JPH0518848B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel living polymer obtained by anionic polymerization of substituted-1,3-butadiene derivatives, and specifically,
This invention relates to a living diene polymer having a reactive silyl group. Conventional reactive silane compounds are often used for the purpose of surface treatment of inorganic materials, and most of them are low-molecular compounds. In addition, there are silane compounds that can be polymerized during reaction, such as vinyl compounds and methacrylic acid compounds that have silyl groups, but these are rarely polymerized alone and are copolymerized in small amounts for the purpose of modifying other plastics. It was at a level where it was possible to do so. The present inventors discovered that a living polymer having a reactive silyl group and a diene structure, which are not found in conventional silane compounds, can be used for various purposes, and completed the present invention. That is, the living polymer of the present invention is also used as an anionic polymerization initiator to produce a polymer that has an affinity for inorganic substances. In addition, the polymer obtained from the living polymer of the present invention can be used in the same way as conventional silane coupling agents, and can also be used to add rubber elasticity to the surface of inorganic fillers by using UV photoresists, reactive silyl groups, and diene structures. Improving the impact resistance of plastics, manufacturing highly dispersed magnetic materials by coating them on the surface of magnetic materials, co-vulcanization after blending with rubber, crosslinking using reactive silyl groups, and treating the surface of inorganic fillers. Improvement of hydrolysis resistance of FRP etc.
It can be used as an adhesive and coupling agent for glass, ceramics, and rubber products, and can be used in a variety of other applications. Additionally, the living polymers of the present invention may contain other monomers such as styrene, α-methylstyrene,
It is useful as a raw material for the synthesis of (living) block copolymers with 1,3-butadiene, isoprene, methyl acrylate, methyl methacrylate, acrylonitrile, methacrylonitrile, etc.
These are used as compatibility improvers in polymer blends, medical applications that take advantage of their microphase-separated structure, impact modifiers, and the like. The living polymer of the substituted-1,3-butadiene derivative of the present invention has the following structural formula [] By anionically polymerizing a substituted-1,3-butadiene derivative represented by

