WO2020116294A1

WO2020116294A1 - ONE TERMINAL METHACRYLIC-MODIFIED ORGANO(POLY)SILOXANE HAVING POLY(ALKYLENE OXIDE) AT ω-TERMINAL, AND METHOD FOR PRODUCING SAME

Info

Publication number: WO2020116294A1
Application number: PCT/JP2019/046469
Authority: WO
Inventors: 守萩原
Original assignee: 信越化学工業株式会社
Priority date: 2018-12-04
Filing date: 2019-11-27
Publication date: 2020-06-11
Also published as: JP2020090580A; TW202031741A

Abstract

[Problem] To provide: a novel one terminal methacrylic-modified organo(poly)siloxane which has a poly(alkylene oxide) at an ω-terminal and which is useful as a synthesis intermediate for a silicone graft polymer having excellent surface characteristics; and a method for producing same. [Solution] A one terminal-reactive organo(poly)siloxane comprising blocks arranged in the following order: A-B¹-C-B²-D-Y (In the formula, A is a monovalent (poly)alkylene oxide group having an alkoxy group at a terminal, B¹ is a substituted or unsubstituted alkylene group, B² is a substituted or unsubstituted alkylene group or alkylene oxide group, C is a divalent (poly)siloxy group, D is a divalent (poly)alkylene oxide group, and Y is a methacrylic group).

Description

One-terminal methacryl-modified organo(poly)siloxane having a polyalkylene oxide group at the ω end and a method for producing the same.

The present invention relates to a methacryl-modified organo(poly)siloxane modified at one end with a hydrophilic polyalkylene oxide at the ω end and a method for producing the same.

It has been conventionally known to synthesize an organopolysiloxane having a (meth)acrylic group at one end by ring-opening polymerization of hexamethylcyclotrisiloxane. For example, in JP-A-59-78236 (Patent Document 1), hexamethylcyclotrisiloxane is subjected to ring-opening polymerization using lithium trimethylsilanolate as a polymerization initiator to give 3-(2-methacryloxyethoxy)propyl. A method of synthesizing an organopolysiloxane having a (meth)acryl group at one end by stopping the reaction with dimethylchlorosilane has been proposed.

Further, in JP-A-7-224168 (Patent Document 2), trimethylsilanol or 3-methacryloxypropyldimethylsilanol is used as an initiator, and hexamethylcyclotrisiloxane is ring-opened in the presence of a pentacoordinated silicon catalyst. A method is known in which an organopolysiloxane having a (meth)acryl group at one end is synthesized by polymerizing and then terminating the reaction with 3-methacryloxypropyldimethylchlorosilane or trimethylchlorosilane, respectively.

However, these one-end reactive organopolysiloxanes are all siloxane polymers composed of only hydrophobic segments.

JP-A-2001-55446 (Patent Document 3) and JP-A-2008-202060 (Patent Document 4) report a single-end reactive polysiloxane containing a hydrophilic group. However, in these one-end reactive polysiloxanes, the hydrophilic group is located between the reactive group block and the polysiloxane block, so when used in paints, etc., the hydrophilic group is covered by the siloxane segment and the coating film There is a problem that it is difficult to obtain the characteristics of microphase separation on the surface.

Japanese Patent No. 5046404 (Patent Document 5) reports a single-end reactive organopolysiloxane having a polyalkylene oxide group at the ω end. Among them, the one-end reactive organopolysiloxane having a (meth)acrylic group, a (meth)acrylamide group, and a styryl group at the α-terminal can be copolymerized with a vinyl-based monomer, resulting in water repellency, releasability, and slipperiness. It can be used as a surface treatment agent having excellent weather resistance and gas permeability.

JP-A-59-78236 JP, 7-224168, A Japanese Patent Laid-Open No. 2001-55446 JP, 2008-202060, A Japanese Patent No. 5046404

The one-terminal methacryl-modified polysiloxane described in Patent Document 5 was devised to solve the above-mentioned problems in Patent Documents 3 and 4, but the characteristics of the coating film surface and other coating compositions The compatibility with the product is insufficient. Further, in the production method described in Patent Document 5, a large amount of impurities are generated during the terminal methacryl group-forming reaction, and since the impurities cannot be removed, the purity is lowered and a coating film having good surface characteristics cannot be obtained. there were.

