Polyorganosiloxane and method for producing the same

Abstract

The present invention provides a polyorganosiloxane which is characterized by being represented by formula (1). Consequently, the present invention provides a polyorganosiloxane which is compatible without any trouble even under the conditions where conventional epoxy-modified silicone cannot be compatible. (In formula (1), each R1 independently represents a group that is selected from among alkyl groups having 1 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms and aralkyl groups having 7 to 12 carbon atoms, or a hydroxyl group; each X independently represents a divalent alkylene group having 1 to 10 carbon atoms; each Y independently represents a group that is selected from among alkylene groups having 5 to 30 carbon atoms and optionally having an ether bond, arylene groups having 6 to 30 carbon atoms and aralkylene groups having 7 to 30 carbon atoms; each Z independently represents an alkylene group having 1 to 20 carbon atoms and optionally having an ether bond; n represents an integer of 0 to 100; and m represents a number of 1 to 2.)

Description

Technical Field

[0001] The present invention relates to a polyorganosiloxane and a method for producing the same.

Background Art

[0002] Epoxy-modified silicone is a polyorganosiloxane having an epoxy group as a reactive group. It is used in applications such as resin modifiers, fiber treating agents, and paint additives that utilize its reactivity (Patent Documents 1 to 3).

[0003] However, in epoxy-modified silicone, there has been a problem that as the chain length of the polyorganosiloxane increases, its compatibility with other polar compounds deteriorates and separation occurs.

[0004] For example, amine-based curing agents known as curing agents for epoxy resins often phase-separate without a solvent when mixed with polydimethylsiloxane having glycidyl groups at both ends. If the polydimethylsiloxane and the curing agent are not compatible, it is difficult to obtain a cured product.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] The present invention has been made in view of such circumstances, and an object thereof is to provide a polyorganosiloxane that can be compatibly mixed without problems even under conditions where it does not compatibly mix well with conventional epoxy-modified silicone.

Means for Solving the Problems

[0007] In order to solve the above problems, the present invention provides a polyorganosiloxane represented by the following formula (1).

Chemical Formula

[0008] Such a polyorganosiloxane will be a polyorganosiloxane that can be compatibly dissolved without problems even under conditions where it is not compatibly dissolved with conventional epoxy-modified silicone.

[0009] In the present invention, in the polyorganosiloxane represented by the formula (1), the number average molecular weight in terms of polystyrene standard substance is preferably 500 to 100,000.

[0010] Such a polyorganosiloxane will have a molecular weight sufficient for the epoxy groups at both ends to react with a curing agent to obtain a cured product.

[0011] In the present invention, in the polyorganosiloxane represented by the formula (1), the epoxy equivalent (g / mol) is preferably 300 to 5,000 g / mol.

[0012] Such a polyorganosiloxane will have an amount sufficient for the epoxy groups at both ends to react with a curing agent to obtain a cured product with good physical properties.

[0013] In the present invention, the polyorganosiloxane represented by the formula (1) preferably contains hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in a total amount of 3,000 ppm or less.

[0014] Such a polyorganosiloxane is preferable because there is little possibility of various problems caused by low-molecular cyclic siloxanes.

[0015] In the present invention, there is provided a method for producing a polyorganosiloxane represented by the following formula (1),

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0016] With such a method for producing a polyorganosiloxane, a polyorganosiloxane that can be compatibly dissolved without problems even under conditions where it does not dissolve well with conventional epoxy-modified silicone can be efficiently produced.

[0017] In addition, in the present invention, as the both-terminal carbinol-modified silicone represented by the formula (2), it is preferable to use a both-terminal carbinol-modified silicone having a hydroxyl value (OH value) of 10 to 500 mgKOH / g.

[0018] With such a method for producing a polyorganosiloxane, the polyorganosiloxane can be produced more efficiently.

[0019] In addition, in the present invention, as the both-terminal carbinol-modified silicone represented by the formula (2), it is preferable to use one containing hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in a total amount of 3,000 ppm or less.

[0020] With such a method for producing a polyorganosiloxane, a polyorganosiloxane in which various problems caused by low-molecular cyclic siloxanes are less likely to occur can be efficiently produced.

[0021] In addition, in the present invention, it is preferable that the reaction is carried out such that the ratio (NCO / OH ratio) of the number of moles of hydroxyl groups (mol OH) of the both-terminal carbinol-modified silicone represented by the formula (2) to the number of moles of isocyanate groups (mol NCO) of the diisocyanate compound represented by the formula (3) is 1.5 to 2.0.

[0022] With such a method for producing a polyorganosiloxane, the polyorganosiloxane can be produced even more efficiently.

Advantages of the Invention

[0023] The present invention relates to a polyorganosiloxane and a method for producing the same, and more particularly, to a polyorganosiloxane having epoxy groups at both ends and urethane bonds in the main chain, and a method for producing the same. Since the polyorganosiloxane of the present invention has epoxy groups, it can be used in various applications by utilizing its reactivity. For example, since it is compatible with an amine-based curing agent, a cured product can be obtained by reacting with the epoxy groups. The obtained cured product has high adhesiveness and adhesion to the substrate due to hydrogen bonds formed by the hydroxyl groups and urethane groups remaining after the reaction, and furthermore, a flexible and high-strength cured product such as a polyurethane resin can be obtained. Since it has characteristics not found in conventional epoxy-modified silicones, it is highly useful. In addition, with respect to low-molecular cyclic siloxanes, by reducing these, it is possible to prevent deposition on the apparatus and malfunctions of equipment caused by their volatilization and diffusion during the production of the cured product.

