JP4568017B2 - Method for producing silicon-containing polymer and silicon-containing polymer - Google Patents

Description

  The present invention relates to a method for producing a silicon-containing polymer and a silicon-containing polymer.

  A polymer of a monomer containing a silicon atom to which a vinyl group is directly bonded, such as vinyltrialkoxysilane, can introduce a crosslinked structure by utilizing an alkoxysilyl group contained in the polymer. Such a crosslinked structure can strongly restrain the mobility of the main chain of the polymer, so that it is expected that a material having high heat resistance and hardness can be obtained. Therefore, a polymer using a monomer containing a silicon atom to which a vinyl group is directly bonded has been studied conventionally.

  For example, a method of radical bulk polymerization of vinyltrimethoxysilane at a temperature of 150 ° C. using di-t-butyl peroxide as a polymerization initiator is disclosed (Non-patent Document 1). This document reports that a polymer having a number average molecular weight of 4000 was obtained in a yield of 97% or more.

On the other hand, alkoxysilanes having vinyl groups are copolymerized with monofunctional vinyl compounds such as styrene, (meth) acrylic acid, (meth) acrylic acid esters, vinyl acetate, ethylene, and maleic anhydride to produce alkoxysilyl groups. There is also disclosed a method for producing a copolymer having the above (for example, see Patent Documents 1 and 2). Moreover, a method for preparing such a copolymer having an alkoxysilyl group as a stable aqueous dispersion is also disclosed (see Patent Document 2).
Japanese Patent Publication No. 63-60046 JP-A-2-228308 Polymer Papers, Vol. 57, no. 4, pp 198-207 (2000)

  However, conventionally used monomers such as vinyltrialkoxysilane have a very low polymerization reactivity, and only a polymer having a low molecular weight can be obtained. In Non-Patent Document 1, a polymer having a number average molecular weight increased to 4000 can be obtained. However, as a result of investigation by the present inventors, even such a polymer has a tensile strength and a tensile elongation. The mechanical properties were low and the practicality was low.

  In addition, the copolymers described in Patent Documents 1 and 2 can be cured by causing cross-linking between molecules by utilizing the hydrolyzability of alkoxysilyl groups, and paints, coating materials, and adhesives. It is described that it is useful. However, in these copolymers, it is said that the content of alkoxysilyl groups present in the molecule should be suppressed to a small amount. The reason is that when the content of the alkoxysilyl group is increased, the cross-linking density between molecules becomes too high to give a brittle film. These copolymers should be understood as modified polymers modified mainly by vinyl silanes with a vinyl polymer as a main component.

  In view of such a situation, the present invention provides a method for producing a polymer using a monomer containing a silicon atom to which a vinyl group is directly bonded, and is capable of producing a high molecular weight polymer. One of the purposes.

  As a result of investigations to achieve the above object, the present inventors have found that silicon having a higher molecular weight than conventional ones can be obtained by copolymerizing a specific monomer with a monomer containing a silicon atom to which a vinyl group is directly bonded. It has been found that a containing polymer can be obtained. The present invention is based on this new finding.

That is, the method of the present invention for producing a silicon-containing polymer includes a polymerization step of polymerizing a plurality of types of monomers including the monomer (A) and the monomer (B), The body (A) is at least one compound represented by the following formula (1), and the monomer (B) is at least one compound represented by the following formula (2). The ratio of the monomer (A) in the total monomer is in the range of 70 to 99.5 mol%, and the ratio of the monomer (B) in the total monomer is 0.5 to It is in the range of 30 mol%.

[Wherein R ¹ is a hydrogen atom . R ² , R ³ and R ⁴ are alkoxy groups. ]
[Wherein, R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group. R ⁷ and R ⁸ are alkoxy groups. ]

  Moreover, this invention contains the silicon containing polymer manufactured with the manufacturing method of the said invention.

The present invention particularly relates to a silicon-containing polymer comprising a structural unit (A) derived from the monomer (A) and a structural unit (B) derived from the monomer (B), wherein the monomer (A) is at least one compound represented by the above formula (1), the monomer (B) is at least one compound represented by the above formula (2), and has a total structure. The proportion of the structural unit (A) in the unit is in the range of 70 to 99.5 mol%, the proportion of the structural unit (B) in the total structural unit is in the range of 0.5 to 30 mol%, Includes those having a number average molecular weight of 10,000 or more.