In order to solve the above problems, the present inventors have an object to obtain a methacryl-modified polysiloxane modified at one end with a hydrophilic group at the ω terminal, a small amount of impurities, and high compatibility with a hydrophilic monomer. To do.

As a result of earnest studies, the present inventor produced an α-terminal silanol-modified organopolysiloxane by the production method described in Patent Document 5, and reacted the compound obtained by reacting the organopolysiloxane with diorganochlorosilane with allyloxy. It was found that a one-terminal methacryl-modified organopolysiloxane having a polyalkylene oxide at the ω terminal can be obtained with high purity by reacting with polyalkyleneoxymethacrylate. Furthermore, they have found that a methacryl-modified organopolysiloxane having one terminal methacryl having a polyalkylene oxide between a polysiloxane group and a methacrylic group exhibits high compatibility with a hydrophilic acrylic monomer, and thus completed the present invention.

That is, the present invention provides a methacryl-modified organo(poly)siloxane modified at one end with a block arranged in the following order, and a method for producing the organo(poly)siloxane.

AB ¹ -CB ² -DY

(In the formula, A is a (poly)alkylene oxide group having an alkoxy group at the terminal, B ¹ is a substituted or unsubstituted alkylene group, and B ² is a substituted or unsubstituted alkylene group or alkylene oxide group. , C is a divalent (poly)siloxy group, D is a divalent (poly)alkylene oxide group, and Y is a methacryl group).

The one-terminal methacryl-modified organo(poly)siloxane of the present invention has a polyalkylene oxide (D) between the polysiloxane (C) and the methacryl group (Y), and therefore, when a silicone graft polymer is formed, other Good compatibility with hydrophilic monomers. Furthermore, according to the production method of the present invention, it is possible to provide a highly-purified methacryl-modified organo(poly)siloxane modified at one end, and the methacryl-modified organo(poly)siloxane modified at one end can provide a coating film having good surface characteristics. it can.

FIG. 1 is a ¹ H-NMR spectrum of the compound produced in Example 1.

The present invention is an organo(poly)siloxane composed of blocks arranged in the following order, which is a methacryl-modified organo(poly)siloxane modified at one end with a polyalkylene oxide at the ω end.

AB ¹ -CB ² -DY

(In the formula, A is a polyalkylene oxide group having an alkoxy group at the terminal, B ¹ is a substituted or unsubstituted alkylene group, B ² is a substituted or unsubstituted alkylene group or alkylene oxide group, and C is Is a divalent polysiloxy group, D is a divalent polyalkylene oxide group, and Y is a methacryl group).

As a preferred organo(poly)siloxane composed of the above block, an organo(poly)siloxane represented by the following formula (1) can be mentioned.

In the formula (1), R ¹ is an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group. .. R ² is H or a methyl group. R ^3's each independently represent an alkylene group having 2 to 10 carbon atoms, preferably an alkylene group having 2 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and further preferably a propylene group. Is. R ⁴ is, independently of each other, an alkyl group, an alkenyl group or an aryl group having 1 to 10 carbon atoms, preferably an alkyl group or an alkenyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, More preferably, it is an alkyl group or alkenyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 8 carbon atoms, and even more preferably a methyl group. m ₁ is an integer of 1 to 100, preferably 1 to 50, more preferably 1 to 10, m ₂ is an integer of 1 to 100, preferably 1 to 50, more preferably 1 to 10, and n is It is an integer of 1 to 100, preferably 1 to 50, more preferably 1 to 10. Further, in the formula (1), Y is a methacrylic group shown below. A compound in which Y is an acrylic group is not preferable because a side reaction may be generated.

Further, the present invention provides a method suitable for producing the above-mentioned one-end-reactive organo(poly)siloxane. That is, a method for producing a methacryl-modified organo(poly)siloxane having one terminal methacryl, which comprises blocks arranged in the following order,
AB ¹ -CB ² -DY
A step of reacting a hydrosilyl group of the compound represented by the following formula (a) with a vinyl group of the compound represented by the following formula (b) to obtain the above-mentioned one-terminal-methacryl-modified organo(poly)siloxane. The above-mentioned manufacturing method is characterized.