Embodiments for Carrying Out the Invention

[0024] As described above, there has been a demand for the development of a polyorganosiloxane that can be compatibly used even under conditions where it does not mix well with conventional epoxy-modified silicones.

[0025] As a result of intensive studies to achieve the above object, the present inventors have found that a polyorganosiloxane having epoxy groups at both ends and urethane bonds in the main chain can achieve the above object, and thus have completed the present invention.

[0026] That is, the present invention is a polyorganosiloxane represented by the following formula (1).

Chemical formula

[0027] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0028] The polyorganosiloxane of the present invention is characterized by being represented by the following formula (1). [Chemical formula] (In formula (1), R 1 represents a group independently selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms, or a hydroxyl group, X represents, independently of each other, a divalent alkylene group having 1 to 10 carbon atoms, Y represents, independently of each other, a group selected from an alkylene group which may have an ether bond having 5 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, and an aralkylene group having 7 to 30 carbon atoms, Z represents, independently of each other, an alkylene group which may have an ether bond having 1 to 20 carbon atoms, n is an integer of 0 to 100, and m is 1 to 2.)

[0029] In formula (1), R 1is independently selected from an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, preferably 6 to 9 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, preferably 7 to 10 carbon atoms, or a hydroxyl group. Specific examples thereof include linear or branched alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, etc.; cycloalkyl groups such as cyclohexyl group; aryl groups such as phenyl group, naphthyl group; aralkyl groups such as benzyl group, etc. Among them, a methyl group or a phenyl group is preferred.

[0030] In formula (1), X is a divalent alkylene group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, independently of each other.

[0031] Specific examples of the alkylene group having 1 to 10 carbon atoms include methylene group, ethylene group, propylene group, n-hexylene group, n-octylene group, etc. Preferably it is a methylene group.

[0032] In formula (1), Y is a group independently selected from an alkylene group having 5 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, and an aralkylene group having 7 to 30 carbon atoms.

[0033] The alkylene group having 5 to 30 carbon atoms may be linear, branched or cyclic. Specific examples thereof include linear or branched alkylene groups such as n-pentylene group, n-hexylene group, n-heptylene group, n-octylene group, 2-ethylhexylene group, n-decylene group, n-undecylene group, n-dodecylene group, n-tridecylene group, n-tetradecylene group, n-pentadecylene group, n-hexadecylene group, n-heptadecylene group, n-octadecylene group, n-nonadecylene group, n-eicosanylene group, etc.

[0034] In addition, the alkylene group may have one or more ether bonds in the middle of the molecular chain. Specifically, it is a group containing an ether bond such as an ethyleneoxy group, a propyleneoxy group, or a butyleneoxy group, and there may be a plurality of ether bonds.

[0035] Examples of the arylene group having 6 to 30 carbon atoms include an o-phenylene group, an m-phenylene group, a p-phenylene group, a 3,5-tolylene group, a 2,4-tolylene group, a 2,6-tolylene group, a 1,2-naphthylene group, a 1,8-naphthylene group, a 2,3-naphthylene group, a 4,4'-biphenylene group, a 4,4'-methylenebisphenyl group, and the like.

[0036] Examples of the aralkylene group having 7 to 30 carbon atoms include an o-xylylene group, an m-xylylene group, a p-xylylene group, a 1,3-phenylenebis(2-propyl) group, and the like.

[0037] Preferably, the following groups are exemplified as the Y. The dotted line indicates the bonding position with the nitrogen atom of the urethane bond in the formula (1), and hydrogen atoms are omitted by convention.

Chemical formula

[0038] In the formula (1), Z is independently an alkylene group having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms. One or more ether bonds may be interposed in the alkylene chain having 1 to 20 carbon atoms. Preferably, it is a propylene group (-CH2CH2CH2-) or an ethyleneoxypropylene group (*-CH2CH2OCH2CH2CH2-), where * indicates the bond with the oxygen atom of the urethane bond in the formula (1).

[0039] In the formula (1), n represents an integer of 0 to 100. Preferably, n is an integer of 0 to 60.

[0040] In formula (1), m represents the average degree of polymerization, where m is from 1 to 2, preferably 1 or 2. If m exceeds 2, it is not preferred because a uniform cured product cannot be obtained.

[0041] The polyorganosiloxane of the present invention preferably has a number average molecular weight of 500 to 100,000, more preferably 500 to 50,000, and even more preferably 500 to 20,000. Within this range, the epoxy groups at both ends can react with the curing agent to obtain a molecular weight sufficient to form a cured product. The number average molecular weight refers to the number average molecular weight in terms of polystyrene standard substance in gel permeation chromatography (GPC) measurement under the following measurement conditions. [Measurement Conditions] Developing solvent: Tetrahydrofuran (THF) Flow rate: 0.6 mL / min Detector: Differential refractive index detector (RI) Column: TSK Guardcolumn SuperH-H TSKgel SuperHM-N (6.0 mm I.D. × 15 cm × 1) TSKgel SuperH2500 (6.0 mm I.D. × 15 cm × 1) (All are manufactured by Tosoh Corporation) Column temperature: 40 °C Sample injection volume: 50 μL (THF solution with a concentration of 0.3 mass%)

[0042] The polyorganosiloxane of the present invention preferably has an epoxy equivalent (g / mol) of 300 to 5,000 g / mol, more preferably 500 to 2,500 g / mol. Within this range, the epoxy groups at both ends can react with the curing agent to obtain an amount sufficient to form a cured product with good physical properties. The epoxy equivalent (g / mol) can be calculated by adding hydrochloric acid to a predetermined mass of the sample dissolved in 1,4-dioxane and performing back-titration using an aqueous sodium hydroxide solution.

