anions.

This color disappeared immediately upon addition of a small amount of water or methanol.

This living polymer was mixed with water at room temperature, extracted with diethyl ether, and dried over magnesium sulfate. Next, diethyl ether was removed to obtain poly[2-(triisopropoxy)silyl-1,3-butadiene]. Yield 90%
(Yield: 0.95 g) The glass transition temperature of this poly C2-, ()liisobrobogyshi)silyl-1゜3-butadiene is -36゛C. It was compatible with the storage medium.

Further, when gel permeation chromatography was performed on this poly(2-(+-lyisobroboxy)silyl-1,3-butadiene) in tetrahydrofuran solvent using standard polystyrene as a reference, the number average molecular weight was 13.500. Note that the calculated number average molecular weight is 17,400.

Furthermore, the ratio of weight average molecular weight/number average molecular weight is 1.07
Met.

Example 2 A mixed solution of 3.81 mmol of 2-(triisopropoxy)silyl-1,3-butadiene and 5 mβ of tetrahydrofuran and a mixed solution of 0.148 mmol of naphthalene lithium salt and 5 ml of tetrahydrofuran were frozen, degassed, and sealed. Use an ampoule with a breaker pull seal, −
1 hour at 78°C, 1 hour at 0°C, and 1 hour at 20°C.
The treatment was carried out in the same manner as in Example 1, except that the reaction was carried out for a certain period of time.

It had a yellow color characteristic of polymerized anions, but
The color disappeared immediately upon addition of a small amount of water or methanol.

The yield of poly(2-()rimethoxy)silyl-1,3-butadiene] was 88% (yield: 0.86 g).

It was also soluble in organic solvents such as ethanol, pyridine, dioxane, tetrahydrofuran, benzene, chloroform, and acetone.

The number average molecular weight is 15,500 and the calculated value is 13°300
Met.

Further, the ratio of weight average molecular weight/number average molecular weight was 1°15.

Example 3 A solution of 4°41 mmol of 2-(trimethoxy)silyl-1,3-butadiene and 5 m6 of tetrahydrofuran and 0.12.4 mmol of naphthalene potassium salt, α-
The same procedure as in Example 1 was used, except that an ampoule with a breaker seal containing a frozen, degassed solution containing 0.248 mmol of methylstyrene and 5 ml of tetrahydrofuran was used.

It exhibited a yellow-brown color characteristic of polymerized exfoliating anions, but this color immediately disappeared when a small amount of water or methanol was added.

The yield of poly(2-(1-limethoxy)silyl-1,3-butadiene) was 100% (yield: 0.83 g).6 Also, the glass transition temperature was -36°C, and ethanol, pyridine, dioxane, It was compatible with organic solvents such as tetrahydrofuran, benzene, chloroform and acetone.

Furthermore, the number average molecular weight is 22.000 and the calculated value is 13.4.
It was 00.

The weight average molecular weight/number average molecular weight of the juice was 1°25.

Claims (1)

[Claims] There are mathematical formulas, chemical formulas, tables, etc. represented by the structural formula [I] (X represents hydrogen or SiR_1R_2R_3, and one of the Xs is always SiR_1R_2R_3. R_1
, R_2, R_3 represent a lower alkoxy group, a lower alkyl group and a tri-lower alkylsilyloxy group, R_1,
Except when R_2 and R_3 are both lower alkyl groups. ) A living polymer obtained by anionically polymerizing a substituted-1,3-butadiene derivative.