AB ¹ -CH (a)

_{^{CH 2 = CH-B 2 '}} -D-Y (b)

(In the formula, A is a polyalkylene oxide group having an alkoxy group at the terminal, B ¹ is a substituted or unsubstituted alkylene group, B ² is a substituted or unsubstituted alkylene group or alkylene oxide group, and B 1 ^2′ is a residue of a group represented by B ² , C is a divalent polysiloxy group, D is a divalent polyalkylene oxide group, and Y is a methacryl group).
A known method can be used for the addition reaction of the hydrosilyl group and the vinyl group, and there is no particular limitation. For example, it is carried out in the presence of an addition reaction catalyst such as a platinum group compound. At that time, a solvent may be used. Details of the addition reaction are as described later.

The compound represented by the above formula (a) is preferably represented by the following general formula (5). The compound represented by the above formula (b) is preferably represented by the following general formula (6).

(In the formula, R ¹ , R ² , R ³ , R ⁴ , m ₁ , and n are as described above.)

(In the formula, R ² and m ₂ are as described above, and R ^3′ is a single bond or an alkylene group having 1 to 8 carbon atoms.)

That is, in the production method of the present invention, preferably, the hydrosilyl group of the compound B represented by the general formula (5) is reacted with the vinyl group of the compound represented by the general formula (6) to obtain the above-mentioned compound. The method is characterized by including a step of obtaining a methacryl-modified organo(poly)siloxane modified at one end represented by the formula (1). By the manufacturing method, a methacryl-modified organo(poly)siloxane having one terminal represented by the following formula (7) can be obtained in high purity.

(R ¹ , R ² , R ³ , R ⁴ , m ₁ , m ₂ , and n are as described above).

The production method of the present invention further comprises a polyalkylene oxide-modified silanol represented by the following general formula (2):

(In the formula, R ¹ , R ² , R ³ , R ⁴ , and m ₁ are as described above.)
By reacting with hexamethylcyclotrisiloxane, the following general formula (3)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , m ₁ , and n are as described above.)
A step of obtaining an intermediate compound A represented by
Then, the silanol group of the intermediate compound A of the general formula (3) is reacted with the organosilicon compound of the following general formula (4) to obtain the intermediate compound B of the general formula (5). Including steps.

(Wherein R ⁴ is as described above)

The above manufacturing method will be described in more detail below.
(I) Synthesis of polyalkylene oxide-modified silanol represented by the general formula (2) The method for producing the polyalkylene oxide-modified silanol represented by the general formula (2) is not particularly limited. It can be obtained by subjecting the terminal vinyl group of the indicated polyalkylene oxide polymer to an addition reaction with one hydrosilyl group of tetramethyldisiloxane and subsequently silanolating the remaining one hydrosilyl group.

(In the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² is H or a methyl group, R ^3′ is a single bond or an alkylene group having 1 to 8 carbon atoms, and m ₁ is 1 To 100, preferably 1 to 50, more preferably 1 to 10).

The polyalkylene oxide polymer and tetramethyldisiloxane are used in an amount such that the Si—H group of tetramethyldisiloxane is 6 to 40 equivalents, preferably 10 to 30 equivalents, relative to 1 equivalent of vinyl groups of the polyalkylene oxide polymer. It is better to react. In the addition reaction, a compound in which a polyalkylene oxide polymer is added to one end of tetramethyldisiloxane and a compound in which a polyalkylene oxide polymer is added to both ends are obtained, but there is a large excess relative to the polyalkylene oxide polymer. By using an amount of tetramethyldisiloxane, a siloxane compound having a Si-H group at one end can be produced at a ratio of 95% or more.

The addition reaction can be carried out in the absence of a solvent, but may be carried out in a solvent such as an ether-based, aromatic-based or aliphatic-based hydrocarbon. Of these, it is preferable to use toluene. In the present invention, a compound in which a polyalkylene oxide polymer is added to both terminals of tetramethyldisiloxane can be used in the following reaction without separation.

A catalyst may be used in the addition reaction. As the catalyst, a known catalyst can be used. Although not particularly limited, a platinum-based catalyst or a palladium-based catalyst is preferable, and a neutral platinum-based catalyst, for example, a 0-valent platinum-based catalyst to which an unsaturated compound is coordinated is preferable. In particular, hexachloroplatinum(IV) acid hexahydrate, platinum carbonyl vinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octyl aldehyde/octanol complex, or supported on activated carbon. Platinum can be used. Above all, it is preferable to use a tetravalent divinyldisiloxane coordinated zero-valent platinum catalyst. The catalyst may be a single type or a mixture of two or more types.
The catalyst is preferably used in an amount of 1 to 100 ppm, preferably 5 to 80 ppm as platinum based on the polyalkylene oxide polymer.