[0043] Regarding low-molecular cyclic siloxanes, as described in International Publication No. 2016 / 111104 etc., various problems may occur and it is preferable to reduce them. Preferably, the polyorganosiloxane represented by the above formula (1) contains hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in a total amount of 3,000 ppm or less, more preferably 2,000 ppm or less, and even more preferably 1,000 ppm or less. The smaller the amount of low-molecular cyclic siloxanes (D3 to D6), the more preferable, and the lower limit is not particularly limited, but can be, for example, 0 ppm or more.

[0044] The amount of the above low-molecular cyclic siloxanes (D3 to D6) can be quantified by gas chromatography (GC) using a sample obtained by extracting and diluting the polyorganosiloxane of the present invention with an organic solvent.

[0045] In addition, the present invention provides a method for producing a polyorganosiloxane represented by the following formula (1),

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0046] Regarding the method for producing the polyorganosiloxane of the present invention, a known method for producing a urethane compound can also be used. However, according to the above production method, the polyorganosiloxane of the present invention can be efficiently obtained.

[0047] For example, a polyol as a raw material, and a catalyst and a solvent are added as necessary, and the temperature is raised under an inert gas atmosphere. Here, the raw material polyisocyanate is added all at once, divided, or dropped to produce an isocyanate prepolymer. Then, as a terminal-blocking raw material, a compound having one or more epoxy groups and one hydroxyl group in one molecule is added and aged to obtain the target polyorganosiloxane.

[0048] Alternatively, first, a catalyst and a solvent are added to the raw material polyisocyanate as necessary, and the reaction is carried out while dropping a compound having one or more epoxy groups and one hydroxyl group in one molecule. After aging, the raw material polyol is added and aged to also obtain the target polyorganosiloxane.

[0049] In the method for producing the polyorganosiloxane of the formula (1), examples of the polyol used as a raw material include both-terminal carbinol-modified silicones represented by the following formula (2) or formula (5). [Chemical formula] (In the formula, R 1 , Z, and n are the same as defined above.) [Chemical formula] (In the formula, R 2 independently represents a group selected from alkyl groups having 1 to 12 carbon atoms and aralkyl groups having 7 to 12 carbon atoms, or a hydroxyl group, R 3 independently represents an aryl group having 6 to 12 carbon atoms, a is an integer of 0 to 100, b is an integer of 1 to 100, a + b is an integer of 1 to 100, and the structural unit in parentheses may be a block or random, and Z is the same as defined above.)

[0050] In formula (5), R 2 independently represents a group selected from alkyl groups having 1 to 12 carbon atoms and aralkyl groups having 7 to 12 carbon atoms, or a hydroxyl group, R 3 independently represents an aryl group having 6 to 12 carbon atoms, a is an integer of 0 to 100, b is an integer of 1 to 100, a + b is an integer of 1 to 100, and the structural unit in parentheses may be a block or random, and Z is the same as defined above.

[0051] As a method for producing the both-terminal carbinol-modified silicone, for example, a polyorganosiloxane having silicon-hydrogen bonds at both ends synthesized using a cyclic siloxane such as 1,1,3,3-tetramethyldisiloxane and 1,1,3,3,5,5,7,7-octamethylcyclotetrasiloxane in the presence of an acid catalyst is reacted with a compound having a hydroxyl group and a carbon-carbon unsaturated bond group at the terminal in the presence of a platinum catalyst such as Karstedt's catalyst.

[0052] Further, as the compound having a hydroxyl group and a carbon-carbon unsaturated bond group at the terminal, a compound in which the hydroxyl group is protected with a trimethylsilyl group may be used. In this case, if the trimethylsilyl group is deprotected with an alcohol compound such as methanol after the reaction, the desired compound can be obtained. Specifically, allyloxytrimethylsilane (manufactured by Fujifilm Wako Pure Chemical Corporation) can be mentioned.

[0053] As the both-terminal carbinol-modified silicone represented by the formula (2) or formula (5), it is preferable to use a both-terminal carbinol-modified silicone having a hydroxyl value (OH value) of 10 to 500 mgKOH / g, and more preferably 20 to 200 mgKOH / g.

[0054] In the method for producing the polyorganosiloxane of the formula (1), examples of the polyisocyanate as another raw material include diisocyanate compounds represented by the following formula (3).

Chemical formula

[0055] Specifically, the following compounds can be mentioned and are also available as commercial products. Note that hydrogen atoms are omitted by convention, and the following structural formulas also include stereoisomers.

Chemical formula

[0056] The m in the formula (1) can be calculated from the ratio (NCO / OH ratio) of the number of moles of hydroxyl groups (moles of OH) of the both-terminal carbinol-modified silicone represented by the formula (2) to the number of moles of isocyanate groups (moles of NCO) of the diisocyanate compound represented by the formula (3). It is preferable to carry out the reaction so that the NCO / OH ratio is 1.5 to 2.0, and more preferably 1.67 to 2.0.

[0057] In the method for producing the polyorganosiloxane of the formula (1), examples of the compound having one or more epoxy groups and one hydroxyl group in the molecule serving as the end-capping raw material include the compound represented by the formula (4). [Chemical formula] (In the formula, X is the same as defined above.)

