JPH0559185A - Silicon-containing macromonomer and its production - Google Patents

Abstract

PURPOSE:To obtain a radically polymerizable macromonomer useful as a synthetic raw material for graft polymer, comprising an organosilicon polymer containing a C-Si-C bond as a main chain. CONSTITUTION:A hydrosilane (e.g. 4-vinylphenyldimethylsilane) shown by formula I (R1 and R2 are 1-6C alkyl or phenyl; m is 0 or 1) is polymerized by hydrosilylation reaction to give a silicon-containing macromonomer shown by formula II containing a styryl group at one end, having 1,000-20,000 number- average molecular weight. A graft polymer obtained by using the macromonomer is useful for coating compound, adhesive, coating material and resist material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a radical-polymerizable and ionic-polymerizable polymer having one end of an organosilicon polymer in which a repeating unit composed of a silicon-containing monomer unit is linked by a C--Si--C bond. The present invention relates to a novel silicon-containing macromonomer having a group and a method for producing the same, and the silicon-containing macromonomer according to the present invention has good radical and ionic polymerizability and is useful as a raw material for synthesizing a graft polymer. It is a substance.

[0002]

2. Description of the Related Art Organosilicon polymers have unique physical properties not found in other resins and are of high practical value. Therefore, various polymers have been studied in addition to conventionally known silicone resins. ing. One example is a silicone-based macromonomer having a radical-polymerizable group introduced at one end of a siloxane polymer, and a silicone-based graft obtained by copolymerizing it with a radical-polymerizable monomer such as alkyl (meth) acrylate. There are polymers, and such graft polymers are used in paints, coating agents, release agents, pressure-sensitive adhesives, etc. by taking advantage of properties such as weather resistance, heat resistance and water / oil repellency derived from silicone units (special characteristics JP-A-58-154766 and JP-A-58-1676.
06 and JP-A-59-78236).

[0003] Inspired by the practical use of the above silicone-based macromonomers and silicone-based graft polymers, recently there has been an interest in radical-polymerizable or ionic-polymerizable macromonomers having an organic silicon polymer different from silicone as a skeleton. Has been. However, at present, no macromonomer having an organosilicon polymer skeleton different from silicone and having a high practical value has been obtained.

Technical literature issued in 1956 [Journal
Of American Chemical Society, 78
Vol., P. 1686 (1956)], reports on the polymerization of vinyldialkylsilanes and vinyldiarylsilanes utilizing a hydrosilylation reaction, that is, an addition reaction of silicon atoms and hydrogen atoms in Si-H bonds to carbon-carbon unsaturated bonds. There, according to which, -Si-CH ₂ -C
H ₂ -Si- binding as a main chain, a number average molecular weight of 750 to
Although a polymer having a vinyl group at the terminal of about 1700 was obtained, the side reaction ratio was high and the yield of the polymer having a vinyl group at the terminal was as low as 57 to 68%.

As described above, it is possible to synthesize an organosilicon macromonomer having a skeleton different from silicone by a hydrosilylation reaction, but regarding the polymerization of a silane compound by a hydrosilylation reaction, for example, _{, H-Si (CH 3)} 2 -O-CH 2 -CH = C
As reported that silane compounds such as H ₂ do not polymerize [Polymer Preprint Japan Vol. 39,
No. 7, p2034 (1990)], a polymer cannot be obtained depending on the kind of the silane compound used. That is, even if an attempt is made to obtain a macromonomer, that is, a polymer having a polymerizable group at one end, in high yield, there is no standard for selecting a silane compound suitable for the purpose.

In the present invention, a repeating unit composed of a silicon-containing monomer unit is C-Si-, which has a structure of a polymer serving as a skeleton significantly different from that of a silicone having a main chain formed by an O-Si-O bond. The purpose of the present invention is to provide a macromonomer having a radical-polymerizable and ionic-polymerizable macromonomer, which has an organic silicon polymer linked by C bonds as a skeleton.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has used a hydrosilane represented by the following chemical formula 2 to polymerize by hydrosilylation reaction. The inventors have found that an organosilicon polymer having a styryl group can be obtained in high yield, and have completed the present invention.