The addition reaction is preferably carried out at a reaction temperature of 30 to 150° C., particularly 80 to 120° C. for 1 to 5 hours. By carrying out the reaction in a closed system such as an autoclave, the reaction time can be shortened and the reaction rate of hydrosilylation can be improved. Then, the completion of the reaction is confirmed by measuring the amount of SiH groups remaining in the reaction system according to a conventional method. For example, the hydrogen gas generation method can be used. Then, the solvent may be distilled off from the reaction solution.

Next, the one-terminal Si—H group siloxane compound thus obtained is converted to silanol by a dehydrogenation reaction in the presence of water. The water used for silanolization is used in an amount of equimolar or more, preferably 3 to 10 times the molar amount of the Si—H group. In addition, a platinum-based, palladium-based, or hydroxyamine-based catalyst may be used as the catalyst, and for example, palladium carbon can be used. The catalyst is used in an amount of 40 to 200 ppm, preferably 60 to 150 ppm as a metal amount based on the polyalkylene oxide polymer having a Si—H bond at one end. Moreover, you may use a solvent as needed in a silanolization reaction. As the solvent, it is preferable to use a water-soluble ketone, alcohol, or ether solvent. The silanolization is preferably carried out at a reaction temperature of 30 to 150°C, preferably 50 to 100°C.

(Ii) Synthesis of Intermediate Compound A Represented by Formula (3) Represented by Formula (3) above by subjecting silanol compound represented by Formula (2) above to ring-opening polymerization of hexamethylcyclotrisiloxane. Intermediate compound A can be obtained. Hexamethylcyclotrisiloxane is used in an amount of 1 to 100 equivalents, preferably 1 to 20 equivalents, relative to 1 equivalent of hydroxyl groups of the silanol compound. The polymerization reaction is carried out in the presence of a polymerization catalyst. As such a polymerization catalyst, known catalysts can be used, but among them, a pentacoordinated silicon catalyst represented by the following formula (8) described in JP-B-45-1070 is preferably used. preferable.

In the formula, R ⁵ is a substituted or unsubstituted monovalent hydrocarbon group, and M is Li, Na, K, NH ₄ or C ₆ H ₅ CH ₂ N(CH ₃ ) ₃ . R ⁵ is preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms.

Examples of such a pentacoordinated silicon catalyst include those shown below.

Among them, it is preferable to use a pentacoordinated silicon catalyst having an alkali metal as a counter ion because the synthesis is easy, the stability over time is good, and the polysiloxane obtained by polymerization is excellent in monodispersity. .. In particular, the following pentacoordinated silicon catalyst is preferable.

The amount of the pentacoordinated silicon catalyst used is preferably 100 to 3000 ppm, particularly preferably 200 to 2000 ppm, based on hexamethylcyclotrisiloxane.

Also, the polymerization reaction is preferably carried out in a solvent. As the reaction solvent, a polar solvent containing no active hydrogen or a non-polar solvent can be used. For example, acetonitrile, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, dimethylsulfoxide, dimethylformamide, hexane, toluene, xylene and the like can be used, and among them, acetonitrile is preferably used. The reaction solvent is preferably dehydrated with a desiccant such as molecular sieves.

The reaction conditions for the polymerization reaction are appropriately selected, but a reaction temperature of 50 to 100° C., preferably 60 to 80° C. is good, and a reaction time is 1 to 20 hours. By the above reaction, an intermediate compound A having polyalkylene oxide at the ω terminal and silanol at the α terminal can be obtained.

(Iii) Synthesis of intermediate compound B represented by the above formula (5) Next, the silanol group of the intermediate compound A obtained by the above reaction is reacted with an organosilicon compound represented by the following general formula (4). ..

(Wherein R ⁴ is as described above)

The organochlorosilane of the above formula (4) is 1.0 to 2.0 mol, preferably 1.2 to 1.5 mol, relative to 1 mol of the organo(poly)siloxane intermediate compound A represented by the above formula (3). It is recommended to use the amount of. ‥

The silylation reaction using the organochlorosilane is performed by directly dropping the organochlorosilane into the reaction solution after the intermediate compound A is produced. The addition reaction is preferably carried out in the presence of a hydrochloric acid scavenger. Examples of the hydrochloric acid scavenger include various amines such as pyridine and triethylamine, and preferably triethylamine is used. The hydrochloric acid scavenger is preferably used in an amount of 1.0 to 2.0 mol, preferably 1.2 to 1.5 mol, based on 1 mol of organochlorosilane.