[0058] Specifically, glycidol can be mentioned and it is available as a commercial product.

[0059] The amount of the compound having an epoxy group and a hydroxyl group may be an amount that reacts all of the remaining NCO in the reaction of the polyol and the polyisocyanate. Preferably, it is 1.0 to 1.1 moles, more preferably 1.0 to 1.05 moles, per mole of the remaining NCO. In addition, the remaining NCO can be confirmed by measuring the isocyanate equivalent.

[0060] The isocyanate equivalent (g / mol) can be determined by adding a solution prepared by adding dibutylamine to dehydrated toluene so as to be 0.1 mol% to a sample of a predetermined mass, diluting with isopropanol, and then performing back-titration using hydrochloric acid.

[0061] In the method for producing the polyorganosiloxane of the present invention, a solvent-free condition is preferred. However, in cases where the thickening is significant, it is more preferred to use a reaction solvent. In that case, an organic solvent that does not react with the isocyanate group or the epoxy group is preferred.

[0062] For example, aromatic compounds such as toluene and xylene; aliphatic compounds such as hexane, heptane, and cyclohexane; ether compounds such as tetrahydrofuran; ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester compounds such as methyl acetate, ethyl acetate, and butyl acetate; and amide compounds such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone can be mentioned.

[0063] In the method for producing the polyorganosiloxane of the present invention, a catalyst may be added to accelerate the reaction, although it may be catalyst-free.

[0064] Examples of the catalyst include amine catalysts such as triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and 1,4-diazabicyclo[2.2.2]octane; tin catalysts such as dibutyltin dilaurate and dioctyltin dilaurate; bismuth catalysts such as bismuth 2-ethylhexanoate and bismuth octanoate; titanium catalysts such as tetrabutyl orthotitanate, tetra(2-ethylhexyl) orthotitanate, and titanium diisopropoxide bis(acetylacetonate); and zirconium catalysts such as zirconium tetrabutoxide and zirconium tetraacetylacetonate.

[0065] As the reaction conditions in the method for producing the polyorganosiloxane of the present invention, it is preferably carried out under an inert gas atmosphere such as nitrogen or argon to prevent the incorporation of moisture. The reaction temperature is preferably from room temperature (20°C) to 150°C, more preferably from room temperature (20°C) to 120°C. The reaction time is preferably from 0.5 hour to 60 hours, more preferably from 0.5 hour to 24 hours.

[0066] In the method for producing the polyorganosiloxane of the present invention, the diol-modified silicone represented by the above formula (2) or the polyorganosiloxane having silicon-hydrogen bonds at both ends, which is a raw material thereof, is purified in advance by stripping under heating and reduced pressure, etc., and it is preferable to use it with the total amount of low molecular cyclic siloxanes (D3 to D6) being 3,000 ppm or less.

[0067] That is, in the method for producing the polyorganosiloxane of the present invention, as the both-terminal carbinol-modified silicone represented by the formula (2), those containing hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in a total amount of 3,000 ppm or less are preferably used. The amount of low-molecular cyclic siloxanes (D3 to D6) is preferably as small as possible, and the lower limit is not particularly limited, but can be, for example, 0 ppm or more.

Examples

[0068] Hereinafter, the present invention will be specifically described using Examples and Comparative Examples, but the present invention is not limited thereto. The viscosity was measured with a B-type viscometer (TVB-10 type manufactured by Toki Sangyo Co., Ltd.). The volatile content was calculated by precisely weighing about 1.5 g of the sample in an aluminum petri dish, heating the sample in a hot air circulation dryer at 105 °C for 3 hours, and measuring the weight change before and after heating. The epoxy equivalent was measured by adding hydrochloric acid to a predetermined mass of the sample dissolved in 1,4-dioxane and performing back titration using a COM-1760S manufactured by Hiranuma Sangyo Co., Ltd. as a titration device with sodium hydroxide. The GPC measurement was performed using an HLC-8320GPC manufactured by Tosoh Corporation, using tetrahydrofuran as a solvent, and the number average molecular weight Mn and the weight average molecular weight Mw were determined.

[0069] [Example 1] 70.15 g (0.631 mol NCO) of isophorone diisocyanate (Desmodur I manufactured by Covestro) was charged into a 500 mL separable flask, and a mechanical stirrer, stirring blade, Dimroth reflux condenser, nitrogen gas inlet, and thermometer were attached, and nitrogen gas was passed through. Next, 0.25 g (0.1 mass%) of K-KAT XK-640 (bismuth carboxylate manufactured by Namboku Kasei Co., Ltd., containing 18% bismuth) as a catalyst was added, and the temperature was raised until the internal temperature reached 60°C. Using a 300 mL dropping funnel, 200.00 g (0.421 mol OH, NCO / OH = 1.5) of 3-(2-hydroxyethoxy)propyldimethylsiloxy-terminated polydimethylsiloxane with D3 of 64 ppm, D4 of 59 ppm, D5 of 23 ppm, and D6 of 226 ppm (n = 8, OH value 118 mgKOH / g) was added in four equal portions over 1 hour, and then aged at 70°C for 3 hours. Thereafter, 15.72 g (0.211 mol) of glycidol (manufactured by Fujifilm Wako Pure Chemical Corporation) was added and aged at 70°C for 2 hours to obtain 240.00 g of a colorless slightly turbid viscous liquid. From NCO / OH = 1.5, m is 2. The physical properties are shown in Table 1. The low molecular weight cyclic siloxanes were extracted from 1 g of the sample with 10 mL of hexane using tetradecane as an internal standard and measured by GC. As a result, the total amount of D3 to D6 was 201 ppm. (D3: 15 ppm, D4: 20 ppm, D5: 16 ppm, D6: 150 ppm)