  According to the present invention, a high molecular weight silicon-containing polymer can be easily obtained. The silicon-containing polymer and the composition containing the same can be applied to various fields, for example, paints, inks, adhesives, and pressure-sensitive adhesives.

  Embodiments of the present invention will be described below. In addition, although a specific compound may be illustrated in the following description, this invention is not limited to this. Moreover, as long as there is no description in particular, the illustrated material may be used independently and may be used in combination of 2 or more type.

(Method for producing silicon-containing polymer)
Hereinafter, the production method of the present invention will be described. The present invention includes a silicon-containing polymer produced by the production method of the present invention.

  The production method of the present invention includes a polymerization step of polymerizing a plurality of types of monomers including the monomer (A) and the monomer (B). The monomer (A) is at least one compound represented by the following formula (1), and the monomer (B) is at least one kind containing two or more carbon-carbon double bonds. A compound. The two carbon-carbon double bonds are preferably not conjugated.

[Wherein R ¹ represents a hydrogen atom or an alkyl group. R ² , R ³ and R ⁴ are each independently one atomic group selected from a halogen atom, an alkyl group, an alkoxy group and a hydroxyl group, and at least one selected from R ² , R ³ and R ⁴ is a halogen atom , An alkoxy group or a hydroxyl group. ]

Examples of the alkyl group applicable to R ¹ , R ² , R ³ and R ⁴ include alkyl groups such as a methyl group, an ethyl group and a propyl group. Examples of the halogen atom applicable to R ² , R ³ and R ⁴ include chlorine and bromine. Examples of the alkoxy group applicable to R ² , R ³ and R ⁴ include alkyloxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group; alkoxyalkyleneoxy groups such as 2-methoxyethoxy group; benzyloxy group And aralkyloxy groups such as In a typical example of R ^{2 to} R ⁴ , R ² , R ³ and R ⁴ are each independently a halogen atom or an alkoxy group.

At least one selected from R ² , R ³ and R ⁴ is preferably a halogen atom or an alkoxy group. In monomer (A-1) which is a preferred example of monomer (A), R ¹ is a hydrogen atom, and R ^{2 to} R ⁴ are halogen atoms. In monomer (A-2) which is another preferred example of monomer (A), R ¹ is a hydrogen atom, and R ^{2 to} R ⁴ are alkoxy groups. In monomer (A-3), which is another preferred example of monomer (A), R ¹ is a hydrogen atom, R ^{2 to} R ⁴ are either an alkoxy group or a halogen atom, and at least 1 One is an alkoxy group and at least one is a halogen atom. Specific examples of the monomer (A) include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltributoxysilane, vinyldimethoxymethylsilane, vinyldiethoxymethylsilane, vinyldiethoxyethylsilane. Vinylethoxydimethylsilane, vinylethoxydiethylsilane, vinyltris (2-methoxyethoxy) silane, and vinyltrichlorosilane.

  Examples of the monomer (B) include triallyl isocyanurate, triallyl trimellitate, diallyl chlorendate, divinyl adipate, divinyl succinate, divinyl ether, divinyl sulfone, divinyl phthalate, diallyl phthalate, and divinyl. Benzene or the compounds described below can be mentioned.

The monomer (B) is a group represented by (CR ⁵ ═CH ₂ ) (where R ⁵ is a hydrogen atom or an alkyl group) and a group represented by (CR ⁶ ═CH ₂ ) (where R ^{6 is} R ^6). Is preferably a hydrogen atom or an alkyl group) and is preferably at least one compound containing a silicon atom to which is bonded. Since such a compound contains two carbon-carbon double bonds, a polymer having a crosslinked structure introduced into the main chain can be obtained by using the compound. When a compound containing a silicon atom is used as the monomer (B), the structural units (A) and (B) both contain a silicon atom, so that mechanical properties expected for a silicon-containing polymer, such as tensile strength, are obtained. A polymer with better mechanical properties such as tensile elongation and flexibility can be obtained. In particular, by using a monomer in which a group represented by (CR═CH ₂ ) (where R is a hydrogen atom or an alkyl group) is directly bonded to a silicon atom, the resulting silicon-containing polymer is When a crosslinked structure is introduced using the silicon atom, the effect of improving the mechanical properties is obtained by strongly restraining the main chain of the polymer.

  Moreover, it is preferable that a monomer (B) is at least 1 type of compound represented by the following formula | equation (2).

[Wherein, R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group. R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or a group represented by (CR ⁹ ═CH ₂ ) (where R ⁹ is a hydrogen atom or an alkyl group). One selected atomic group. ]

At least one selected from R ⁷ and R ⁸ is preferably a halogen atom, an alkoxy group, a hydroxyl group, or a group represented by (CR ⁹ ═CH ₂ ), and particularly preferably a halogen atom or an alkoxy group. preferable.

Examples of the alkyl group applicable to R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ include a methyl group, an ethyl group and a propyl group. Examples of the halogen atom applicable to R ⁷ and R ⁸ include chlorine and bromine. Examples of the alkoxy group applicable to R ⁷ and R ⁸ include alkyloxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group; alkoxyalkyleneoxy groups such as 2-methoxyethoxy group; aralkyl such as benzyloxy group An oxy group is mentioned.

Examples of the monomer (B) represented by the formula (2) will be described below. In the first monomer (B-1), at least one of R ⁷ and R ⁸ is an alkoxy group, and preferably R ⁷ and R ⁸ are both alkoxy groups. In the second monomer (B-2), at least one of R ⁷ and R ⁸ is a halogen atom, and preferably R ⁷ and R ⁸ are both halogen atoms. In the third monomer (B-3), R ⁷ is a vinyl group, and R ⁸ is an alkoxy group, a halogen atom, or an alkyl group. In the monomers (B-1) to (B-3), R ⁵ and R ⁶ may be a hydrogen atom or an alkyl group.

  Specific examples of the compound represented by the formula (2) include, for example, diethoxydivinylsilane, dimethoxydivinylsilane, methoxymethyldivinylsilane, dichlorodivinylsilane, methyltrivinylsilane, chlorotrivinylsilane, methoxytrivinylsilane, ethoxytrivinylsilane. Is mentioned.

  The monomer (A) described above and the monomer (B) described above can be arbitrarily combined. For example, the monomer (A-1) and the monomer (B-1), (B-2), or (B-3) may be combined. Moreover, you may combine a monomer (A-2) and a monomer (B-1), (B-2), or (B-3). Moreover, you may combine a monomer (A-3) and a monomer (B-1), (B-2), or (B-3). An example of such a combination is shown in the examples.

  In addition, the monomer (A) and the monomer (B) may use what is marketed, and may synthesize | combine by a well-known method.

  The polymerization step can be performed according to a known polymerization method such as anionic polymerization, cationic polymerization, or radical polymerization, but is preferably performed by radical polymerization. When carried out by radical polymerization, the polymerization step is preferably carried out at a temperature of 80 ° C. or higher in the presence of a polymerization initiator. The polymerization initiator to be used is not particularly limited, but the activation energy for the decomposition of the polymerization initiator is preferably 30 kcal / mol or more. The activation energy is more preferably 35 kcal / mol or more. Specific examples of the polymerization initiator having an activation energy of 30 kcal / mol or more include cumene hydroperoxide, t-butyl hydroperoxide, sec-butyl peroxide, dicumyl peroxide, di-t-butyl peroxide. , T-amyl peroxide, t-butyl-α-cumyl peroxide, 1,4-dimethylhydroperoxide, t-butyl perbenzoate, 2,2′-azobis (2-methylpropane), 1,1′- And azobis (cyclohexane-1-carbonitrile). In particular, the polymerization step is performed at a temperature of 80 ° C. or higher in the presence of a polymerization initiator, and the polymerization initiator is cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide. It is preferably at least one selected from oxide, t-butyl perbenzoate, and 1,1′-azobis (cyclohexane-1-carbonitrile). These polymerization initiators have a decomposition activation energy of 35 kcal / mol or more.

  The amount of the polymerization initiator used is preferably in the range of 0.01 to 0.5 mol, more preferably 0.02 to 0.2 mol, per mol of all the monomers (plural types of monomers). More preferably, it is the range of 0.03-0.1 mol. When the usage-amount of a polymerization initiator exists in a preferable range, a higher molecular weight silicon-containing polymer is easy to be obtained.

  The preferred proportion of monomer (A) and monomer (B) in the total monomer (plural monomers) is the type of monomer (A) and monomer (B) and the silicon-containing weight. Since it changes depending on the intended use of the merger, it cannot be specified unconditionally. In a typical example, the ratio of the monomer (A) in the total monomer (a plurality of monomers) is in the range of 70 to 99.5 mol%, and the monomer ( The proportion of B) is in the range of 0.5 to 30 mol%. The molar ratio of monomer (A) / monomer (B) is preferably in the range of 70/30 to 99.5 / 0.5, more preferably in the range of 85/15 to 97/3. More preferably, it is in the range of 85/15 to 95/5. In the production method of the present invention, typically, only monomer (A) and monomer (B), or substantially only monomer (A) and monomer (B) are polymerized. As long as the effect of the present invention is obtained, another monomer different from the monomer (A) and the monomer (B) may be polymerized. As the other monomer, a vinyl compound having only one vinyl group contained therein (hereinafter sometimes referred to as a vinyl compound (C)) can be used. For example, a vinyl ester such as vinyl acetate, Examples thereof include vinyl compounds having a nitrogen-containing heterocyclic ring (for example, vinyl compounds having a pyrrolidone partial structure such as N-vinylpyrrolidone and vinyl compounds having an imidazole partial structure such as N-vinylimidazole). Among these, the vinyl compound (C) having a nitrogen-containing heterocyclic ring is preferable from the viewpoint of polymerizability with the monomer (A) and the monomer (B). The proportion of other monomers (for example, vinyl compound (C)) in the total monomers (plural types of monomers) is preferably 60 mol% or less, more preferably 50 mol% or less.

  In the production method of the present invention, the polymerization step may be performed by bulk polymerization without using a solvent, or the polymerization step may be performed in the presence of a solvent. When carrying out the polymerization step in the presence of a solvent, it is preferable to use an organic solvent as the solvent. As the organic solvent, for example, dioxane, chlorobenzene, methyl benzoate, toluene, xylene, mesitylene, decalin, ethylene glycol dimethyl ether, and acetonitrile can be used.

  When the polymerization step is carried out in the presence of a solvent, a polymerizable mixture containing the monomer (A), the monomer (B) and an organic solvent is prepared. During the polymerization step, the mixture is preferably bubbled with an inert gas. Moreover, it is preferable to perform a superposition | polymerization process in inert gas atmosphere. For example, nitrogen gas or argon gas can be used as the inert gas. The temperature of the mixture in the polymerization step is preferably adjusted to 80 ° C. or higher, and more preferably adjusted to 100 ° C. or higher (for example, 120 ° C. or higher). The temperature of the mixture is preferably adjusted to 50 ° C. or less of the boiling point of the monomer (A), and more preferably adjusted to 40 ° C. or less (eg, 30 ° C. or less) of the boiling point of the monomer (A). .

  The polymerization initiator may be mixed in advance with the monomer (A) or the monomer (B), or may be added to the above-described polymerizable mixture. The total amount of the polymerization initiator may be added at once, or may be added in several divided portions. Although there is no particular limitation on the timing of adding the polymerization initiator, it is preferable to add the polymerization initiator after starting bubbling with an inert gas. The polymerization initiator may be added after adjusting the mixture to the polymerization temperature, or may be added before adjusting the mixture to the polymerization temperature. In particular, when using a polymerization initiator having an activation energy of 30 kcal / mol or less, it is preferable to add the polymerization initiator after adjusting the mixture to the polymerization temperature.

  In the production method of the present invention, the monomer (A) and the monomer (B) are copolymerized, and the molecular weight of the resulting silicon-containing polymer is dramatically increased by the presence of the monomer (B). Can be big. According to the production method of the present invention, a silicon-containing polymer having a number average molecular weight of 10,000 or more, more preferably 12,000 or more, and further preferably 15,000 or more can be produced. In addition, by using a monomer containing a silicon atom as the monomer (B), a polymer having high characteristics (for example, heat resistance and hardness) expected for a silicon-containing polymer can be obtained.

  The production method of the present invention may further include a step of removing a component dissolved in the hydrocarbon solvent from the polymer obtained by the polymerization step. According to this step, since the low molecular weight component dissolved in the hydrocarbon solvent can be removed, a polymer having a higher number average molecular weight, for example, a polymer having a number average molecular weight of 15000 or more can be obtained. The low molecular weight component can be removed, for example, by immersing the polymer in a hydrocarbon solvent and then performing filtration. A high molecular weight silicon-containing polymer is usually not soluble in a hydrocarbon solvent and can be easily separated by filtration. Polymers with higher number average molecular weights thus obtained are usually polar organic solvents (eg tetrahydrofuran; amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; alcohols such as methanol, ethanol, propanol, ethylene glycol). A polymer that dissolves in chloroform, dimethyl sulfoxide, acetone, sulfolane, etc.) and is not produced by gelation (hydrolytic condensation reaction between polymers).

  The hydrocarbon solvent is a solvent composed of hydrocarbon, and for example, at least one selected from n-hexane, cyclohexane, n-heptane, toluene, benzene and xylene can be used. Among these, n-hexane is preferable. The amount of the hydrocarbon solvent to be used is not particularly limited, but it is preferably 5 to 100 times the weight of the silicon-containing polymer, more preferably 10 to 50 times the weight. The temperature of the hydrocarbon solvent to be used is not particularly limited, but when the boiling point of the hydrocarbon solvent is T ° C., the temperature is preferably in the range of 20 ° C. to T ° C., and 20 ° C. to (T-20) ° C. A range is more preferable. The time for immersing the silicon-containing polymer in the hydrocarbon-based solvent is not particularly limited, but it is preferably immersed for 30 minutes or more, and more preferably for 60 minutes or more. The immersion of the silicon-containing polymer in the hydrocarbon solvent is preferably performed with stirring or shaking.

(Silicon-containing polymer)
Next, the silicon-containing polymer of the present invention will be described. This silicon-containing polymer can be produced by the production method of the present invention described above. The silicon-containing polymer of the present invention is a copolymer containing a structural unit (A) derived from the monomer (A) and a structural unit (B) derived from the monomer (B).

  Since the compounds applicable to the monomer (A) and the monomer (B) have been described above, the description thereof will be omitted.

  The preferred proportion of the structural unit (A) and the structural unit (B) in the total structural units varies depending on the types of the monomer (A) and monomer (B) as materials and the purpose of use of the polymer. Therefore, it cannot be specified in general. In a typical example, the proportion of the structural unit (A) in the total structural unit is in the range of 70 to 99.5 mol%, and the proportion of the structural unit (B) in the total structural unit is 0.5 to 30 mol. % Is preferable. The molar ratio of structural unit (A) / structural unit (B) is in the range of 70/30 to 99.5 / 0.5. By setting the molar ratio of structural unit (A) / structural unit (B) within this range, gelation during polymerization can be prevented and a high molecular weight polymer can be obtained. Moreover, this molar ratio becomes like this. Preferably it is the range of 85 / 15-97 / 3, More preferably, it is the range of 85 / 15-95 / 5. The silicon-containing polymer of the present invention typically comprises only the structural unit (A) and the structural unit (B), or substantially consists of only the structural unit (A) and the structural unit (B). Other structural units may be included as long as the effect is obtained. Examples of other structural units include structural units derived from a vinyl compound (vinyl compound (C)) containing only one vinyl group, such as vinyl esters such as vinyl acetate, nitrogen Exemplified structural units derived from vinyl compounds such as vinyl compounds having a heterocyclic ring (for example, vinyl compounds having a pyrrolidone partial structure such as N-vinylpyrrolidone and vinyl compounds having an imidazole partial structure such as N-vinylimidazole) it can. The proportion of other structural units (for example, structural units derived from the vinyl compound (C)) in the total structural units is preferably 60 mol% or less, more preferably 50 mol% or less.

  The silicon-containing polymer of the present invention has a number average molecular weight of 10,000 or more, preferably 12000 or more, more preferably 15000 or more. When the number average molecular weight is 10,000 or more, mechanical properties such as tensile strength, tensile elongation, and flexibility are particularly good. A silicon-containing polymer having a number average molecular weight of 10,000 or more has been made possible for the first time by adopting the production method described above. The upper limit of the number average molecular weight is not particularly limited, but is preferably within a range that dissolves in the above-described polar organic solvent. The number average molecular weight and the weight average molecular weight referred to in the present specification are values in terms of polystyrene measured by GPC (Gel Permeation Chromatography) as described in Examples.

  In the silicon-containing polymer of the present invention, the molecular weight distribution, that is, the value represented by the ratio “Mw / Mn” between the weight average molecular weight Mw and the number average molecular weight Mn is preferably 2 to 15, more preferably 3 to 3. It is the range of 12, More preferably, it is the range of 4-12. When the molecular weight distribution is in a preferred range, the mechanical properties such as tensile strength and flexibility of the silicon-containing polymer are good.

  The silicon-containing polymer of the present invention may be used alone, or may be mixed with other polymers to form a composition. Examples of other polymers include polyamide, polyurethane, polyester, polycarbonate, polyoxymethylene resin, acrylic resin, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, polyolefin, polystyrene, and styrene. Examples include block copolymers and silicone resins. When used as a composition, stabilizers, lubricants, pigments, impact resistance improvers, processing aids, crystal nucleating agents, reinforcing agents, colorants, flame retardants, weather resistance improvers, UV absorbers, antioxidants, Various additives such as hydrolysis resistance improvers, fungicides, antibacterial agents, light stabilizers, anti-static agents, silicone oil, anti-blocking agents, mold release agents, foaming agents, fragrances; glass fibers, polyester fibers, carbon Components such as various fibers such as fibers; fillers such as talc and wood powder; various coupling agents may be blended as necessary.

  The silicon-containing polymer of the present invention or a composition using the same can be molded by a known method. Examples of the molding method include (1) a method in which a polymer or composition is dissolved in an organic solvent to form a solution, and this solution is molded by a casting method or a coating method, and (2) the polymer or composition is melted. A method of forming by an injection method or an extrusion method can be applied.

  In the silicon-containing polymer of the present invention or a composition using the same, the reaction between functional groups (for example, alkoxysilyl groups) of the silicon-containing polymer after molding or after molding, or other than the functional group and the silicon-containing polymer A reaction with a functional group (for example, a hydroxyl group) of the component may be caused. By such a reaction, a material excellent in tensile strength, bending strength, heat resistance and the like can be obtained. The reaction between the alkoxysilyl groups of the silicon-containing polymer and the reaction between the alkoxysilyl group of the silicon-containing polymer and other functional groups may occur after the alkoxysilyl group is once hydrolyzed and converted to a silanol group. .

  The silicon-containing polymer of the present invention can be used for various applications such as paints, inks, adhesives, pressure-sensitive adhesives, compatibilizing agents, and sealing materials. Moreover, it can also shape | mold into a fiber form and can also be set as fiber structures, such as a fabric. Furthermore, it can be used for various applications as a laminate with other materials such as various thermoplastic resins or compositions thereof, thermosetting resins, paper, fabric, metal, wood, ceramics.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. As the silane compound used in the following examples, those manufactured by Shin-Etsu Chemical Co., Ltd. were used. Measurements in the following examples were carried out by the following methods.
(1) Measurement of number average molecular weight and weight average molecular weight A silicon-containing polymer was dissolved in tetrahydrofuran so that the concentration was 0.5% by weight, and used as a sample for GPC (Gel Permeation Chromatography) measurement. The measurement of GPC was performed using Shimadzu Corporation Chromatopack CR-4A (main body), RID-6A (refractive index detector), and CIO-6A (column oven). As the column, HSG-4OH (Shimadzu Corporation) was used. Tetrahydrofuran was used as the eluent, and the eluent was allowed to flow at a flow rate of 1.0 mL / min. The column oven was set to 40 ° C. A calibration curve for determining the molecular weight was prepared using polystyrene standard (polystyrene standard sample manufactured by Chemco Co., Ltd.). That is, polystyrene having a known molecular weight was dissolved in tetrahydrofuran so as to have a concentration of 0.5% by weight, GPC measurement was performed, and a calibration curve showing the relationship between elution time and molecular weight was prepared. The number average molecular weight and weight average molecular weight of the silicon-containing polymer were determined from the GPC elution curve (elution time-elution amount) of the silicon-containing polymer and the calibration curve. Further, the molecular weight distribution, that is, the value of “weight average molecular weight / number average molecular weight” was calculated.

<Example 1>
1740 mmol of trimethoxyvinylsilane (monomer (A)) and 260 mmol of diethoxydivinylsilane (monomer (B)) were added to a flask equipped with a reflux tube under a nitrogen atmosphere. The mixture of monomer (A) and monomer (B) was bubbled with nitrogen gas. This bubbling was continued until the polymerization reaction was stopped. 30 minutes after the start of bubbling, the flask was immersed in an oil bath adjusted to 130 ° C., and 100 mmol of dicumyl peroxide (polymerization initiator) was immediately added to the mixture to initiate polymerization. Five minutes after immersing the flask in an oil bath, the temperature of the mixture reached 130 ° C. The polymerization reaction was continued for 5 hours after adding the polymerization initiator while stirring the mixture and in an oil bath. Thereafter, the flask was taken out from the oil bath, and the temperature in the flask was lowered to room temperature. It was confirmed by gas chromatography that neither the monomer (A) nor the monomer (B) remained in the reaction product in the flask. A part of the obtained polymer was dissolved in tetrahydrofuran, and the molecular weight was measured by GPC. As a result, the obtained polymer had a number average molecular weight of 12500, a weight average molecular weight of 113,000, and a molecular weight distribution of 9.0.

A part of the obtained polymer was dissolved in deuterated chloroform containing tetramethylsilane as an internal standard, and the structure was analyzed by ¹ H-NMR. As a result, a peak corresponding to the methine proton bonded to the silicon atom was confirmed at 0.7 ppm, a peak corresponding to the methylene proton in the main chain was observed at 1.2 ppm, and a peak corresponding to the methyl group in the ethoxysilyl group was observed. A peak corresponding to the methyl proton in the methoxysilyl group and the methylene proton in the ethoxysilyl group was observed at 3.6 ppm. From the integrated value of each peak, the molar ratio between the structural unit (A) derived from the monomer (A) and the structural unit (B) derived from the monomer (B), [structural unit (A) / structure The unit (B)] value was calculated to be approximately 9/1.

<Example 2>
1940 mmol of trimethoxyvinylsilane (monomer (A)) and 60 mmol of diethoxydivinylsilane (monomer (B)) were added to a flask equipped with a reflux tube under a nitrogen atmosphere. The mixture of monomer (A) and monomer (B) was bubbled with nitrogen gas. This bubbling was continued until the polymerization reaction was stopped. 30 minutes after the start of bubbling, the flask was immersed in an oil bath adjusted to 130 ° C., and 100 mmol of dicumyl peroxide (polymerization initiator) was immediately added to the mixture to initiate polymerization. Five minutes after immersing the flask in the oil bath, the temperature of the mixture reached 130 ° C. The polymerization reaction was continued in the oil bath while stirring the mixture for 5 hours after the addition of the polymerization initiator. Thereafter, the flask was taken out from the oil bath, and the temperature in the flask was lowered to room temperature. It was confirmed by gas chromatography that neither monomer (A) nor monomer (B) remained in the reaction product in the flask.