The reaction conditions are preferably a reaction temperature of 20 to 100° C., particularly 50 to 80° C., and a reaction time of 1 to 10 hours. After completion of the reaction, residual chlorosilane is deactivated by adding methanol. It is preferable to use methanol in an amount of 1.0 to 4.0 mol, preferably 1.2 to 3.0 mol, based on 1 mol of organochlorosilane. The reaction solvent and the deactivated chlorosilane are removed by distillation under reduced pressure at 100° C./10 mmHg. By this method, a hydrosilylorgano(poly)siloxane having one end having a polyalkylene oxide at the ω terminal (intermediate compound B) can be obtained.

(Iv) Synthesis of methacryl-modified organo(poly)siloxane modified at one end As described above, after obtaining the hydrosilylorgano(poly)siloxane at one end represented by the above formula (5) (intermediate compound B), the following formula (6) ) A vinyl group-containing compound represented by the formula (1) is subjected to an addition reaction to obtain a methacryl-modified organo(poly)siloxane modified at one end.

Examples of such a vinyl group-containing compound include the following.

Among them, the vinyl group-containing compounds shown below are particularly preferable because they are easily available as commercial products, side reactions in the hydrosilyl addition reaction hardly occur, and unreacted substances are easily removed by distillation under reduced pressure after the reaction.

A known method can be used for the hydrosilyl addition reaction between the hydrosilyl group and the vinyl group, and there is no particular limitation. For example, it is performed in the presence of an addition reaction catalyst such as a platinum group compound. At that time, a solvent may be used, and for example, an aliphatic or aromatic solvent such as hexane, methylcyclohexane, ethylcyclohexane or toluene, or an alcohol solvent such as ethanol or IPA can be preferably used.

In a preferred embodiment, for example, the vinyl group-containing compound represented by the formula (6) is diluted with a solvent as needed, and the platinum hydrosilylation catalyst is added thereto. The vinyl group-containing compound represented by the formula (6) is used in an amount such that the vinyl group is 1 to 3 equivalents relative to 1 equivalent of the hydrosilyl group of the organo(poly)siloxane. The type of platinum-based hydrosilylation catalyst is not particularly limited, and conventionally known ones can be used. The platinum concentration is preferably 1 to 30 ppm with respect to the total amount of reaction substrate and solvent. Next, hydrosilylorgano(poly)siloxane with one terminal (intermediate compound B) is added dropwise at room temperature or higher to react. The reaction temperature is 30 to 150° C., particularly 60 to 120° C., and it is preferably carried out for 1 to 5 hours. The unreacted vinyl group-containing compound can be removed together with the solvent by distillation after the reaction is completed.

Further, in the above reaction, a polymerization inhibitor may be added if necessary. As the polymerization inhibitor, those conventionally used for methacrylic compounds may be used. For example, phenol such as hydroquinone, methylhydroquinone (MQ), hydroquinone monomethyl ether (MEHQ), 2-t-butylhydroquinone, 4-methoxyphenol, and 2,6-di-t-butyl-4-methylphenol (BHT) Examples include system polymerization inhibitors. These polymerization inhibitors may be used alone or in combination of two or more. The amount of the polymerization inhibitor is not particularly limited, but is preferably an amount of 5 to 500 ppm, more preferably 20 to 200 ppm, with respect to the mass of the compound obtained.

The reaction solvent and unreacted low-molecular components are removed by distillation under reduced pressure at 120°C/10 mmHg, and the platinum catalyst is removed by filtration using activated carbon. By this method, a methacryl-modified organo(poly)siloxane modified at one end with a polyalkylene oxide group at the ω end can be obtained.

Hereinafter, the present invention will be described in more detail by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples.

The measuring device used in the examples is as follows.
Infrared spectrophotometer (IR): SPECTRUM 2000 (manufactured by PERKIN ELMER)
Gel permeation chromatograph (GPC): HLC-8220 (manufactured by Tosoh Corporation)
Column: TSKgel Super H2500 6.0 mmI. D. ×15cm, 3μm
TSKgel Super HM-H 6.0 mmI. D. ×15cm, 3μm
Reference column: TSKgel SuperH-RC
Solvent: Tetrahydrofuran Flow rate: 0.6 mL/min Column temperature: 40°C
Detector: RI (differential refraction detector)
¹ H-NMR: AVANCEIII-400 (manufactured by Bruker), deuterated chloroform used as a measuring solvent.