【formula】

【formula】

[Formula] and

[Formula] (In the formula, X represents SiR ₁ R ₂ R ₃ , and R ₁ , R ₂ , R ₃ are
Represents an alkoxy group having 1 to 3 carbon atoms, an alkoxy group or an alkyl group having 1 to 3 carbon atoms, and R ₁ , R ₂ ,
Except when R ₃ is also an alkyl group, and
a, b, c, and d indicate the weight percent of each repeating unit produced by polymerization of the substituted butadiene derivative, and when a+b+c+d=100%, a=50 to 100,
b=0-50, c=0-50, d=0-50. ) with a weight average molecular weight of 500,000 to 500,000, and at least one end is an anion. The substituted-1,3-butadiene derivatives of the present invention include 1-(trimethoxy)silyl-1,3-butadiene, 1-(triisopropoxy)silyl-
1,3-butadiene, 1-(methoxydimethyl)
Examples include 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)
Also included are silyl-1,3-butadiene and 2-(dimethoxymethyl)silyl-1,3-butadiene. The living polymer of the present invention is produced by anionic polymerization. Examples of anionic polymerization initiators include 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, n-butyllithium, etc. can be mentioned. Anionic polymerization is performed at low temperatures ranging from room temperature to -100°C, with 0.1
~20 hours, preferably in the presence of a solvent. As such a solvent, one or more of ether solvents such as benzene, triene, hexane, 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 living polymer has a molecular weight of -1,3-substituted
It can be controlled by changing the ratio of butadiene derivative/anionic polymerization initiator, and by increasing the ratio, the molecular weight can be increased. The living polymer thus obtained usually has a physical property value of about 500 to about 500,000, preferably about 2,000 to about
It has a number average molecular weight of 200,000, more preferably about 5,000 to about 100,000. Furthermore, a living polymer with an extremely narrow molecular weight distribution in which the weight average molecular weight/number average molecular weight ratio is close to 1 can be easily produced. The repeating unit structure of the living polymer thus obtained is as shown in formula [], cis-1,4
bond, trans-1,4 bond, 1,2 bond, 3,
Although there are four isomers of 4 bonds, in the above-mentioned living anionic polymerization method, cis-1,4 bonds and trans-1,4 bonds are preferentially produced. EXAMPLES Hereinafter, the present invention will be described in more detail with reference to 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, 0.238 mmol of α-methylstyrene and 5 ml of tetrahydrofuran was connected to a high vacuum line.
Anionic polymerization was carried out in the following manner using an apparatus consisting of a reaction flask and an ampoule with a breakable seal containing a frozen and degassed mixed solution. That is, after keeping at 10 ^-6 mmHg for 5 hours and degassing -
A solution of naphthalene potassium salt, α-methylstyrene and tetrahydrofuran cooled to -78°C was placed in a reaction flask cooled to 78°C by breaking the seal of the ampoule, introducing the solution into the reaction flask, and then adding 2-(triisopropoxy ) silyl-1,3-
Similarly, 2-(triisopropoxy) was prepared from an ampoule containing a solution of butadiene in tetrahydrofuran.
A solution of silyl-1,3-butadiene in tetrahydrofuran was introduced into the reaction flask and reacted at -78°C for 0.5 hours, at 0°C for 1.5 hours, and further at 20°C for 1 hour. The polymerized system had a yellowish brown color characteristic of living 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 and poly[2-
(triisopropoxy)silyl-1,3-butadiene] was obtained. Yield: 90% (yield: 0.95 g) The glass transition temperature of this poly[2-(triisopropoxy)silyl-1,3-butadiene] is -36
℃, it was soluble in organic solvents such as ethanol, pyridine, dioxane, tetrahydrofuran, benzene, chloroform and acetone. Further, when this poly[2-(triisopropoxy)silyl-1,3-butadiene] was measured by gel permeation chromatography in a tetrahydrofuran solvent using standard polystyrene as a reference, the number average molecular weight was 13,500. . still,
The calculated number average molecular weight is 17,400. Furthermore, the ratio of weight average molecular weight/number average molecular weight is
It was 1.07. Example 2 2-(triisopropoxy)silyl-1,3-
Butadiene 3.81 mmol and tetrahydrofuran 5
ml of a mixed solution and a mixed solution of 0.148 mmol of naphthalene lithium salt and 5 ml of tetrahydrofuran were frozen, degassed, and sealed in an ampoule with a breakable seal. The treatment was carried out in the same manner as in Example 1, except that the reaction was carried out at ℃ for 1 hour. The polymerized system had a yellow color characteristic of living anions, but this color disappeared immediately when a small amount of water or methanol was added. Poly[2-(trimethoxy)silyl-1,3-
butadiene] yield 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 was 15,500, and the calculated value was 13,300. Also, the ratio of weight average molecular weight/number average molecular weight is
It was 1.15. Example 3 A mixed solution of 4.41 mmol of 2-(trimethoxy)silyl-1,3-butadiene and 5 ml of tetrahydrofuran and 0.124 mmol of naphthalene potassium salt.
The same procedure as in Example 1 was used, except that an ampoule with a breakable seal containing a frozen and degassed mixed solution of 0.248 mmol of α-methylstyrene and 5 ml of tetrahydrofuran was used. The polymerized system had a yellowish brown color characteristic of living anions, but this color immediately disappeared when a small amount of water or methanol was added. Poly[2-(trimethoxy)silyl-1,3-
butadiene] yield was 100% (yield: 0.83 g). Also, the glass transition temperature is -36℃, and ethanol,
It was soluble in organic solvents such as pyridine, dioxane, tetrahydrofuran, benzene, chloroform and acetone. Furthermore, the number average molecular weight was 22,000 and the calculated value was 13,400. In addition, the ratio of weight average molecular weight/number average molecular weight is
It was 1.25.

Claims (1)

[Claims] 1. Structural formula [] By _anionically polymerizing the substituted- _{1,3 -} butadiene derivative represented by R ₁ , R ₂ , R ₃ are
Represents an alkoxy group having 1 to 3 carbon atoms, an alkoxy group or an alkyl group having 1 to 3 carbon atoms, and R ₁ , R ₂ ,
Except when R ₃ is also an alkyl group. or,
a, b, c, and d indicate the weight percent of each repeating unit produced by polymerization of the substituted butadiene derivative, and when a+b+c+d=100%, a=50 to 100,
b=0-50, c=0-50, d=0-50. ), with a weight average molecular weight of 500 to 500,000,
A living polymer in which at least one end is an anion.