That is, the first aspect of the present invention is that the number average molecular weight represented by the following chemical formula 1 is 1,000 to 2
Is a silicon-containing macromonomer of 0000,

(In the above chemical formula 1, R ₁ and R ₂ are an alkyl group having 1 to 6 carbon atoms or a phenyl group, and they may be the same or different. Is a positive number, and m is 0 or 1.) The second invention is the production of the above silicon-containing macromonomer, which comprises polymerizing a hydrosilane represented by the following chemical formula 2 by a hydrosilylation reaction. Is the way.

(In the above chemical formula 2, R ₁ and R ₂ are an alkyl group having 1 to 6 carbon atoms or a phenyl group, which may be the same or different. Is 0 or 1.)

The number average molecular weight in the present invention is a polystyrene equivalent number average molecular weight measured by gel permeation chromatography. Hereinafter, the present invention will be described in more detail.

The hydrosilane monomer used in the present invention is a silane compound represented by the above formula 2, specifically, 4-vinylphenyldimethylsilane, 4-vinylphenyldiethylsilane and 4-vinylphenyl. Dipropylsilane, 4-vinylphenyldibutylsilane, 4-
Vinylphenyldipentylsilane, 4-vinylphenyldihexylsilane, 4-vinylphenyldiphenylsilane, 4-vinylphenylphenylmethylsilane, 4-vinylbenzyldimethylsilane, 4-vinylbenzyldiethylsilane, 4-vinylbenzyldipropylsilane, 4
-Vinylbenzyldibutylsilane, 4-vinylbenzyldipentylsilane, 4-vinylbenzyldihexylsilane, 4-vinylbenzyldiphenylsilane, 4-vinylbenzylphenylmethylsilane and the like.

A method for synthesizing the above hydrosilane will be described. For example, in the case of 4-vinylphenyldimethylsilane, 4-chlorostyrene and magnesium are reacted at room temperature in a tetrahydrofuran solution to obtain 4-vinylphenylmagnesium chloride, and this is reacted with dimethylchlorosilane. Can be synthesized [Macro Molecules, Volume 20, p1505]
(1987)]. Other 4-vinylphenyldialkyl (or aryl) silanes can also be synthesized in a similar manner from the corresponding dialkylchlorosilanes or diarylchlorosilanes and 4-chlorostyrene. Furthermore, 4-vinylbenzyldialkylsilane and 4-vinylbenzyldiarylsilane are also prepared from 4-vinylbenzyl chloride as a starting material.
It can be synthesized by a similar method.

Next, a polymerization method by the hydrosilylation reaction of the above hydrosilane, that is, a method for producing the macromonomer of the present invention will be described. The hydrosilylation reaction in the present invention is preferably carried out in a solvent in the presence of a catalyst, and the catalyst is preferably a transition metal complex soluble in an organic solvent.

Specific examples of the catalyst include chloroplatinic acid, tris (triphenylphosphine) rhodium chloride, bis (triphenylphosphine) carbonylrhodium chloride, pentahaptocyclopentadienylcarbonylnickel, and tris (triphenylphosphine) ruthenium chloride. And bis (triphenylphosphine) palladium chloride and the like, and chloroplatinic acid is preferable from the viewpoint of high activity. The amount of the catalyst used is preferably 0.001 to 0.1 mol of the catalyst, more preferably 0.0 to 1 mol, per 1 mol of the monomer.
It is from 02 mol to 0.06 mol.

Further, the reaction solvent is preferably an organic solvent which is inert to the reaction and dissolves the produced polymer, that is, the macromonomer, for example, benzene, toluene,
There are xylene, chloroform, dichloromethane, tetrahydrofuran, dioxane, acetonitrile and the like, and more preferably toluene. The concentration of the hydrosilane monomer in the reaction solution is preferably 1% by weight or more. The hydrosilylation reaction can be carried out without a solvent, but in that case, it is necessary to remove the heat of reaction to the outside of the system. The preferred reaction temperature in the hydrosilylation reaction is 0 to 140 ° C, more preferably 0 to 90 ° C.
Is. When the reaction temperature exceeds 140 ° C., the rate of side reaction increases, and it is difficult to obtain a high-purity macromonomer. The reaction time varies depending on the temperature and the amount of the catalyst, but is usually 2
20 hours is appropriate.

Further, a vinyl monomer such as styrene may be added in an appropriate amount in order to adjust the molecular weight of the macromonomer to be synthesized. When a vinyl monomer other than the hydrosilane monomer is added to the reaction system, Si-H at the polymerization growth end is added to the vinyl monomer and the hydrosilylation reaction is stopped.

The macromonomer synthesized by the hydrosilylation reaction under the above conditions is obtained as a white precipitate by pouring the reaction solution into a large amount of methanol at room temperature after the completion of the reaction. After separating this precipitate by filtration,
The white powdery macromonomer can be obtained by reprecipitation, purification, and drying under reduced pressure.

[0017]

EXAMPLES The present invention will be described more specifically by showing reference examples and examples. Reference Example 1: Synthesis of 4-vinylphenyldimethylsilane 97 g of 4-vinylphenyl chloride and 24.3 g of metallic magnesium were dried with tetrahydrofuran (hereinafter referred to as THF).
A solution of 62.4 g of dimethylchlorosilane dissolved in 450 ml of THF was added dropwise to a solution of 4-vinylphenylmagnesium chloride obtained by reacting in 1 liter at room temperature over 1 hour. The reaction mixture was stirred for 12 hours under a nitrogen atmosphere, and THF was distilled under reduced pressure. After ether was added to the residue and the insoluble matter was filtered,
The ether was removed from the filtrate by distillation under reduced pressure, and 96 g of a fraction having a boiling point of 58-59 ° C./2 mmHg was obtained as a colorless liquid. The obtained distillate was confirmed to be 4-vinylphenyldimethylsilane by measuring the nuclear magnetic resonance spectrum.

Reference Example 2: Synthesis of 4-vinylbenzyldimethylsilane 4-vinylbenzyl chloride 12 was added to a liquid prepared by dispersing 24.3 g of magnesium metal in 650 ml of dry ether.
A solution prepared by dissolving 2 g in 300 ml of dry ether is
Added at 30 ° C. over 1 hour. Then, while stirring, 3
Over time, the temperature was gradually raised from -30 ° C to 0 ° C. While maintaining the obtained solution at 0 ° C., a solution prepared by dissolving 73.3 ml of dimethylchlorosilane in 400 ml of THF was added to the solution, and the mixture was further stirred at room temperature overnight. The solution was distilled under reduced pressure to remove the solvent until a white precipitate was formed from the resulting reaction solution. Ether was added to the obtained residue and the insoluble matter was filtered off, then the ether was distilled off from the filtrate, followed by vacuum distillation to give a boiling point of 67-68 ° C / 1m.
105 g of mHg fraction was obtained.

By measuring the nuclear magnetic resonance spectrum of the obtained distillate, it was confirmed that it was 4-vinylbenzyldimethylsilane. The nuclear magnetic resonance spectrum (measuring solvent is deuterated chloroform) is as shown in FIG.

[Figure 1]

The resonance signal is as follows. δ (ppm); 0.07 (6H, Me-Si), 2.15
_{(2H, -CH 2 -Si),} 3.97 (1H, Si-
H), 5.16 (1H, CH 2 = CH -), 5.68 (1
_{H, CH 2 = CH -)} , 6.68 (1H, CH 2 = CH
−) 7.00 (2H, benzene ring), 7.29 (2H, benzene ring)

Example 1 A polydimethylsilylene ethylene phenylene type macromonomer was produced by the following procedure. Chloroplatinic acid (13.5 g) was dissolved in 2-propanol (200 ml) to prepare a catalyst solution. Under a nitrogen atmosphere, 100 g of 4-vinylphenyldimethylsilane obtained in Reference Example 1 was dissolved in 1 liter of toluene, 1 ml of the catalyst solution was added, and the resulting solution was stirred at 60 ° C. for 9 hours and then cooled to room temperature. did.
The solution was poured into 35 liters of methanol to obtain a white precipitate. This precipitate was separated, dissolved in THF, and then poured again into a large amount of methanol to reprecipitate.
The obtained precipitate was dried under reduced pressure to obtain 90 g of white powder.

By measuring the nuclear magnetic resonance spectrum and the infrared absorption spectrum of the obtained powder, it was confirmed that the powder was a polydimethylsilyleneethylenephenylene type macromonomer having a styryl group at one end. The nuclear magnetic resonance spectrum (the measurement solvent is deuterated chloroform) is as shown in FIG. 2, and the infrared absorption spectrum is as shown in FIG.

[Fig. 2]

[Figure 3]

The resonance signal of hydrogen nuclear magnetism is as follows. δ (ppm); 0.27 (Me-Si), 1.05-1.18
_{(Si-CH 2 -C),} 2.55-2.68 (C-CH 2 -
φ), 3.42 (Si-H), 5.25 (CH ₂ = CH
_{-), 5.78 (CH 2 =} CH -), 6.71 (CH 2 = C
H-) 7.17 (benzene ring), 7.42 (benzene ring) Further, the polystyrene reduced number average molecular weight measured by gel permeation chromatography is 43.
And the dispersity Mw / Mn was 1.38.

Example 2 Production of polydimethylsilylene ethylenephenylene methylene type macromonomer A solution of 100 g of 4-vinylbenzyldimethylsilane obtained in Reference Example 2 in 1 liter of toluene and 2 ml of a catalyst solution were used under other conditions. Was subjected to a polymerization reaction by hydrosilylation in the same manner as in Example 1 to obtain 92 g of a white powder polymer. The nuclear magnetic resonance spectrum and infrared absorption spectrum of the obtained powder are as shown in FIGS. 4 and 5, respectively, and it was confirmed that the powder was a polydimethylsilyleneethylenephenylenemethylene type macromonomer having a styryl group at one end. The polystyrene-reduced number average molecular weight of this macromonomer was 3100, and the dispersity Mw / Mn was 1.6.
It was 1.

[Figure 4]

[Figure 5]

[0025]

INDUSTRIAL APPLICABILITY According to the present invention, at one end of an organosilicon polymer in which a repeating unit consisting of a silicon-containing monomer unit is linked by a C--Si--C bond, radically polymerizable and ionic polymerizable are added. A novel organosilicon-based macromonomer having a rich styryl group is obtained in high yield, and the macromonomer is different from the conventional silicone-based macromonomer and is an organosilicon polymer containing a C—Si—C bond in the main chain. It has characteristic physical properties based on. The macromonomer of the present invention is extremely useful as a raw material for a graft polymer, and the resulting graft polymer can be used for paints, adhesives, coating materials, resist materials and the like.

[0026]

[Brief description of drawings]

1 is a nuclear magnetic resonance spectrum of hydrosilane synthesized in Reference Example 2, FIGS. 2 and 3 are a nuclear magnetic resonance spectrum and an infrared absorption spectrum of the polymer obtained in Example 1, respectively. 4 and 5 are the nuclear magnetic resonance spectrum and infrared absorption spectrum of the polymer obtained in Example 2, respectively.

Claims (2)

[Claims] 1. A silicon-containing macromonomer represented by the following chemical formula 1 and having a number average molecular weight of 1,000 to 20,000. [Chemical 1] (In the above chemical formula 1, R ₁ and R ₂ have 1 to 10 carbon atoms.
6 alkyl or phenyl groups, which may be the same or different. In addition, n is a positive number and m is 0 or 1. ) 2. The method for producing a silicon-containing macromonomer according to claim 1, wherein the hydrosilane represented by the following chemical formula 2 is polymerized by a hydrosilylation reaction. [Chemical 2] (In the above chemical formula 2, R ₁ and R ₂ have 1 to 1 carbon atoms.
6 alkyl or phenyl groups, which may be the same or different. Further, m is 0 or 1. )