[Example 1]
(I) Synthesis of methoxytriethylene oxide-modified silanol 120 g of ω-terminal methoxytriethylene glycol monoallyl ether (molecular weight 204) in a 3 L glass reactor equipped with a stirrer, thermometer, reflux condenser, dropping funnel, 1, 1,788 g of 1,3,3-tetramethyldisiloxane (SiH group/SiVi group=20) and 1.76 g of a toluene solution of a tetramethyldivinyldisiloxane coordinated zero-valent platinum catalyst having a platinum content of 0.5% by weight, After reacting at 70° C. for 2 hours, the reaction solution was distilled off under reduced pressure to remove volatile matter, and 198 g of a pale brown liquid was obtained. In the obtained product, absorption of Si—H bond (2,125 cm ⁻¹ ) was confirmed by IR measurement, and the average molecular weight of the obtained compound determined from the amount of generated hydrogen gas was 340.

The hydrogen gas generation amount is measured by the following method.
A 10 g sample was accurately taken into a clean 100 ml Meyer flask, and then 20 ml of a 20% aqueous sodium hydroxide solution was gradually added to a solution dissolved in 10 ml of n-butanol, and the amount of hydrogen gas generated was measured with a gas buret. It was converted to a gas generation amount at 0° C. and 1 atmosphere by applying the following formula.
Hydrogen gas generation rate (ml/g)=0.359×P×V/T×S
(P: atmospheric pressure (mmHg) at measurement, V: generated hydrogen gas amount (ml), T: 273 + t°C (t°C: generated hydrogen gas temperature = temperature at measurement), S: sample amount)

Next, in a 500 ml flask equipped with a thermometer, a cooling tube and a stirring blade, 195 g of the above product, 100 g of tetrahydrofuran and 0.5 g of palladium carbon having a palladium content of 5.0% by weight were charged, and 32 g of water in an ice bath. Was added dropwise and reacted for 2 hours at 70° C., the reaction solution was distilled off under reduced pressure to remove volatile matter, and palladium carbon was removed by filtration to obtain 190 g of a colorless transparent liquid.

Upon IR measurement of the above product, absorption of Si—H bond (2,125 cm ⁻¹ ) disappeared and absorption of Si—OH bond (3,400 cm ⁻¹ ) was observed. Further, from the hydrogen gas generation amount, there was no residual Si—H group, and the reaction rate was 100%. The polystyrene reduced average molecular weight measured by GPC is about 400, and the obtained product is a silanol compound represented by the following formula (9).

(Ii) Synthesis of methoxytriethylene oxide modified intermediate compound A Next, in a 500 ml flask equipped with a thermometer, a cooling tube and a stirring blade, 50 g (0.14 mol) of the silanol compound of the above formula (9) and hexamethyl 104.5 g (0.47 mol) of cyclotrisiloxane and 200 g of dehydrated acetonitrile were charged, and the contents were made into a uniform solution by heating to 50° C. in an oil bath. To this solution was added 0.16 g of a pentacoordinated silicon catalyst represented by the following formula (10), and the mixture was stirred at 60° C. for 3 hours to carry out a polymerization reaction.

(Iii) Synthesis of methoxytriethylene oxide-modified intermediate compound B After the reaction of (ii) above, 25.6 g of triethylamine was added and mixed, and the reaction solution was ice-cooled, followed by 20.0 g of dimethylchlorosilane at 10° C. ( (0.21 mol) was added dropwise, the reaction solution was heated and stirred at 70° C. for 2 hours to carry out a terminal blocking reaction, and then 10 g of methanol was added to deactivate the remaining chlorosilane. Subsequently, the deactivated product of toluene and chlorosilane was removed by performing vacuum distillation under the condition of 100° C./10 mmHg, and the polymerization catalyst was removed by extracting with 300 g of hexane to obtain a colorless transparent liquid (intermediate). Body compound B). The yield was 121 g, and the yield based on the above-mentioned intermediate compound A was 62.8%.