[0070] [Example 2] In a 500 mL separable flask, 35.71 g (0.321 mol NCO) of isophorone diisocyanate was charged, and a mechanical stirrer, stirring blade, Dimroth reflux condenser, nitrogen gas inlet, and thermometer were attached, and nitrogen gas was passed through. Next, 0.25 g (0.1 mass%) of K-KAT XK-640 as a catalyst was added, and the temperature was raised until the internal temperature reached 60°C. Using a 300 mL dropping funnel, 200.00 g (0.214 mol OH, NCO / OH = 1.5) of 3-(2-hydroxyethoxy)propyldimethylsiloxy-terminated polydimethylsiloxane with D3 < 5 ppm, D4 24 ppm, D5 24 ppm, and D6 107 ppm (n = 20, OH value 60 mgKOH / g) was added in four equal portions over 1 hour, and then aged at 70°C for 3 hours. Thereafter, 8.05 g (0.108 mol) of glycidol was added and aged at 70°C for 2 hours to obtain 277.05 g of a colorless slightly turbid viscous liquid. From NCO / OH = 1.5, m is 2. The physical properties are shown in Table 1. The low molecular cyclic siloxanes were diluted with 10 mL of acetone using tetradecane as an internal standard per 1 g of the sample and measured by GC. As a result, the total amount of D3 to D6 was <20 ppm. (D3: <5 ppm, D4: <5 ppm, D5: <5 ppm, D6: <5 ppm)

[0071] [Example 3] Into a 500 mL separable flask, 20.80 g (0.187 mol NCO) of isophorone diisocyanate was charged, and a mechanical stirrer, stirring blade, Dimroth reflux condenser, nitrogen gas inlet, and thermometer were attached, and nitrogen gas was passed through. Next, 0.23 g (0.1 mass%) of K-KAT XK-640 as a catalyst was added, and the temperature was raised until the internal temperature reached 60°C. Using a 300 mL dropping funnel, 200.00 g (0.124 mol OH, NCO / OH = 1.5) of 3-(2-hydroxyethoxy)propyldimethylsiloxy-terminated polydimethylsiloxane with D3 < 5 ppm, D4 15 ppm, D5 22 ppm, and D6 439 ppm (n = 40, OH value 35 mgKOH / g) was added over 40 minutes, and then aged at 70°C for 3 hours. Thereafter, 4.70 g (0.063 mol) of glycidol was added and aged at 70°C for 2.5 hours to obtain 214.09 g of a colorless slightly turbid viscous liquid. From NCO / OH = 1.5, m is 2. The physical properties are shown in Table 1. The low molecular cyclic siloxanes were diluted with 10 mL of acetone using tetradecane as an internal standard with respect to 1 g of the sample, and measured by GC. As a result, the total amount of D3 to D6 was < 320 ppm. (D3: < 5 ppm, D4: < 5 ppm, D5: < 5 ppm, D6: 305 ppm)

[0072] [Example 4] Into a 500 mL separable flask, 91.95 g (0.827 mol NCO) of isophorone diisocyanate was charged, and a mechanical stirrer, stirring blade, Dimroth reflux condenser, nitrogen gas inlet, and thermometer were attached, and nitrogen gas was passed through. Next, 0.32 g (0.1 mass%) of K-KAT XK-640 as a catalyst was added, and the temperature was raised until the internal temperature reached 60°C. Using a 300 mL dropping funnel, 200.00 g (0.413 mol OH, NCO / OH = 2.0) of 3-(2-hydroxyethoxy)propyldimethylsiloxy-terminated polydimethylsiloxane with D3 of 64 ppm, D4 of 59 ppm, D5 of 23 ppm, and D6 of 226 ppm (n = 8, OH value 116 mgKOH / g) was added over 30 minutes, and then aged at 70°C for 3 hours. Thereafter, 30.80 g (0.415 mol) of glycidol was added and aged at 70°C for 2 hours to obtain 319.17 g of a colorless slightly turbid viscous liquid. From NCO / OH = 2.0, m is 1. The physical properties are shown in Table 1. The low molecular cyclic siloxanes were extracted from 1 g of the sample with 10 mL of hexane using tetradecane as an internal standard and measured by GC. As a result, the total amount of D3 to D6 was 305 ppm. (D3: 54 ppm, D4: 52 ppm, D5: 16 ppm, D6: 183 ppm)

[0073] [Example 5] Into a 500 mL separable flask, 26.22 g (0.236 mol NCO) of isophorone diisocyanate was charged, and a mechanical stirrer, stirring blade, Dimroth reflux condenser, nitrogen gas inlet, and thermometer were attached, and nitrogen gas was passed through. Next, 0.24 g (0.1 mass%) of K-KAT XK-640 as a catalyst was added, and the temperature was raised until the internal temperature reached 60 °C. Using a 300 mL dropping funnel, 200.00 g (0.118 mol OH, NCO / OH = 2.0) of 3-(2-hydroxyethoxy)propyldimethylsiloxy-terminated polydimethylsiloxane with D3 < 5 ppm, D4 15 ppm, D5 22 ppm, and D6 439 ppm (n = 40, OH value 33 mgKOH / g) was added in four equal portions over 1 hour, and then aged at 70 °C for 3.5 hours. Thereafter, 8.87 g (0.120 mol) of glycidol was added and aged at 70 °C for 3 hours to obtain 233.30 g of a colorless slightly turbid viscous liquid. From NCO / OH = 2.0, m is 1. The physical properties are shown in Table 1. The low molecular cyclic siloxanes were diluted with 10 mL of acetone using tetradecane as an internal standard per 1 g of the sample and measured by GC. As a result, the total amount of D3 to D6 was < 353 ppm. (D3: < 5 ppm, D4: < 5 ppm, D5: < 5 ppm, D6: 338 ppm)