  Next, the entire amount of the obtained polymer was put into 1000 ml of n-hexane and stirred for 60 minutes. After 60 minutes, the polymer that did not dissolve in n-hexane was collected by filtration. The recovered polymer was dried at room temperature under reduced pressure. The weight of the recovered polymer after drying was 15% of the total weight of the monomer (A) and the monomer (B). A part of the polymer thus obtained was dissolved in tetrahydrofuran, and the molecular weight was measured by GPC. As a result, the obtained polymer had a number average molecular weight of 15500, a weight average molecular weight of 60000, and a molecular weight distribution of 3.9.

<Comparative Example 1>
2000 mmol of trimethoxyvinylsilane (monomer (A)) was added to a flask equipped with a reflux tube under a nitrogen atmosphere. The monomer (A) was bubbled with nitrogen gas. This bubbling was continued until the polymerization reaction was stopped. 30 minutes after the start of bubbling, the flask was immersed in an oil bath adjusted to 130 ° C., and 100 mmol of dicumyl peroxide (polymerization initiator) was immediately added to initiate polymerization. Five minutes after immersing the flask in the oil bath, the temperature of the mixture reached 130 ° C. The polymerization reaction was continued in the oil bath while stirring the mixture for 5 hours after the addition of the polymerization initiator. Thereafter, the flask was taken out from the oil bath, and the temperature in the flask was lowered to room temperature. It was confirmed by gas chromatography that no monomer (A) remained in the reaction product in the flask. A part of the polymer thus obtained was dissolved in tetrahydrofuran, and the molecular weight was measured by GPC. As a result, the obtained polymer had a number average molecular weight of 3200, a weight average molecular weight of 6100, and a molecular weight distribution of 1.9.

  According to the present invention, a silicon-containing polymer having a number average molecular weight larger than that of the conventional one can be obtained. The polymer and the composition containing the polymer can be applied to various fields, typically, for example, paints, inks, adhesives, and pressure-sensitive adhesives.

Claims (7)

Including a polymerization step of polymerizing a plurality of types of monomers including the monomer (A) and the monomer (B),
The monomer (A) is at least one compound represented by the following formula (1):
The monomer (B) is Ri least one compound der represented by the following formula (2),
The proportion of the monomer (A) in the total monomer is in the range of 70-99.5 mol%,
The manufacturing method of the silicon-containing polymer whose ratio of the said monomer (B) to all the monomers is the range of 0.5-30 mol% .
[Wherein R ¹ is a hydrogen atom . R ² , R ³ and R ⁴ are alkoxy groups. ]
[Wherein, R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group. R ⁷ and R ⁸ are alkoxy groups. ] The polymerization step is performed at a temperature of 80 ° C. or higher in the presence of a polymerization initiator;
The polymerization initiator is cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, t-butyl perbenzoate, and 1,1′-azobis (cyclohexane-1-carbohydrate). The method for producing a silicon-containing polymer according to claim 1, wherein the method is at least one selected from nitrile). The plural types of monomers include a vinyl compound (C) different from the monomer (A) and the monomer (B),
Method for producing a silicon-containing polymer according to claim 1 or 2 vinyl group Ru 1 Tsudea contained in the vinyl compound (C). The method for producing a silicon-containing polymer according to claim 3, wherein the vinyl compound (C) has a nitrogen-containing heterocyclic ring. 5. The method according to claim 1 , further comprising a step of removing a component dissolved in at least one selected from n-hexane, cyclohexane, n-heptane, toluene, benzene and xylene from the polymer obtained by the polymerization step. A method for producing a silicon-containing polymer according to claim 1 . The silicon-containing polymer manufactured with the manufacturing method of any one of Claims 1-5 . A silicon-containing polymer comprising a structural unit (A) derived from the monomer (A) and a structural unit (B) derived from the monomer (B),
The monomer (A) is at least one compound represented by the following formula (1):
The monomer (B) is at least one compound represented by the following formula (2) :
The proportion of the structural unit (A) in all structural units is in the range of 70 to 99.5 mol%,
The proportion of the structural unit (B) in the total structural units is in the range of 0.5 to 30 mol%,
A silicon-containing polymer having a number average molecular weight of 10,000 or more.
[Wherein R ¹ is a hydrogen atom . R ² , R ³ and R ⁴ are alkoxy groups. ]
[Wherein, R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group. R ⁷ and R ⁸ are alkoxy groups. ]