(Iv) Synthesis of methacryl-modified organopolysiloxane modified at one end In a 500 ml flask equipped with a thermometer, a cooling tube, and a stirring blade, allyloxyethoxymethacrylate (product name; AOEMA, manufactured by Mitsubishi Rayon) 28.3 g, 2,6- 0.014 g of di-t-butyl-4-methylphenol (BHT), 0.014 g of methylhydroquinone (MQ), 75 g of toluene, tetramethyldivinyldisiloxane coordination 0-valent platinum catalyst having a platinum content of 0.5% by weight After charging 0.068 g of a toluene solution and dropping 120 g of the above intermediate compound B and reacting at 75 to 80° C. for 2 hours, the reaction solution was distilled off under reduced pressure at 120° C./10 mmHg to remove toluene and unreacted products. The low molecular weight component was removed, and the platinum catalyst was removed by filtration using activated carbon to obtain a colorless transparent liquid. The yield was 131 g, and the yield based on the above-mentioned intermediate compound B was 94.0%.

Viscosity (measured by Canon-Fenske viscometer), specific gravity (measured by flotation scale), refractive index (measured by digital refractometer RX-5000 (manufactured by Atago)), weight average of the obtained product at 25° C. The molecular weight (measured by gel permeation chromatography) was measured.
Viscosity: 100 mm ² /s
Specific gravity: 0.999
Refractive index: 1.4139
Weight average molecular weight: 1300

From the result of ¹ H-NMR, it was found that the obtained product was a compound having a structure represented by the following formula (11). The result of ¹ H-NMR is shown in FIG.

[Comparative Example 1]
A silanol compound of the above formula (9) was produced in the same manner as in Example 1, and a polymerization reaction with hexamethylcyclotrisiloxane was performed. After the reaction was completed, 0.11 g of BHT, 24.0 g of pyridine and 82 g of toluene were added and mixed, and the reaction solution was ice-cooled, and then 45.3 g (0.21 mol) of methacryloylpropyldimethylchlorosilane was added dropwise at 10°C. The reaction solution was heated and stirred at 70° C. for 2 hours to carry out an end-capping reaction, and then 20 g of methanol was added to deactivate the remaining chlorosilane. Then, toluene and low volatile matter were removed by performing vacuum distillation under the conditions of 120° C./10 mmHg, and the polymerization catalyst was removed by filtration using activated carbon to obtain a light brown transparent oil. The yield was 151 g, and the yield based on the silanol compound of the formula (9) was 84.0%. ^From the results of ¹ H-NMR and GPC, the obtained product was a compound represented by the following formula (12).

[Comparative Example 2]
In the same manner as in Example 1, after obtaining the hydrosilylorganopolysiloxane at one end of the intermediate compound B, when synthesizing the organopolysiloxane modified at one end with methacryl, 21.0 g of allyloxymethacrylate was used instead of allyloxyethoxymethacrylate. The compound was obtained in the same manner except that (obtained from Tokyo Chemical Industry) was used. The yield was 123 g, and the yield based on the silanol compound of the formula (9) was 92.0%. ^From the results of ¹ H-NMR and GPC, the obtained product was the compound represented by the above formula (12).

The compounds obtained in Example 1 and Comparative Examples 1 and 2 and hydroxymethacrylate were mixed in an amount such that the mixing weight ratio was compound/hydroxymethacrylate=8:2, and the compatibility was evaluated. When it was soluble (that is, the mixed solution became colorless and transparent), it was evaluated as ◯, and when it was insoluble (that is, the mixed solution became cloudy), it was evaluated as x.
Furthermore, the amount of impurities (amount other than the target substance) contained in each of the compounds obtained in Example 1 and Comparative Examples 1 and 2 was calculated from NMR and GPC. The results are shown in Table 1 below.

The one-terminal methacryl-modified organo(poly)siloxane of the present invention has excellent compatibility with other hydrophilic monomers and can be produced with high purity, and therefore can provide a silicone graft polymer having excellent surface characteristics. .. Therefore, the one-end methacryl-modified organo(poly)siloxane of the present invention is used as a water repellent for concrete, anti-sticking paint, antifouling paint in the sea, weather resistant paint, anti-sticking agent for thermal transfer recording film, water landing, snow landing. It is useful as a synthetic intermediate (monomer component) for graft copolymers used in applications such as anti-corrosion paints, cosmetics, and contact lens materials.