[0074] [Comparative Example 1] 61.25 g (0.551 mol NCO) of isophorone diisocyanate was charged into a 500 mL separable flask, and a mechanical stirrer, stirring blade, Dimroth reflux condenser, nitrogen gas inlet, and thermometer were attached, and nitrogen gas was passed through. Next, 0.26 g (0.1 mass%) of K-KAT XK-640 as a catalyst was added, and the temperature was raised until the internal temperature reached 60 °C. Therein, using a 300 mL dropping funnel, 200.00 g (0.413 mol OH, NCO / OH = 1.33) of 3-(2-hydroxyethoxy)propyldimethylsiloxy-terminated polydimethylsiloxane with D3 of 64 ppm, D4 of 59 ppm, D5 of 23 ppm, and D6 of 226 ppm (n = 8, OH value 116 mg KOH / g) was added over 30 minutes, and then aged at 70 °C for 3 hours. Thereafter, 10.46 g (0.141 mol) of glycidol was added and aged at 70 °C for 2 hours to obtain 266.50 g of a colorless slightly turbid viscous liquid. From NCO / OH = 1.33, m is 3. The low molecular cyclic siloxanes were extracted from 1 g of the sample with 10 mL of hexane using tetradecane as an internal standard and measured by GC. As a result, the total amount of D3 to D6 was 348 ppm. (D3: 62 ppm, D4: 58 ppm, D5: 18 ppm, D6: 210 ppm)

[0075] [Table 1]

[0076] [Example 6] In a 500 mL separable flask, 9.90 g (0.118 mol NCO) of hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged. A mechanical stirrer, stirring blade, Dimroth reflux condenser, nitrogen gas inlet, and thermometer were attached, and nitrogen gas was passed through. Next, 0.11 g (0.1 mass%) of K-KAT XK-640 as a catalyst was added, and the temperature was raised until the internal temperature reached 60°C. Then, using a 300 mL dropping funnel, 100.00 g (0.059 mol OH, NCO / OH = 2.0) of 3-(2-hydroxyethoxy)propyldimethylsiloxy-terminated polydimethylsiloxane (n = 40, OH value 33 mg KOH / g) was added in 1 / 4 liquid volume portions over 40 minutes, and then aged at 70°C for 3 hours. Thereafter, 4.38 g (0.059 mol) of glycidol was added, and aged at 70°C for 2 hours to obtain 111.98 g of a white solid. From NCO / OH = 2.0, m is 1. The physical properties are shown in Table 2.

[0077] [Example 7] In a 500 mL separable flask, 15.43 g (0.118 mol NCO) of dicyclohexylmethane diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd., isomer mixture) was charged. A mechanical stirrer, stirring blade, Dimroth reflux condenser, nitrogen gas inlet, and thermometer were attached, and nitrogen gas was passed through. Next, 0.11 g (0.1 mass%) of K-KAT XK-640 as a catalyst was added, and the temperature was raised until the internal temperature reached 60°C. Then, using a 300 mL dropping funnel, 100.00 g (0.059 mol OH, NCO / OH = 2.0) of 3-(2-hydroxyethoxy)propyldimethylsiloxy-terminated polydimethylsiloxane (n = 40, OH value 33 mg KOH / g) was added in 1 / 4 liquid volume portions over 40 minutes, and then aged at 70°C for 3 hours. Thereafter, 4.40 g (0.059 mol) of glycidol was added, and aged at 70°C for 2 hours to obtain 117.59 g of a white solid. From NCO / OH = 2.0, m is 1. The physical properties are shown in Table 2.

[0078] [Example 8] Into a 500 mL separable flask, 11.07 g (0.118 mol NCO) of xylylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged. A mechanical stirrer, stirring blade, Dimroth reflux condenser, nitrogen gas inlet, and thermometer were attached, and nitrogen gas was passed through. Next, 0.11 g (0.1 mass%) of K-KAT XK-640 as a catalyst was added, and the temperature was raised until the internal temperature reached 60°C. Therein, using a 300 mL dropping funnel, 100.00 g (0.059 mol OH, NCO / OH = 2.0) of 3-(2-hydroxyethoxy)propyldimethylsiloxy-terminated polydimethylsiloxane (n = 40, OH value 33 mg KOH / g) was added in portions of 1 / 4 of the liquid volume over 40 minutes, and then aged at 70°C for 3.5 hours. Thereafter, 4.40 g (0.059 mol) of glycidol was added and aged at 70°C for 2.5 hours to obtain 113.19 g of a white gel. From NCO / OH = 2.0, m is 1. The physical properties are shown in Table 2.

[0079] [Example 9] Into a 500 mL separable flask, 22.87 g (0.235 mol NCO) of di(isocyanatomethyl)cyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged. A mechanical stirrer, stirring blade, Dimroth reflux condenser, nitrogen gas inlet, and thermometer were attached, and nitrogen gas was passed through. Next, 0.22 g (0.1 mass%) of K-KAT XK-640 as a catalyst was added, and the temperature was raised until the internal temperature reached 60°C. Therein, using a 300 mL dropping funnel, 200.00 g (0.118 mol OH, NCO / OH = 2.0) of 3-(2-hydroxyethoxy)propyldimethylsiloxy-terminated polydimethylsiloxane (n = 40, OH value 33 mg KOH / g) was added in portions of 1 / 4 of the liquid volume over 40 minutes, and then aged at 70°C for 3.5 hours. Thereafter, 8.78 g (0.118 mol) of glycidol was added and aged at 70°C for 2.5 hours to obtain 228.22 g of a colorless slightly turbid viscous liquid. From NCO / OH = 2.0, m is 1. The physical properties are shown in Table 2.

[0080] [Example 10] In a 500 mL separable flask, 20.50 g (0.235 mol NCO) of 2,4-toluene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged. A mechanical stirrer, stirring blades, Dimroth reflux condenser, nitrogen gas inlet, and thermometer were attached, and nitrogen gas was passed through. Next, 100.00 g of dehydrated toluene (manufactured by Kanto Chemical Co., Inc.) was added, and the temperature was raised until the internal temperature reached 70°C. Using a 300 mL dropping funnel, 200.00 g (0.118 mol OH, NCO / OH = 2.0) of 3-(2-hydroxyethoxy)propyldimethylsiloxy-terminated polydimethylsiloxane (n = 40, OH value 33 mgKOH / g) was added over 1 hour and 15 minutes, and the mixture was aged at 70°C for 6 hours. Thereafter, 9.23 g (0.124 mol) of glycidol was added, and the mixture was aged at 70°C for 4 hours, 80°C for 28 hours, and 90°C for 19 hours to obtain 134.40 g of a colorless transparent liquid. Since NCO / OH = 2.0, m is 1. The physical properties are shown in Table 2.

[0081] [Example 11] In a 500 mL separable flask, 24.95 g (0.199 mol NCO) of 4,4'-bis(phenylisocyanato)methane (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged. A mechanical stirrer, stirring blades, Dimroth reflux condenser, nitrogen gas inlet, and thermometer were attached, and nitrogen gas was passed through. Next, 67.73 g of dehydrated toluene (manufactured by Kanto Chemical Co., Inc.) was added, and the temperature was raised until the internal temperature reached 70°C. Using a 300 mL dropping funnel, 169.50 g (0.100 mol OH, NCO / OH = 2.0) of 3-(2-hydroxyethoxy)propyldimethylsiloxy-terminated polydimethylsiloxane (n = 40, OH value 33 mgKOH / g) was added over 40 minutes, and the mixture was aged at 70°C for 8 hours. Thereafter, 7.50 g (0.101 mol) of glycidol was added, and the mixture was aged at 70°C for 11 hours, 80°C for 8.5 hours, and 90°C for 5 hours to obtain 232.64 g of a white gel. Since NCO / OH = 2.0, m is 1. The physical properties are shown in Table 2.

[0082] [Example 12] 49.30 g (0.443 mol NCO) of isophorone diisocyanate was charged into a 500 mL separable flask, and a mechanical stirrer, stirring blade, Dimroth reflux condenser, nitrogen gas inlet, and thermometer were attached, and nitrogen gas was passed through. Next, 0.25 g (0.1 mass%) of K-KAT XK-640 as a catalyst was added, and the temperature was raised until the internal temperature reached 60°C. Using a 300 mL dropping funnel, 200.30 g (0.222 mol OH, NCO / OH = 2.0) of 3-(2-hydroxyethoxy)propyldimethylsiloxy-terminated poly(dimethylsiloxane-diphenylsiloxane) copolymer (n = 12 (dimethylsiloxy units: 8, diphenylsiloxy units: 4), OH value 62 mg KOH / g) with D3 - D6 at 0 ppm was added over 1 hour, and then aged at 70°C for 2 hours. Thereafter, 16.61 g (0.224 mol) of glycidol was added and aged at 70°C for 2 hours to obtain 259.70 g of a colorless slightly turbid viscous liquid. From NCO / OH = 2.0, m is 1. The physical properties are shown in Table 2. The low molecular cyclic siloxanes were extracted from 1 g of the sample with 10 mL of hexane using tetradecane as an internal standard and measured by GC. As a result, the total amount of D3 - D6 was 0 ppm.

[0083] [Table 2]

[0084] [Evaluation] Compatibility study To 5 g of the samples obtained from Examples 1, 2, 4, 5, 12, and Comparative Example 1, 1 g of tetraethylenepentamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and mixing (2,000 rpm) and defoaming (2,200 rpm) were repeated 1 - 4 times using ARE-310 manufactured by Shinky Co., Ltd., and the appearance was confirmed (Examples 13 - 17, Comparative Example 2). Also, as epoxy-modified silicones, KF-105 (epoxy equivalent 510 g / mol) and X-22-163A (epoxy equivalent 1,000 g / mol) manufactured by Shin-Etsu Chemical Co., Ltd. were prepared in the same manner, and the appearance (immediately after mixing, 1 week later) was compared (Comparative Examples 3 - 4). The results are shown in Table 3 below.

[0085]

Table 3

[0086] Hardening study Samples (40 g) obtained from Examples 1 to 5, 7 to 12, and Comparative Example 1 were used to prepare cured products using diphenyldiaminomethane (DDM) (manufactured by Tokyo Chemical Industry Co., Ltd.) as an amine curing agent (Examples 18 to 28, Comparative Example 5). The amount of DDM added was such that the amount of N-H of DDM was 1 equivalent per mole of each epoxy group. For comparison, samples were similarly prepared using KF-105 and X-22-163A (Comparative Examples 6 to 7). The sample and DDM were mixed at 100 °C, poured into a mold of 170 × 130 × 2 mm, covered, and cured at 150 °C for 3 hours. In Examples 10 and 11, after removing the solvent with an evaporator, the sample was poured into the mold to prepare a cured product. The hardness was measured 5 times using a digi test manufactured by bareiss, and the average value was determined. For the breaking strength and elongation at break, after punching out with a No. 2 dumbbell cutter, measurements were taken 3 times using AGS-X manufactured by SHIMADZU Corporation (tensile speed: 500 mm / min), and the average value was determined. The results are shown in Tables 4 and 5.

[0087]

Table 4

[0088]

Table 5

[0089] As shown in Examples 13 to 17, the polyorganosiloxane of the present invention has good compatibility with an amine curing agent (tetraethylenepentamine) at room temperature and does not separate even after one week. On the other hand, the epoxy-modified silicones of Comparative Examples 3 and 4 showed remarkable separation from the amine curing agent.

[0090] In addition, when heat curing was carried out at a high temperature with an amine curing agent added, the polyorganosiloxane of the present invention with good compatibility gave a cured product without problems regardless of the value of the epoxy equivalent (Examples 18 to 28). Also, both the breaking strength and the elongation at break showed excellent values.

[0091] On the other hand, for the epoxy-modified silicones of Comparative Examples 6 and 7, separation was a problem for the epoxy-modified silicone with a high epoxy equivalent (Comparative Example 7), and it remained uncured. Also, for the epoxy-modified silicone with a low epoxy equivalent (Comparative Example 6), although it cured by high-temperature heating to obtain a pale yellow transparent cured product, both the breaking strength and the elongation at break showed low values. Further, for the polyorganosiloxane (Comparative Example 1) with a degree of polymerization outside the range of the present invention, it was shown from the results of Comparative Example 5 that the dispersibility in the epoxy resin deteriorated. From this, it was shown that the polyorganosiloxane of the present invention has excellent performance.

[0092] Note that the present invention is not limited to the above-described embodiments. The above-described embodiments are examples, and any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits the same operational effects is included in the technical scope of the present invention.

Claims

1. A polyorganosiloxane represented by the following formula (1). 【Chemical 1】 (In formula (1), R １ represents a group independently selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms, or a hydroxyl group, X represents a divalent alkylene group having 1 to 10 carbon atoms independently of one another, Y represents a group independently selected from an alkylene group which may have an ether bond having 5 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, and an aralkylene group having 7 to 30 carbon atoms, Z represents an alkylene group which may have an ether bond having 1 to 20 carbon atoms independently of one another, n is an integer of 0 to 100, and m is 1 to 2.)

2. The polyorganosiloxane represented by the formula (1), wherein the number average molecular weight in terms of polystyrene standard substance is 500 to 100,000. The polyorganosiloxane according to Claim 1.

3. The polyorganosiloxane represented by the formula (1), wherein the epoxy equivalent (g / mol) is 300 to 5,000 g / mol. The polyorganosiloxane according to Claim 1 or Claim 2.

4. The polyorganosiloxane represented by the formula (1) contains hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in a total amount of 3,000 ppm or less and 0 ppm or more. The polyorganosiloxane according to any one of Claims 1 to 3.

5. A method for producing a polyorganosiloxane represented by the following formula (1), [Chemical 2] (In formula (1), R １ represents a group independently selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms, or a hydroxyl group, X represents a divalent alkylene group having 1 to 10 carbon atoms independently of each other, Y represents a group independently selected from an alkylene group which may have an ether bond having 5 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, and an aralkylene group having 7 to 30 carbon atoms, Z represents an alkylene group which may have an ether bond having 1 to 20 carbon atoms independently of each other, n is an integer of 0 to 100, and m is 1 to 2.) in the presence or absence of a catalyst and in the presence or absence of a solvent, reacting a both-end carbinol-modified silicone represented by the following formula (2), a diisocyanate compound represented by the following formula (3), and a compound having an epoxy group and a hydroxyl group represented by the following formula (4). A method for producing a polyorganosiloxane. 【Chemical Formula 3】 【Chemical 4】 [Chemical Formula 5] (Each R １ , X, Y, Z, and n are the same as described above.)

6. As the both-end carbinol-modified silicone represented by the formula (2), a both-end carbinol-modified silicone having a hydroxyl value (OH value) of 10 to 500 mgKOH / g is used. The method for producing a polyorganosiloxane according to Claim 5.

7. As the both-end carbinol-modified silicone represented by the formula (2), a compound containing hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in a total amount of 3,000 ppm or less and 0 ppm or more is used. The method for producing a polyorganosiloxane according to Claim 5 or Claim 6.

8. The method for producing a polyorganosiloxane according to any one of claims 5 to 7, characterized in that the reaction is carried out such that the ratio (NCO / OH ratio) of the number of moles of hydroxyl groups (OH) of the both-terminal carbinol-modified silicone represented by the formula (2) to the number of moles of isocyanate groups (NCO) of the diisocyanate compound represented by the formula (3) is 1.5 to 2.

0. **Claim 9** A composition comprising the polyorganosiloxane according to any one of claims 1 to 4 and an amine curing agent.

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