Claims

Methacryl-modified organo(poly)siloxane modified at one end with blocks arranged in the following order:
AB 1 -CB 2 -DY

(In the formula, A is a (poly)alkylene oxide group having an alkoxy group at the terminal, B 1 is a substituted or unsubstituted alkylene group, and B 2 is a substituted or unsubstituted alkylene group or alkylene oxide group. , C is a divalent (poly)siloxy group, D is a divalent (poly)alkylene oxide group, and Y is a methacryl group).
The one-terminal methacryl-modified organo(poly)siloxane according to claim 1, which is represented by the following general formula (1).

(In the formula (1), R 1 is an alkyl group having 1 to 10 carbon atoms, R 2 is H or a methyl group, R 3 is independently of each other, an alkylene group having 2 to 10 carbon atoms, and R 4 is independently of each other, An alkyl group, an alkenyl group or an aryl group having 1 to 10 carbon atoms, m 1 is an integer of 1 to 100, m 2 is an integer of 1 to 100, n is an integer of 1 to 100, and Y is methacryl. Is the base).
A method for producing a methacryl-modified organo(poly)siloxane having one terminal methacryl, which comprises blocks arranged in the following order:

AB 1 -CB 2 -DY

(In the formula, A is a (poly)alkylene oxide group having an alkoxy group at the terminal, B 1 is a substituted or unsubstituted alkylene group, and B 2 is a substituted or unsubstituted alkylene group or alkylene oxide group. , C is a divalent (poly)siloxy group, D is a divalent (poly)alkylene oxide group, and Y is a methacryl group)

A step of reacting a hydrosilyl group of the compound represented by the following formula (a) with a vinyl group of the compound represented by the following formula (b) to obtain the above-mentioned one-terminal-methacryl-modified organo(poly)siloxane. The manufacturing method characterized by the above
AB 1 -CH (a)

CH 2 = CH-B 2 ' -D-Y (b)

(In the formula, A, B 1 , C, D and Y are as described above, and B 2 ′ is the residue of the group represented by B 2 ).
The hydrosilyl group of the compound B represented by the following general formula (5) is reacted with the vinyl group of the compound represented by the following general formula (6) to give a methacryl-modified organomethacrylate having one terminal represented by the following formula (1). The manufacturing method according to claim 3, further comprising a step of obtaining a (poly)siloxane.

(In the formula (5), R 1 is an alkyl group having 1 to 10 carbon atoms, R 2 is H or a methyl group, R 3 is independently of each other, an alkylene group having 2 to 10 carbon atoms, and R 4 is independently of each other, (Alkyl group, alkenyl group or aryl group having 1 to 10 carbon atoms, m 1 is an integer of 1 to 100, and n is an integer of 1 to 100)

(In the formula (6), R 2 is H or a methyl group, m 2 is an integer of 1 to 100, and R 3′ is a single bond or an alkylene group having 1 to 8 carbon atoms)

(In the formula (1), R 1 is an alkyl group having 1 to 10 carbon atoms, R 2 is H or a methyl group, R 3 is independently of each other, an alkylene group having 2 to 10 carbon atoms, and R 4 is independently of each other, An alkyl group, an alkenyl group or an aryl group having 1 to 10 carbon atoms, m 1 is an integer of 1 to 100, m 2 is an integer of 1 to 100, n is an integer of 1 to 100, and Y is methacryl. Is the base).
A step of reacting a polyalkylene oxide-modified silanol represented by the following general formula (2) with hexamethylcyclotrisiloxane to obtain a compound A represented by the following general formula (3), and

(In the formula, R 1 , R 2 , R 3 , R 4 , and m 1 are as described above.)

(In the formula, R 1 , R 2 , R 3 , R 4 , m 1 , and n are as described above.)
The method further includes a step of reacting the compound A represented by the general formula (3) with an organosilicon compound represented by the following general formula (4) to obtain the compound B represented by the general formula (5). The manufacturing method according to claim 4.

(Wherein R 4 is as described above).
The reaction of the polyalkylene oxide-modified silanol represented by the general formula (2) and hexamethylcyclotrisiloxane is represented by the following general formula (8).

(In the formula, R 5 is a substituted or unsubstituted monovalent hydrocarbon group, and M is Li, Na, K, NH 4 or C 6 H 5 CH 2 N(CH 3 ) 3 )
The production method according to claim 5, which is carried out in the presence of a pentacoordinated silicon catalyst represented by: