Method for treating waste hydrogenpolysiloxane and hydrogenpolysiloxane treatment device

Abstract

To provide a method for safely and efficiently reducing the amount of residual silicon-hydrogen bonds in hydrogen polysiloxane waste containing water, wherein the method can be implemented with inexpensive equipment, and the method has reduced load on the equipment in the treatment process.SOLUTION: The hydrogen polysiloxane waste that occurs in the process of producing an emulsion containing hydrogen polysiloxane is treated with an emulsion of a hydrocarbon compound having only one carbon-carbon double bond in the molecule.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a method for treating waste hydrogenpolysiloxane generated in the process of producing an emulsion containing organohydrogenpolysiloxane (hereinafter also simply referred to as hydrogenpolysiloxane), and to an apparatus for treating hydrogenpolysiloxane. [Background technology]

[0002] Hydrogenpolysiloxanes are often used in the process of producing organopolysiloxanes into which various organic groups have been introduced by addition reaction with organic unsaturated compounds having aliphatic unsaturated bonds in the presence of a catalyst. The obtained organopolysiloxanes are widely used in the fields of paints, molding materials, medical materials, various coating materials, cosmetics, personal care compositions, home care compositions, release agents, fiber treatment agents, etc.

[0003] Hydrogenpolysiloxanes are not only used as they are in the form of oils or diluted with any solvent, but in recent years they are increasingly being used in the form of aqueous emulsions from the standpoint of working environment safety and reducing the environmental burden.

[0004] When hydrogen polysiloxane comes into contact with water or substances that contain active hydrogen, such as amino groups, it undergoes intermolecular dehydrogenation and releases hydrogen gas. Hydrogen gas can be flammable and explosive, so care must be taken when handling it. Emulsion-type hydrogen polysiloxane coexists with water, which is an active hydrogen source, and releases hydrogen gas over time as a result of a hydrolysis reaction, so safety is required in terms of storage and handling. This safety is required not only for the product, but also for the waste generated during the manufacturing process.

[0005] In processes for producing hydrogen polysiloxane emulsions and processes for producing organo polysiloxanes that use such emulsions, waste emulsions of hydrogen polysiloxanes are generated for reasons such as pre-cutting, post-cutting, cleaning of the inside of the equipment, etc. Such waste emulsions are usually stored until a certain amount is reached, after which they are transported to an incineration facility and disposed of by incineration.

[0006] However, hydrogen gas gradually evolves from the stored waste emulsion, posing a risk of the storage container exploding or the hydrogen gas catching fire. Although measures such as attaching a gas vent cap have been taken to prevent the container from bursting, there is a risk of the hydrogen gas released from the container catching fire. Also, while it is possible to reduce the amount of hydrogen polysiloxane stored in the container to suppress the increase in the container's internal pressure, this would result in a problem that the container volume would be large compared to the amount stored, requiring a large storage space. Therefore, unlike oil-like or solvent-diluted hydrogenpolysiloxanes, which can be stably stored without the risk of hydrogen generation, it has been difficult to safely store hydrogenpolysiloxane emulsions until they can be disposed of.

[0007] One possible measure to suppress hydrogen generation over time is to physically separate the active hydrogen source from the hydrogenpolysiloxane. However, in the case of, for example, hydrogenpolysiloxane containing water, it is difficult to completely remove the water from the mixture. Methods of removing water by applying external energy such as heat promote the generation of hydrogen gas and there is a risk of the hydrogen gas igniting, raising safety concerns. Another method for suppressing hydrogen generation over time is to reduce the amount of residual silicon-hydrogen bonds in the hydrogenpolysiloxane. For example, Patent Document 1 discloses a method of blowing ethylene gas into the hydrogenpolysiloxane. However, this method involves a reaction at the gas-liquid interface, so it is difficult to increase the reaction efficiency, and the amount of residual hydrogen in the hydrogenpolysiloxane cannot be sufficiently reduced. In addition, advanced equipment capable of controlling pressure and temperature is required.

[0008] Furthermore, the addition reaction between a hydrogenpolysiloxane and an organic unsaturated compound having an aliphatic unsaturated bond in the presence of a catalyst is an exothermic reaction, so care must be taken to prevent the temperature of the system from increasing due to the heat of the addition reaction, and in some cases a special reactor or the like may be required.

[0009] Patent Document 2 discloses a method for obtaining a silicone oil emulsion by mixing an emulsion of an alkenylsiloxane having alkenyl groups at both ends with an emulsion of an organohydrogenpolysiloxane. In this method, the hydrogen-silicon bond of the hydrogenpolysiloxane and the vinyl group bonded to the silicon atom of the alkenylsiloxane undergo a crosslinking reaction in a ratio of 1:1, resulting in a reduction in the amount of residual silicon-hydrogen bonds in the hydrogenpolysiloxane. This method is safe in that it does not apply external energy (heat, pressure, etc.) to the system. However, as mentioned above, the reaction is (hydrogen-silicon bond):(vinyl group) = 1:1, so the more functional groups (hydrogen-silicon bonds) contained in the hydrogen polysiloxane, the more corresponding alkenyl siloxane is required, which increases the amount of waste. In addition, silicone itself is expensive, and in the case of siloxanes with multiple Si-H groups per molecule, there are problems such as insufficient reaction rate due to steric hindrance. Therefore, even with this method, it is difficult to reduce the amount of hydrogen remaining in the hydrogen polysiloxane to a safe level. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] JP 2001-114895 A [Patent Document 2] JP 2020-12076 A Summary of the Invention [Problem to be solved by the invention]

[0011] Therefore, there has been a demand for a processing method that can sufficiently reduce the amount of hydrogen remaining in discarded hydrogenpolysiloxane. The present invention has been made in view of the above, and aims to provide a method for safely and efficiently reducing the amount of hydrogen remaining in waste hydrogen polysiloxane containing water, which can be realized using inexpensive equipment and imposes a small burden on the equipment in the treatment process. Here, "safe" means that an excessively exothermic reaction does not occur, "highly efficient" means that the amount of hydrogen remaining is sufficiently reduced without using an excessive amount of chemical substance relative to the hydrogen polysiloxane (for example, by using a theoretical amount of chemical substance), "inexpensive equipment" means that equipment that can withstand high temperatures and high pressures or highly airtight equipment is not required, and "low burden on equipment" means that components such as piping and valves in the equipment are less likely to become clogged. Another object of the present invention is to provide an apparatus that can sufficiently reduce the amount of residual hydrogen in water-containing hydrogenpolysiloxane using safe and inexpensive equipment. [Means for solving the problem]

[0012] As a result of intensive research conducted by the present inventors in order to achieve the above-mentioned object, it has been found that by using an emulsion (hereinafter also referred to as an emulsion) of a compound having one carbon-carbon double bond in the molecule, the amount of Si-H can be reduced to a safe range in an inexpensive and safe process. In addition, it was discovered that a hybrid apparatus that combines a batch system and a continuous system enables efficient treatment even when the process includes a step of reducing the amount of hydrogen remaining in the hydrogenpolysiloxane, which takes a certain amount of time.

[0013] The method of the present invention for reducing the amount of residual silicon-hydrogen bonds (also referred to as residual hydrogen) in waste hydrogen polysiloxane comprises: A method for treating waste hydrogen polysiloxane generated in a process for producing an emulsion containing hydrogen polysiloxane, the method comprising a mixing step of mixing the following component (A) with an emulsion containing the following component (B) to obtain an alkyl-modified silicone emulsion composition, the method comprising the steps of: The component (A) is (A) the waste hydrogenpolysiloxane contains water and an organohydrogensiloxane having one or more hydrogen atoms bonded to silicon atoms in each molecule, The component (B)-containing emulsion is (B) a hydrocarbon compound having only one carbon-carbon double bond in the molecule; (C) water; (D) Platinum group catalysts (E) an emulsifier. Here, the water as component (C) is water for emulsifying component (B) and includes water added at the initial stage of emulsification (hereinafter also referred to as initial water), water added to dilute the mixture of component (B) and initial water (hereinafter also referred to as dilution water), and water added to adjust the temperature of the mixture containing component (B), initial water, and dilution water (hereinafter also referred to as temperature adjustment water).

[0014] In the process of producing an emulsion containing hydrogenpolysiloxane, waste containing hydrogenpolysiloxane and water (i.e., waste hydrogenpolysiloxane) is generated due to pre-cutting, post-cutting, cleaning of the inside of the equipment, etc. This waste hydrogenpolysiloxane is usually in an emulsion or liquid crystal state. The hydrogen polysiloxane contained in the waste hydrogen polysiloxane gradually reacts with the water contained in the waste hydrogen polysiloxane to generate hydrogen gas. Therefore, in the present invention, waste hydrogenpolysiloxane is reacted with a compound (B) having only one carbon-carbon double bond in the molecule, thereby reducing the number of remaining silicon-hydrogen bonds in the waste hydrogenpolysiloxane molecule and suppressing the generation of hydrogen gas.

[0015] If component (B) is oily, it cannot be mixed uniformly with component (A), which is an emulsion, and phase separation occurs. As a result, the reaction efficiency decreases. Therefore, in the present invention, component (E), which is an emulsifier, and water (component (C), which is water for emulsifying component (B), are mixed with component (B) and emulsified to form an emulsion. Since component (B) in an emulsion state can be mixed uniformly with component (A), which is also an emulsion, the amount of remaining silicon-hydrogen bonds contained in component (A) can be reduced with high efficiency.

[0016] Component (B) having only one carbon-carbon double bond in the molecule has less steric hindrance during the addition reaction with component (A) compared to when it has two or more carbon-carbon double bonds, and therefore the amount of remaining silicon-hydrogen bonds in component (A) can be reduced more efficiently. Furthermore, when there is only one carbon-carbon double bond in a molecule, no cross-linking reaction occurs, so no gel-like or solid products are produced. This means that there is less strain on the equipment, such as clogging of pipes in the processing facility, and maintenance is easy.

[0017] The platinum group catalyst, component (E), is a catalyst necessary for the addition reaction of components (A) and (B). This reaction is carried out at room temperature and pressure, and does not require high temperature and pressure conditions, making it very safe and possible to carry out the reaction using simple equipment.

[0018] The present invention also provides An apparatus for treating component (a) containing water and an organohydrogensiloxane having one or more hydrogen atoms bonded to silicon atoms in each molecule, with component (b) containing a compound having only one carbon-carbon double bond in the molecule, comprising: A component (a) storage tank for storing the component (a); The component (a) outlet flow rate adjustment mechanism; An apparatus for producing the component (b)-containing emulsion; The component (b) flow rate control mechanism; A reaction vessel for receiving the component (a) and an emulsion containing the component (b); A water line equipped with a flow rate control mechanism for introducing water into the reaction tank; A temperature measuring means for measuring the internal temperature of the reaction vessel; a control means for controlling an amount of at least one of the component (a), the component (b)-containing emulsion, and water introduced into the reaction tank based on the temperature measured by the temperature measuring means; and and a detection means (not shown) for detecting the amount of SiH remaining in the product stored in the reaction tank. This is a hydrogen polysiloxane treatment device.

[0019] To carry out the addition reaction between component (a) containing water and hydrogen polysiloxane and component (b) containing a compound having only one carbon-carbon double bond in the molecule, a very simple facility can be used. For example, the components (a) and (b) can be manually introduced into a container having an opening. However, depending on the background of an increase in the amount of processing, a reduction in personnel, a request to reduce processing time, etc., a certain degree of automation is required. However, when the reaction between components (a) and (b) takes a long time, full automation such as continuously adding both components is difficult, and the facility becomes large-scale. Therefore, the present invention provides a processing device that is simple yet efficiently performing processing by performing part of the processing continuously, and then detecting the end point of the addition reaction and discharging the product in a batch process.

[0020] In the treatment device of the present invention, component (a) and component (b) are each introduced into the reaction tank at a predetermined flow rate. Water can be introduced into the reaction tank at a predetermined flow rate. The flow rates of component (a), component (b), and water are adjusted according to the temperature in the reaction tank. This makes it possible to perform treatment while automatically adding component (a) and component (b) to the reaction tank while suppressing sudden temperature changes. This automatic process ends when the predetermined amounts of component (a) and component (b) have been added to the reaction tank.

[0021] The reaction vessel further includes a means for detecting the amount of silicon-hydrogen bonds remaining in component (a). This allows detection of the end point of the addition reaction with component (b), which indicates that the amount of silicon-hydrogen bonds remaining in component (a) has been sufficiently reduced. After the end point of the reaction is detected, the reaction product is discharged from the reaction vessel. This end point detection and discharge of the reaction product are batch processes.

[0022] By making the processing equipment capable of combining the automatic process and the batch process in this way, processing can be performed even in equipment with low airtightness at room temperature and pressure. Therefore, there is no need to use heat-resistant materials that can withstand high temperatures, highly airtight equipment, pressure adjustment equipment, etc., and processing can be performed using inexpensive and simple processing equipment. [Brief description of the drawings]

[0023] [Figure 1] FIG. 1 is a diagram showing an example of the configuration of a hydrogen polysiloxane treatment apparatus according to the present invention. [Diagram 2] FIG. 2 is a diagram showing an example of the configuration of an apparatus for producing an emulsion containing component (b) according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] The method for reducing the amount of residual silicon-hydrogen bonds in waste hydrogenpolysiloxane and the hydrogenpolysiloxane treatment apparatus according to the present invention will be described in detail below.

[0025] The method of the present invention for reducing the amount of residual silicon-hydrogen bonds in waste hydrogen polysiloxane comprises the steps of: A method for treating waste hydrogen polysiloxane generated in a process for producing an emulsion containing hydrogen polysiloxane, the method comprising a mixing step of mixing the following component (A) with an emulsion containing the following component (B) to obtain an alkyl-modified silicone emulsion composition, the method comprising the steps of: The component (A) is (A) the waste hydrogenpolysiloxane contains water and an organohydrogensiloxane having one or more hydrogen atoms bonded to silicon atoms in each molecule, The component (B)-containing emulsion is (B) a hydrocarbon compound having only one carbon-carbon double bond in the molecule; (C) water; (D) Platinum group catalysts (E) an emulsifier.

[0026] (Regarding component (A)) Component (A) is a waste hydrogenpolysiloxane that contains water and an organohydrogensiloxane having one or more hydrogen atoms bonded to silicon atoms in each molecule. The waste hydrogenpolysiloxane is generated in the process of producing an emulsion containing hydrogenpolysiloxane. Waste organohydrogensiloxanes having at least one hydrogen atom bonded to a silicon atom in each molecule are represented by the following general formula (1). R 1 a SiO (4-a) / 2 (1) (In formula (1), R 1 may be the same or different in the molecule and are a group selected from a substituted or unsubstituted saturated monovalent hydrocarbon group having 1 to 25 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or a hydrogen atom. a is an integer from 1 to 3.

[0027] The above R1 Specific examples of the alkyl group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, 2-ethylhexyl, heptyl, octyl, nonyl, decyl, and dodecyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl; aryl groups such as phenyl, tolyl, xylyl, biphenyl, and naphthyl; substituted hydrocarbon groups such as benzyl, phenylethyl, and phenylpropyl, in which some or all of the hydrogen atoms in the hydrocarbon group have been replaced with halogen atoms, cyano groups, and the like, such as chloromethyl, 2-bromoethyl, 3,3,3-trifluoropropyl, 3-chloropropyl, chlorophenyl, dibromophenyl, tetrachlorophenyl, difluorophenyl, β-cyanoethyl, γ-cyanopropyl, and β-cyanopropyl; alkoxy groups such as methoxy, ethoxy, and propyl; hydroxyl; and hydrogen. Particularly preferred is a methyl group.

[0028] The above organohydrogensiloxane is produced by a method known to those skilled in the art, and specific examples thereof include methylhydrogenpolysiloxane, dimethylsiloxane-methylhydrogensiloxane copolymer, methylphenylsiloxane-methylhydrogensiloxane copolymer, etc. These may be used alone or in combination. The structure of the organohydrogensiloxane is not particularly limited, but may be cyclic, linear, or partially branched linear. The hydrogen atoms contained in the organohydrogenpolysiloxane may be bonded only to the silicon atoms at the ends of the molecular chain of the organohydrogenpolysiloxane, or may be bonded to silicon atoms at the ends of the molecular chain or non-terminals of the molecular chain. The number of hydrogen atoms per molecule of the organohydrogenpolysiloxane is not particularly limited. Hereinafter, the organohydrogenpolysiloxane will also be simply referred to as hydrogenpolysiloxane.

[0029] The process of producing an emulsion containing hydrogen polysiloxane is a process of producing an emulsion of hydrogen polysiloxane, which is an emulsion, from oily hydrogen polysiloxane. The production method is not particularly limited, and may be a known method such as liquid crystal emulsification, mechanical emulsification, phase inversion emulsification, phase inversion temperature emulsification, or D phase emulsification. The obtained emulsion is preferably an oil-in-water type.

[0030] The liquid crystal emulsification method is a technique for producing fine emulsion particles that disperse and hold a dispersed phase (oil phase in O / W emulsions) in liquid crystal formed by a surfactant. Mechanical emulsification is an emulsification method that utilizes physical convection, and is performed using a homogenizer or agitator. Agitators mix substances vigorously to create physical convection, while homogenizers use ultrasound or high pressure to create physical convection to mix substances together. The phase inversion emulsification method is a method for producing an O / W emulsion by dissolving a surfactant in an oil phase, then adding an aqueous phase while stirring, and inverting the continuous phase from the oil phase to the aqueous phase. The phase inversion temperature emulsification method is an emulsification method that utilizes the phase inversion temperature in a three-component system of nonionic surfactant, oil, and water, in which, at a certain temperature, the nonionic surfactant associates infinitely and separates into a macroscopic phase containing a large amount of oil and water, and when the temperature is further raised, the nonionic surfactant dissolves in the oil phase, forming reverse micelles and solubilizing the water. The D-phase emulsification method is a method in which a polyhydric alcohol is added as a fourth component to a surfactant, oil, and water to produce a fine O / W emulsion.

[0031] Waste hydrogen polysiloxane generated in the process of manufacturing an emulsion containing hydrogen polysiloxane includes those discarded in pre-cutting or post-cutting in the manufacturing process, those washed away for reasons such as cleaning inside the equipment, and those extracted from the manufacturing process for inspection. The form of the waste hydrogen polysiloxane varies depending on the process in which it is generated and the storage conditions after generation. There are forms such as an emulsion state, a liquid crystal state, an oil state containing a trace amount of water, or a state in which it is phase-separated into an oil phase and an aqueous phase. In any case, since hydrogen polysiloxane and water coexist, hydrogen gas is gradually generated by the hydrolysis reaction.

[0032] When component (A) is in a liquid crystal state, a polyhydric alcohol can be added to component (A). Examples of polyhydric alcohols include ethylene glycol, polyethylene glycol, propylene glycol, glycerin, 1,3-butanediol, and D-sorbitol. By adding a polyhydric alcohol, the cohesive force of the surfactant can be alleviated and fluidity can be obtained. In the case of solid-liquid coexistence, the homogeneity is poor, and uneven processing occurs when mixed with component (B) and processed, and silicon-hydrogen bonds may remain. In the case of fluidity (all liquid), the homogeneity is excellent, so uneven processing is less likely to occur.

[0033] These waste hydrogen polysiloxanes must be stored in a state in which hydrogen gas generation is suppressed, either immediately after generation or after a certain amount has been stored. A state in which hydrogen gas generation is suppressed means a state in which the amount of silicon-hydrogen bonds remaining in the hydrogen polysiloxane is small. For example, 0.001% by mass or less, and more preferably 0.0001% by mass or less. If 0.001% by mass or more of silicon-hydrogen bonds remain, a large amount of hydrogen gas may be generated in a short period of time, reducing safety.

[0034] When the volume of the storage container and the amount of hydrogenpolysiloxane enclosed in the container are limited as a measure to prevent an increase in the internal pressure of the storage container, the allowable amount of residual silicon-hydrogen bonds is not limited to the above. For example, when the waste hydrogen polysiloxane (a) is filled in a 200 L non-pressure resistant container to 30% of the container volume, the upper limit of the silicon-hydrogen bond residual amount is preferably 0.02% by mass, and when the container volume is filled to 80% of the container volume, the upper limit is preferably 0.001% by mass or less. According to Charles' law, when the pressure is constant, the volume is proportional to the temperature, so when the temperature during storage is high, it is preferable to further lower the upper limit. If the parts by mass of the waste hydrogen polysiloxane and the amount of residual silicon-hydrogen bonds (mass%) are known, the volume of hydrogen that may be generated can be estimated using formula (2).

number

[0035] The concentration of hydrogenpolysiloxane contained in component (A) is not particularly limited, and when component (A) is in the form of an emulsion, it is, for example, 5 to 70% by mass, and preferably 10 to 60% by mass.

[0036] The concentration of water contained in component (A) is not particularly limited, and when component (A) is in the form of an emulsion, it is, for example, about 30 to 95% by mass, and preferably 40 to 90% by mass.

[0037] Component (A) may contain components other than hydrogenpolysiloxane and water, and other optional components (for example, surfactants, stabilizers, preservatives) may be added as necessary.

[0038] (Regarding component (B)) The hydrocarbon compound having only one carbon-carbon double bond in the molecule may be an alkene or a cycloalkene, or a mixture thereof, preferably an alkene.

[0039] When component (B) is an unsaturated hydrocarbon having only one carbon-carbon double bond in the molecule, it is preferable in that it is easily available.

[0040] It is more preferable that component (B) is an α-olefin having a double bond at the end, because it has less steric hindrance during the reaction and is highly reactive. Therefore, it is preferably a straight-chain type.

[0041] When component (B) is a hydrocarbon, the number of carbon atoms is not particularly limited and may be, for example, 2 to 20, and a smaller carbon number is more preferable because of higher reactivity. A carbon number of 10 to 14 is even more preferable for reasons of handling (flash point, handling, etc.). The component (b) in the present invention is an α-olefin having a carbon number of 10 to 14. This α-olefin having a carbon number of 10 to 14 may be linear or branched, and is preferably linear. Specific examples include 1-decene, 1-dodecene, and 1-tetradecene.

[0042] The amount of component (B) to be added must depend on the amount of residual silicon-hydrogen bonds in component (A). Specifically, the amount of component (B) is the amount required to make the amount of silicon-hydrogen bond residues in component (A) detectable by alkali titration 0% or more and 0.001% or less. In consideration of reaction efficiency, it is preferable to use an amount such that there are 1.0 to 2.0 alkenyl groups in component (B) per one hydrogen atom bonded to a silicon atom contained in the entire component (A). The emulsion containing component (B) is mixed with component (A) after being emulsified with the following components (C) to (E). In general, emulsions become unstable over time and cause separation, sedimentation, and other losses. For this reason, it is more preferable to use component (B) promptly after emulsification. The elapsed time after emulsification is preferably, for example, 1 to 10 days depending on the properties and concentrations of components (B) to (E).

[0043] Although the component (C) is not particularly limited, it is preferable to use ion-exchanged water. The pH of the ion-exchanged water is preferably pH 3 to 10, and particularly preferably pH 5 to 8. It is not recommended to use mineral water, but when it is used, it is preferable to use it together with a metal deactivator or the like.

[0044] Water, which is component (C), can be divided into initial water, dilution water, and temperature-adjusting water depending on its role. Water added during emulsification of component (B) is called initial water, water added during dilution of the component (B) emulsion is called dilution water, and water acting as a medium to maintain the temperature of the reaction system below a certain level when the temperature of the reaction system rises due to heat generated by the reaction of components (B) and (A) is called temperature-adjusting water here.

[0045] The initial water and dilution water used to emulsify component (B) also function to control the temperature of the system. Therefore, the amount of temperature-adjusting water required to maintain the temperature of the reaction system below a certain level is the amount obtained by subtracting the amounts of initial water and dilution water required to emulsify component (B) from the total amount derived from formula (3).

[0046] The amount of temperature-adjusting water required to maintain the temperature of the reaction system can be calculated using the following formula (3) and parameters according to the amount of component (B) or component (A) (g / mol) and the upper limit of temperature rise (any temperature).

number

[0047] For example, if 10 parts by mass of n-octene emulsion (50% solid content) is used as component (B), 7 parts by mass (40% solid content) of CROSSLINKER V 72 JP manufactured by Wacker Asahi Kasei Silicone is used as component (A), and the allowable temperature rise is set to 20°C (upper limit temperature 45°C) from 25°C, the amount of component (C) required is calculated based on the specific heat of water, n-octene, and silicone being 4.18 [kJ / kg·°C], 2.18 [kJ / kg·°C], and 1.51 [kJ / kg·°C], respectively, and the heat of addition reaction being 168 kJ / mol. The amount of reactant = hydrogen content, and the hydrogen content in 7 parts by mass (40% solid content) of CROSSLINKER V 72 JP is 20.22 mol, so

number

[0048] In other words, taking the result of the above formula 4 as an example, the total amount of component (C) required to maintain and control the temperature of the reaction system is 25.7 parts by mass, but because 5 parts by mass are used to emulsify component (B), the amount of component (C) that should be added to the mixed system is 20.7 parts by mass.

[0049] (Regarding component (D)) Component D is a catalyst for reacting component (A) with component (B), and is not particularly limited as long as it is a platinum catalyst, and a known addition reaction catalyst can be used. For example, platinum-based, palladium-based, rhodium-based, ruthenium-based catalysts can be mentioned, and among these, platinum-based catalysts are particularly preferably used. Examples of the platinum catalyst include chloroplatinic acid, alcoholic or aldehyde solutions of chloroplatinic acid, and complexes of chloroplatinic acid with various olefins or vinylsiloxanes. The amount of these platinum group metal catalysts added is a catalytic amount, and the platinum metal amount may be in the range of 1 to 50 ppm, and more preferably 3 to 20 ppm. The dispersion state is not particularly limited, and may be an organic solvent dispersion, a mixture with a polymer compound, or an emulsion obtained by emulsifying them.

[0050] (Regarding component (E)) Component (E) is an emulsifier that emulsifies component (B). The type of emulsifier is not particularly limited as long as it can emulsify component (B), and may be, for example, an ionic surfactant such as an anionic surfactant, a cationic surfactant, or an amphoteric surfactant, or may be a nonionic surfactant. Since compounds containing amines may inhibit the action of the platinum group catalyst, it is more preferable to use nonionic surfactants and anionic surfactants. For example, the nonionic surfactant may be polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ethers and polyoxyethylene polyoxypropylene alkyl ethers; polyoxyethylene alkylphenyl ethers; polyoxyethylene alkyl esters; polyoxyethylene sorbitan esters; polyhydric alcohol fatty acid esters such as glycerin esters, sorbitan fatty acid esters, and sucrose fatty acid esters; ethoxylated fatty acids; ethoxylated fatty acid amides, among which polyoxyethylene alkyl ethers and polyoxyethylene polyoxypropylene alkyl ethers are preferred. The total HLB (hydrophilic group / lipophilic group balance) of the nonionic surfactant used is preferably within the range of 8 to 17, and more preferably within the range of 10 to 16. Examples of the anionic surfactant include alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, polyoxyethylene alkyl ether sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, sulfate salts of fatty acid alkylolamides, alkyl benzene sulfonates, polyoxyethylene alkyl phenyl ether sulfonates, α-olefin sulfonates, α-sulfofatty acid ester salts, alkyl naphthalene sulfonates, alkyl diphenyl ether disulfonates, alkanesulfonates, N-acyltaurate salts, dialkyl sulfosuccinates, monoalkyl sulfosuccinates, polyoxyethylene alkyl ether sulfosuccinates, fatty acid salts, polyoxyethylene alkyl ether carboxylates, N-acyl amino acid salts, monoalkyl phosphate salts, dialkyl phosphate salts, polyoxyethylene alkyl ether phosphate salts, and the like.

[0051] The blending amount of the (E) component is 1 to 10 parts by mass, assuming that the (B) component is 100 parts by mass. If it is less than 1 part by mass, dispersion is difficult, and if it exceeds 10 parts by mass, the viscosity of the composition increases and handling becomes difficult. More preferably, it is 3 to 6 parts by mass.

[0052] Component (E) may be inorganic particles that are oriented at the interface between component (B) and water to form a dispersed state. In particular, silica particles having a hydrophobic portion and silanol groups on the surface have a suitable affinity for both the oil phase and the water phase, and can be arranged at the oil / water phase interface to give an oil-in-water emulsion in which the water phase is the continuous phase.

[0053] The silica particles have hydrophobized portions and silanol groups on the surface, and can be arranged at the oil / water phase interface of the organopolysiloxane oil droplets (component (A)) in the aqueous phase of the emulsion. The surface of such silica particles contains hydrophilic silanol groups and hydrophobized silanol groups in a predetermined ratio, so that the balance between the hydrophilicity and hydrophobicity of the particles is controlled, and the particles are arranged at the oil / water phase interface composed of the organopolysiloxane (component (A)), and exhibit the emulsifying function that conventional organic surfactants have.

[0054] The silica particles are silicon dioxide particles produced by a synthetic method, and do not include mineral silica such as diatomaceous earth or crystalline quartz. Examples of silicon dioxide produced by a synthetic method include fine powder produced by a dry method such as fumed silica, calcined silica, and fused silica, and precipitated silica or colloidal silica produced by a wet method. These are known to those skilled in the art. Among these, it is preferable to use calcined silica, precipitated silica, or colloidal silica. The silica particles may be hydrophilic silica with silanol groups remaining on the surface, or hydrophobic silica with silanol groups on the surface silylated. The hydrophobic silica can be produced by a known method of treating hydrophilic silica with halogenated organosilicon such as methyltrichlorosilane, alkoxysilanes such as dimethyldialkoxysilane, silazane, or low molecular weight methylpolysiloxane.

[0055] When silica having a hydrophobic portion and a silanol group on the surface is used, the surface tension of the silica particles is set to a region required for surface activity, so that the silica particles can be arranged at the oil phase / water phase interface of the oil droplets and stabilized even in the absence of a normal surfactant. The ratio of silanol remaining after silylation to the silanol groups before silylation is preferably within the range of 50 to 95%. If the residual rate of silanol is less than 50% or exceeds 95%, the function corresponding to that of a surfactant at the oil phase / water phase interface cannot be exerted. The silylation or residual rate of silanol can be determined by measuring the carbon content by elemental analysis or measuring the amount of reactive silanol groups remaining on the silica surface. The silica particles used for preparation may include particles whose entire surface is silylated or particles whose entire surface is not silylated. However, as long as the overall silylation rate is within the above range and the required emulsification function can be expressed, it can be used.

[0056] The carbon content of the silica particles having a hydrophobized portion and a silanol group, which is preferably used as component (E), is not limited as long as the purpose of functioning as a surfactant is achieved, but is preferably within the range of 0.1 to 10%. If it is less than 0.1% or exceeds 10%, a stable emulsion cannot be obtained. It is more preferably within the range of 0.1 to 10%.

[0057] The method for treating waste hydrogen polysiloxane comprises mixing components (A) to (E): an emulsification step B of blending component (B), component (E), initial water, and dilution water to obtain an emulsion containing component (B); and a mixing step of mixing the component (B)-containing emulsion with the component (A) in an emulsified state to obtain an alkyl-modified silicone emulsion composition.

[0058] The component (B) emulsification step is a step of making an emulsion of the oily component (B), and the production method is not particularly limited, and may be a known method such as mechanical emulsification, phase inversion emulsification, D-phase emulsification, phase inversion temperature emulsification, gel emulsification, liquid crystal emulsification, etc. In particular, an oil-in-water type is preferable.

[0059] The emulsification step of component (B) can be carried out by a known method as long as an emulsion of component (B) is obtained. For example, a method of mixing and emulsifying the components using a homogenizer, colloid mill, homomixer, high-speed stator rotor stirring device, etc. can be adopted. Specifically, by adding initial water to components (B) and (E) and stirring to make them water-in-oil type, and then adding dilution water to make them oil-in-water type, the dispersion of component (B) becomes easy and the stability of the emulsion is improved. In addition, in order to control the particle size (reducing the particle size), it is preferable to provide the following steps. The component (B) emulsification step includes a first step of mixing component (B) in an amount corresponding to component (A), component (E), and a predetermined amount of water (initial water) by shear action to form an initial dispersion containing component (B); Optionally, a second step of adding an oily component (D) to the mixture obtained in the first step; Optionally, a third step of adding dilution water to the mixture obtained in the first step or the second step to form an emulsion containing component (B); Optionally, the method may include a fourth step of adding an emulsion, component (D), to the emulsion containing component (B) obtained in the third step.

[0060] The first step is a part of the emulsification step of component (B). Component (B), which is an oil phase, is added to a mixture of component (E) surfactant and initial water, and a water-in-oil type dispersion system is prepared using a stirring device such as a homogenizer, colloid mill, homomixer, or high-speed stator rotor stirring device. By going through this first step, it is expected that the particle size will be reduced. The amount of component (E) to be blended is preferably 3 to 6 parts by mass, assuming that component (B) is 100 parts by mass. The amount of initial water must be sufficient to prepare this coexisting phase, and is determined by the amount of emulsifier (E). The amount of water added is 1 to 100 parts by weight, preferably 40 to 70 parts by weight, per 100 parts by weight of the emulsifier. The order of addition is preferably such that 0.5 to 3 parts of initial water is added to 3 to 15 parts of emulsifier, and then the oil phase is added thereto.

[0061] The second step is a step of optionally adding component (D) during the emulsifying step of component (B) and emulsifying at the same time. This step is suitable when component (D) is in the form of oil. By emulsifying it together with component (B), it becomes easy to disperse it in water. When it is already emulsified, such as in the form of an emulsion, and is easy to disperse in water, this step can be omitted. The amount of component (D) to be added is an amount that provides 1 to 100 ppm of platinum, preferably 2 to 20 ppm.

[0062] The third step is a part of the emulsification step of component (B), and is a step of adding dilution water to the mixture obtained in the first and second steps, dispersing and diluting in water. The dilution water added in the third step is water as a dispersion medium (water that becomes a continuous phase). The amount of addition can be set to any amount, and can be adjusted according to the solid content of the emulsion to be obtained. For example, it may be 0 to 10,000 parts by mass with respect to 100 parts by mass of the obtained mixture. It is preferably 50 to 150 parts by mass.

[0063] The fourth step is a step of optionally adding component (D) to the emulsion containing component (B). This step may be performed when component (D) is water-soluble, such as in an emulsion state, and this step may be omitted when component (D) is added in the second step.

[0064] The mixing step is a step of mixing an emulsion containing component (B) with component (A) in an emulsified state to obtain an alkyl-modified silicone emulsion composition, A fifth step of blending component (A) with the emulsion containing component (B); Optionally, a sixth step of adding temperature adjusted water to the mixture obtained in the fifth step; Optionally, the method may include a seventh step of adding component (D) to the mixture obtained in the fifth or sixth step.

[0065] The mixing step is a process in which an alkyl-modified silicone emulsion is obtained by an addition reaction occurring in the emulsion particles. Therefore, the alkyl-modified silicone emulsion composition obtained in the mixing step is a composition containing an emulsion of the addition reaction product of component (A) and component (B).

[0066] The fifth step is a part of the process of mixing component (A) and component (B) to obtain an addition reaction product. The order of addition is not important. The material of the container used for mixing is not particularly limited as long as it is a commonly used material, and plastics, metals, etc. can be used. PTFE is particularly preferred.

[0067] The sixth step is a step of optionally adding water for the purpose of suppressing the heat of reaction generated when mixing components (A) and (B). There is no particular designation for the substance applicable in this step as long as it is a substance that can suppress (absorb) the heat of reaction, but water is the most suitable in view of the fact that it has a high specific heat capacity, that the dispersion medium is water, and that it is intended for disposal. The temperature of the water applied is below room temperature, and is preferably 4 to 20°C. If the reaction heat is not a consideration, this step can be omitted.

[0068] The seventh step is a step of optionally adding component (D) to the mixture of component (A) and component (B). This step may be performed when component (D) is water-soluble, such as in an emulsion state, and this step may be omitted when component (D) is added in the second or fourth step.

[0069] The platinum group component (D) is added in at least one of the second step, the fourth step, and the seventh step. Component (D) functions as a catalyst that promotes the addition reaction of components (A) and (B). Since its catalytic function does not change regardless of the step in which it is added, it may be added in any step.

[0070] The total amount of water added in the first, third and sixth steps can be determined according to the silicon-hydrogen bond content in component (A) and the target reaction temperature that is arbitrarily set. The target reaction temperature that is arbitrarily set is a temperature that is determined in consideration of the safety of the process, the heat resistance of the equipment, etc., and is preferably 0°C or higher and 80°C or lower. If it is 0°C or lower, it will be below the melting point of water, which is expected to cause process problems, and if it is 80°C or higher, it will be difficult to handle. More preferably, it is 10°C or higher and 60°C or lower.

[0071] The total amount of water added in the first step, the third step, and the sixth step can be derived by the following procedure. The derivation process is not limited to the method described. Assuming that all the reaction heat is used to change the temperature of the system, the following equation (5) holds true.

number

[0072] Here, the amount of reactants is equal to the amount of silicon-hydrogen bonds remaining in component (A). Equation (6), which determines the amount of water required to be added after setting the target temperature after the reaction, can be derived from equation (5) above.

number

[0073] The time required for the mixing step may be adjusted by adjusting the amount of water added in the first step (initial water). Here, the time required for the mixing step refers to the time from when component (A) and component (B) are mixed until the hydrogen concentration becomes equal to or less than a predetermined value. In consideration of safety, the predetermined value or less is preferably 0.001% or less.

[0074] The time required depends on the reaction rate. To control (adjust) the reaction rate, you can increase the contact area between component (A) and component (B). In other words, by reducing the emulsion particle size, you can increase the specific surface area, which increases the contact area.

[0075] The emulsion particle size may be adjusted by the magnitude of the shear force during emulsification. However, since emulsions created with insufficient shear force tend to be less stable, it is preferable to adjust the particle size by the amount of water (initial water).

[0076] The mixing step may further include an eighth step of measuring the temperature (mixture temperature) of the mixture containing the component (B)-containing emulsion. When the total amount of water added in the first, third and sixth steps is not calculated using the formula shown in Equation 6 above, the amount of component (C) added can be controlled by measuring the temperature, thereby controlling the temperature. For example, if the temperature detected in the eighth step is higher than the target temperature, the sixth step is carried out again. The eighth step and the sixth step may be repeated until the mixture temperature reaches the target reaction temperature. By repeating the steps, the temperature of the system can be controlled, and the process can be made safe. The end point of the repetition is the point at which the temperature falls below the target temperature and begins to drop.

[0077] The alkyl-modified silicone emulsion composition produced by the above-mentioned method for treating waste hydrogenpolysiloxane may be discarded, but it can also be used as a release agent, an antifoaming agent, a car polish, a fiber treatment agent, or an antistatic agent.

[0078] Next, an apparatus for treating component (a), which contains water and an organohydrogensiloxane having one or more hydrogen atoms bonded to silicon atoms in each molecule, with component (b), which contains a compound having only one carbon-carbon double bond in the molecule, will be described. The embodiment described below is an example of the present invention. The present invention is not limited to the following embodiment, and includes various modified forms that are implemented within the scope of the present invention. Note that not all of the configurations described below are necessarily essential configurations of the present invention.

[0079] The hydrogen polysiloxane treatment apparatus 1 of the present invention shown in FIG. An apparatus for treating component (a) containing water and an organohydrogensiloxane having one or more hydrogen atoms bonded to silicon atoms in each molecule with component (b) containing a compound having only one carbon-carbon double bond in each molecule, comprising: A component (a) storage tank 110 for storing the component (a); The component (a) outlet flow rate adjustment mechanism 111; A component (b)-containing emulsion producing apparatus 200 for producing the component (b)-containing emulsion; The component (b) flow rate control mechanism 121; A reaction vessel 140 for receiving the component (a) and an emulsion containing the component (b); A water line 131 equipped with a water flow rate control mechanism 132 for introducing water into the reaction tank 140; A temperature measuring means 150 for measuring the internal temperature of the reaction vessel 140; A control means 160 that controls the amount of at least one of the component (a), the component (b)-containing emulsion, and water introduced into the reaction tank based on the temperature measured by the temperature measuring means 150; and a detection means 170 (not shown) for detecting the amount of SiH remaining in the product stored in the reaction tank. This is a hydrogen polysiloxane treatment device.

[0080] Component (a) has the same composition as component (A) above, and may be any mixture containing water and hydrogen polysiloxane, and does not necessarily have to be waste hydrogen polysiloxane. Organohydrogen siloxanes having one or more hydrogen atoms bonded to silicon atoms per molecule are represented by the following general formula (1). R 1 a SiO (4-a) / 2 (1) (In formula (1), R 1 may be the same or different in the molecule and are a group selected from a substituted or unsubstituted saturated monovalent hydrocarbon group having 1 to 25 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or a hydrogen atom. a is an integer from 1 to 3. Component (a) may be in an emulsion state or a liquid crystal state, or may be in a state in which the hydrogenpolysiloxane and water are separated. Component (a) may be a composition prepared in advance, or it may be a waste product discharged during the process of producing an emulsion containing hydrogenpolysiloxane and collected in a waste container.

[0081] Component (a) storage tank 110 may be any container capable of storing component (a), which contains water and an organohydrogensiloxane having one or more hydrogen atoms bonded to silicon atoms per molecule, and may be a sealable container or an open storage tank.

[0082] The flow rate adjustment mechanism 111 is not particularly limited as long as it is a means capable of adjusting the flow rate of the component (a), and may be a manually operated valve, a combination of a flow meter and a valve whose opening can be adjusted, or a flow rate control valve that automatically controls the flow rate to a predetermined flow rate. For example, the flow rate is 0.01 m 3 / h or more 1m3 / h or less.

[0083] The component (b) is equivalent to the above-mentioned component (B). The flow rate adjustment mechanism 121 is not particularly limited as long as it is a means capable of adjusting the flow rate of the component (b), and may be a manually opened / closed valve, a combination of a flow meter and a valve whose opening can be adjusted, or a flow rate control valve that automatically controls the flow rate to a predetermined flow rate. For example, the flow rate is 0.01 m 3 / h or more 1m 3 / h or less.

[0084] Component (c) is the same as component (C) described above. A component (c) outlet line 131 for leading component (c) to the reaction tank 140 is provided with a flow rate adjustment mechanism 132 for adjusting the flow rate of component (c). The flow rate adjustment mechanism 132 is not particularly limited as long as it is a means capable of adjusting the flow rate of component (c), and may be a manually opened / closed valve, a combination of a flow meter and a valve whose opening can be adjusted, or a flow rate control valve that automatically controls the flow rate to a predetermined flow rate. For example, the flow rate is 0.01 m 3 / h or more 1m 3 / h or less.

[0085] The reaction vessel 140, which receives the component (a), the component (b)-containing emulsion, and the component (c) from each of the outlet lines, can be equipped with a temperature measuring means 150 and a detection means 170 for detecting the amount of remaining SiH. The detection means 170 can also be installed outside the reaction vessel 140, independent of the reaction vessel 140 (for example, an analysis device installed in a room separate from the hydrogen polysiloxane treatment device). In this case, the sample to be provided to the detection means 170 is extracted from inside the reaction vessel 140. In addition, a feedback control mechanism is provided for transmitting the measurement results by the temperature measuring means 150 to the control device 160 and controlling the flow rate adjustment mechanisms (111, 121, 132) of each component based on the measurement results. This feedback control is applied when the temperature inside the reaction vessel 140 is higher or lower than a target temperature set arbitrarily, and operation at an arbitrarily set temperature is possible. For example, when the temperature inside the reaction tank is higher than the target temperature, the flow rate is reduced in flow rate adjustment mechanisms 111 and 121, and the flow rate of component (c) is increased in flow rate adjustment mechanism 132. This control is continued until the temperature measured by temperature measurement means 150 becomes equal to or lower than the target reaction temperature.

[0086] The component (b)-containing emulsion production apparatus 200 shown in Fig. 2 includes a component (b) receiving tank 210, a first emulsifier 211, and a second emulsifier 212. The apparatus also includes two component (c) outlet lines, each of which includes a predetermined amount of water outlet line 221 and an emulsion dilution water outlet line 222. Each outlet line is provided with flow control mechanisms 231 and 232. The flow rate adjustment mechanisms 231 and 232 are not particularly limited as long as they are means capable of adjusting the flow rate of the component (c), and may be a manually opened / closed valve, a combination of a flow meter and an adjustable valve, or a flow rate control valve that automatically controls the flow rate to a predetermined flow rate. Furthermore, as long as it is possible to supply an amount of component (b) emulsion corresponding to the amount of component (a), the component (b)-containing emulsion manufacturing apparatus 200 may operate alone to prepare and store the emulsion in the component (b)-containing emulsion storage tank 120, or may operate in conjunction with the operation of the reaction tank 140. The first emulsifier 211 and the second emulsifier 212 have different roles, with the first emulsifier 211 performing emulsification and the second emulsifier 212 performing assistance for dilution into the dispersion medium (water). The first emulsifier 211 and the second emulsifier 212 operate simultaneously and are not operated independently. EXAMPLES

[0087] The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited thereto. In the following examples, the physical properties shown in the tables were measured by the following test methods.

[0088] <Emulsification of component (B)> (Emulsion Example 1) 8 parts by weight of Arscope LS-25B (22% ammonium lauryl sulfate) manufactured by Toho Chemical Industry Co., Ltd. as component (E), 4.2 parts by weight of a given amount of water as component (C), and 50 parts by weight of Linearene 12 (1-dodecene>95%, specific gravity 0.759 at 20°C) manufactured by Idemitsu Kosan Co., Ltd. as component (B) are mixed to obtain an initial dispersion. 0.05 parts by weight of Wacker Catalyst OL (a mixture of platinum complex dispersed in polyorganosiloxane) manufactured by Wacker Chemie AG is added as component (D) and stirred and mixed at 2000 rpm using an ULTRA-TURRAX T50 Basic Shaft Generator G45M manufactured by IKA. After mixing uniformly, 37.8 parts by weight of water is gradually added to obtain an emulsion.

[0089] (Emulsion Example 2) 8 parts by weight of Arscope LS-25B (22% ammonium lauryl sulfate) manufactured by Toho Chemical Industry Co., Ltd. as component (E), 21 parts by weight of a given amount of water as component (C), and 50 parts by weight of Linearene 12 (1-dodecene > 95%, specific gravity 0.759 at 20°C) manufactured by Idemitsu Kosan Co., Ltd. as component (B) are mixed to obtain an initial dispersion. 0.05 parts by weight of Wacker Catalyst OL (a mixture of platinum complex dispersed in polyorganosiloxane) manufactured by Wacker Chemie AG is added as component (D) and stirred and mixed at 2000 rpm using an ULTRA-TURRAX T50 Basic Shaft Generator G45M manufactured by IKA. After mixing uniformly, 21 parts by weight of water is gradually added to obtain an emulsion.

[0090] (Emulsion Example 3) 8 parts by weight of Arscope LS-25B (22% ammonium lauryl sulfate) manufactured by Toho Chemical Industry Co., Ltd. as component (E), 42 parts by weight of a given amount of water as component (C), and 50 parts by weight of Linearene 12 (1-dodecene > 95%, specific gravity 0.759 at 20°C) manufactured by Idemitsu Kosan Co., Ltd. as component (B) are mixed to obtain an initial dispersion. 0.05 parts by weight of Wacker Catalyst OL (a mixture of platinum complex dispersed in polyorganosiloxane) manufactured by Wacker Chemie AG is added as component (D) and stirred and mixed at 2000 rpm using an ULTRA-TURRAX T50 Basic Shaft Generator G45M manufactured by IKA. After mixing uniformly, 21 parts by weight of water is gradually added to obtain an emulsion.

[0091] (Emulsion Example 4) 5 parts by weight of silica particles manufactured by Wacker Chemie AG as component (E) and 44.95 parts of water as component (C) are added, and stirred and mixed at 2000 rpm using an ULTRA-TURRAX (registered trademark) T50 basic shaft generator G45M manufactured by IKA Corporation to obtain a silica dispersion. To this are added 50 parts by weight of Linearene 12 (1-dodecene > 95%, specific gravity 0.759 at 20°C) manufactured by Idemitsu Kosan Co., Ltd. as component (B) and 0.05 parts by weight of Wacker (registered trademark) Catalyst OL (a mixture of platinum complex dispersed in polyorganosiloxane) manufactured by Wacker Chemie AG as component (D), and the mixture is stirred and mixed at 2000 rpm using an ULTRA-TURRAX (registered trademark) T50 Basic Shaft Generator G45M manufactured by IKA to obtain an emulsion.

[0092] <Mixing process> The target upper limit temperature in the mixing process was 60° C. The temperature at the start of the reaction was 25° C.

[0093] Example 1 10 parts by weight of Wacker (registered trademark) CROSSLINKER V 72 JP manufactured by Wacker Asahi Kasei Silicones Co., Ltd. was added as component (A), 11.1 parts by weight of the emulsion of Linearene 12 prepared in emulsification example 1 was added as component (B), and 20 parts by weight of water was added as component (C), and the mixture was mixed by hand for 10 minutes. The amount of this component (C) was set based on the following calculation results.

number

[0094] Example 2 As component (A), 10 parts by weight of Wacker (registered trademark) CROSSLINKER V 72 JP manufactured by Wacker Asahi Kasei Silicones Co., Ltd., and as the emulsion of component (B), 22.2 parts by weight of the emulsion of Linearene 12 prepared in emulsification example 1 and 20 parts by weight of water are added, and mixed by hand for 10 minutes.

[0095] Example 3 As component (A), 10 parts by weight of Wacker (registered trademark) CROSSLINKER V 72 JP manufactured by Wacker Asahi Kasei Silicones Co., Ltd., and as an emulsion of component (B), 11.1 parts by weight of the emulsion of Linearene 12 prepared in emulsification example 2 and 20 parts by weight of water are added, and mixed by hand for 10 minutes.

[0096] Example 4 As component (A), 10 parts by weight of Wacker (registered trademark) CROSSLINKER V 72 JP manufactured by Wacker Asahi Kasei Silicones Co., Ltd., and as an emulsion of component (B), 11.1 parts by weight of the emulsion of Linearene 12 prepared in emulsification example 3 and 20 parts by weight of water are added, and mixed by hand for 10 minutes.

[0097] Example 5 10 parts by weight of Wacker (registered trademark) CROSSLINKER V 72 JP manufactured by Wacker Asahi Kasei Silicones Co., Ltd. are added as component (A), and 11.1 parts by weight of the emulsion of Linearene 12 prepared in emulsification example 4 and 20 parts by weight of water are added as the emulsion of component (B), and the mixture is mixed by hand for 10 minutes.

[0098] Example 6 As component (A), 10 parts by mass of hydrogen siloxane-containing waste (solid) generated during the manufacturing process of Wacker (registered trademark) CROSSLINKER V 72 JP manufactured by Wacker Asahi Kasei Silicone Co., Ltd., 2 parts by mass of PEG400 manufactured by Toho Co., Ltd. as an additive, 29.1 parts by mass of the emulsion of Linearene 12 prepared in Emulsion Example 1 as an emulsion of component (B), and 20 parts by mass of water are added, and mixed by hand stirring for 10 minutes. Comparative Example

[0099] Comparative Example 1 10 parts by mass of Wacker (registered trademark) CROSSLINKER V 72 JP manufactured by Wacker Asahi Kasei Silicones Co., Ltd. are added as component (A), 5.5 parts by mass of Linealene 12 as component (B), and 25 parts by mass of water are added, and mixed by hand stirring for 10 minutes.

[0100] Comparative Example 2 As component (A), 10 parts by mass of Wacker (registered trademark) CROSSLINKER V 72 JP manufactured by Wacker Asahi Kasei Silicones Co., Ltd., and as the emulsion of component (B), 3.3 parts by mass of the emulsion of Linearene 12 prepared in emulsification example 1 and 20 parts by mass of water are added, and mixed by hand for 10 minutes.

[0101] Comparative Example 3 As component (A), 10 parts by weight of Wacker (registered trademark) CROSSLINKER V 72 JP manufactured by Wacker Asahi Kasei Silicones Co., Ltd., and as the emulsion of component (B), 5.5 parts by weight of the emulsion of Linearene 12 prepared in emulsification example 1 and 20 parts by weight of water are added, and mixed by hand for 10 minutes.

[0102] <Measurement of residual silicon-hydrogen bonds> The amount of silicon-hydrogen bond residue in a mixture of component (A) and component (B) was measured by alkaline titration. A bifurcated flask containing 0.1-15 parts by mass of the substance to be measured and 5 parts by mass of Kanto Chemical's special grade ethanol (95) as a solvent on one side of the flask, and 5 parts by mass of Kanto Chemical's special grade ethanol (95) on the other side, and 2 parts by mass of Kanto Chemical's sodium hydroxide on the other side, was connected to a glass tube filled with water, and the hydrolysis reaction was started by mixing the solutions. The volume of the generated gas was determined from the water level in the glass tube, and the amount of silicon-hydrogen bond residue was calculated by the following formula.

number

[0103] The above P is the vapor pressure of ethanol and is calculated using the Antoine equation (logP = A-(B / (C+T)). Here, A = 8.21337, B = 1652.05, C = 231.48, and T = room temperature [℃]. As an example, the calculation results of ethanol vapor pressure P when the room temperature is 18 to 26°C are shown in Table 1 below. [Table 1]

[0104] <Silicon-hydrogen bond residual amount evaluation criteria> When the amount of residual silicon-hydrogen bonds was 0.001% or less, it was determined that the amount of residual silicon-hydrogen bonds was effectively reduced.

[0105] <Particle size measurement (median diameter D50 measurement)> The particle size was measured using a Mastersizer 3000 manufactured by Spectris Corporation, and D50 was used as the particle size of the measured sample. The results are shown in Tables 2 and 3.

[0106] [Table 2] [Table 3]

[0107] Examples 1 and 2 are examples in which the (B) component was added in amounts such that the emulsion of Linearene 12 had 1.0 and 2.0 alkenyl groups per hydrogen atom bonded to a silicon atom in the entire composition, respectively.

[0108] In Examples 1 and 2, the residual silicon-hydrogen bond amount was 0.0001% or less 90 days after mixing, and the residual silicon-hydrogen bond amount was effectively reduced. The obtained composition is represented by the following general formula (5). R 1 a SiO (4-a) / 2 (5) (In formula (5), R 1 may be the same or different in the molecule and are groups selected from substituted or unsubstituted saturated monovalent hydrocarbon groups having 1 to 25 carbon atoms, substituted or unsubstituted aromatic groups having 6 to 30 carbon atoms, hydroxyl groups, and alkoxy groups having 1 to 6 carbon atoms. a is an integer from 1 to 3.

[0109] Examples 3 and 4 are examples in which component (B) was added in an amount such that the Linearene 12 emulsion had 1.0 alkenyl group per hydrogen atom bonded to a silicon atom in the entire composition.

[0110] In Examples 3 and 4, the residual silicon-hydrogen bond amount was 0.0001% or less 90 days after mixing, and the residual silicon-hydrogen bond amount was effectively reduced. The obtained composition is represented by the following general formula (5). R 1 a SiO (4-a) / 2 (5) (In formula (5), R 1 may be the same or different in the molecule and are groups selected from substituted or unsubstituted saturated monovalent hydrocarbon groups having 1 to 25 carbon atoms, substituted or unsubstituted aromatic groups having 6 to 30 carbon atoms, hydroxyl groups, and alkoxy groups having 1 to 6 carbon atoms. a is an integer from 1 to 3.

[0111] In addition, in Examples 1, 3, and 4, the materials prepared in the emulsification Examples 1, 2, and 3 were added as component (B), respectively. The smaller the particle size, the greater the rate of decrease in the amount of residual silicon-hydrogen bonds per unit time. In other words, it was suggested that the smaller the particle size, the faster the reaction rate.

[0112] Example 5 is an example in which component (B) was added in an amount such that the Linearene 12 emulsion contained 1.0 alkenyl group per hydrogen atom bonded to a silicon atom in the entire composition, and silica particles were used to emulsify component (B).

[0113] In Example 5, the residual silicon-hydrogen bond content was 0.0001 mass% or less 90 days after mixing, and the residual silicon-hydrogen bond content was effectively reduced. The obtained composition is represented by the general formula (5).

[0114] Example 6 is an example in which component (B) was added in an amount such that the Linearene 12 emulsion had 1.0 alkenyl group per hydrogen atom bonded to a silicon atom in the entire composition, and a polyhydric alcohol was added as an additive.

[0115] In Example 6, the residual silicon-hydrogen bond content was 0.0001 mass% or less 90 days after mixing, and the residual silicon-hydrogen bond content was effectively reduced. The obtained composition is represented by the general formula (5).

[0116] In Comparative Example 1, Linearene 12 was used as component (B) without being emulsified.

[0117] In Comparative Example 1, 90 days after mixing, the residual silicon-hydrogen bond ratio was 0.17 mass %, and the residual silicon-hydrogen bond amount had not decreased to the allowable value.

[0118] Comparative Example 2 is an example in which component (B) was added in an amount such that the Linearene 12 emulsion contained 0.3 alkenyl groups per hydrogen atom bonded to a silicon atom in the entire composition.

[0119] In Comparative Example 2, 90 days after mixing, the residual silicon-hydrogen bond ratio was 0.11 mass %, and the residual silicon-hydrogen bond amount had not decreased to the allowable value.

[0120] Comparative Example 3 is an example in which component (B) was added in an amount such that the Linearene 12 emulsion contained 0.5 alkenyl groups per hydrogen atom bonded to a silicon atom in the entire composition.

[0121] In Comparative Example 3, 90 days after mixing, the residual silicon-hydrogen bond ratio was 0.04 mass %, and the residual silicon-hydrogen bond amount had not decreased to the allowable value. [Explanation of symbols]

[0122] 1. Hydrogen polysiloxane processing equipment 110. Component (a) Storage tank 121. Component (b) Flow rate adjustment mechanism 131. Water line 132. Water flow rate adjustment mechanism 140. Reactor 150. Temperature measuring means 160. Control Measures 200. Equipment for producing emulsions containing component (b) 210. Receiving tank 211. First emulsifier 212. Second emulsifier

Claims

1. A method for treating waste hydrogenpolysiloxane generated in a process for producing an emulsion containing hydrogenpolysiloxane, the method comprising the step of mixing component (A) with an emulsion containing component (B) described below to obtain an alkyl-modified silicone emulsion composition, the method comprising the steps of: The component (A) is (A) the waste hydrogen polysiloxane contains water and an organohydrogen siloxane having one or more hydrogen atoms bonded to silicon atoms in each molecule, The component (B)-containing emulsion is (B) an unsaturated hydrocarbon having 10 to 14 carbon atoms and having only one carbon-carbon double bond in the molecule; (C) Water (initial water, dilution water, temperature-adjusted water); (D) a platinum group catalyst; (E) an emulsifier, The amount of the component (B) is an amount such that the number of alkenyl groups in the component (B) is 1.0 or more per one hydrogen atom bonded to a silicon atom contained in the entire component (A). method.

2. The component (B) emulsification step is a first step of mixing the component (B) in an amount corresponding to the component (A), the component (E), and initial water by shear action to form an initial dispersion containing the component (B); Optionally, a second step of adding the oily component (D) to the mixture obtained in the first step; Optionally, a third step of adding dilution water for diluting the mixture obtained in the first step to the mixture obtained in the first step or the second step to form an emulsion containing component (B); Optionally, a fourth step of adding the component (D) which is an emulsion to the component (B)-containing emulsion obtained in the third step, The mixing step comprises: A fifth step of blending the component (A) with the component (B)-containing emulsion; Optionally, a sixth step of adding temperature adjusted water to the mixture obtained in the fifth step; Optionally, a seventh step of adding the component (D) to the mixture obtained in the fifth step or the sixth step, The component (D) is added in at least one of the second step, the third step, or the fifth step, The method according to claim 1, wherein the total amount of water added in the first step, the third step, and the sixth step is an amount depending on the silicon-hydrogen bond content in component (A) and an arbitrarily set target reaction temperature.

3. The method according to claim 2 , wherein the total amount of water added in the first step, the third step, and the sixth step is represented by the following formula (1): [0010]

4. 4. The method according to claim 2 or 3, wherein the time required for the mixing step is adjusted by adjusting at least one of the magnitude of the shear force in the first step, the amount of component (E) blended in the first step, the amount of water added in the third step, or the time from the end of the first step or the second step to the start of the third step.

5. 5. The method according to claim 2, wherein the mixing step further comprises an eighth step of measuring a temperature (mixture temperature) of the mixture containing the component (B)-containing emulsion, and when the mixture temperature is higher than the target reaction temperature, the sixth step is carried out, and the eighth step and the sixth step are repeated until the mixture temperature reaches the target reaction temperature.

6. 6. The method according to claim 1, wherein the component (E) is at least one of an ionic surfactant, a nonionic surfactant, and silica particles having a hydrophobic portion and a silanol group on the surface.

7. 7. The method according to claim 2, further comprising the step of adding a polyhydric alcohol in the mixing step when the component (A) is in a liquid crystal state.

8. The method according to any one of claims 1 to 7, wherein the component (B) is an α-olefin having a terminal double bond and having 10 to 14 carbon atoms.

9. The method according to any one of claims 1 to 8, wherein component (B) is 1-decene, 1-dodecene or 1-tetradecene.

10. The method according to claim 1, wherein component (B) is 1-dodecene.

11. The method according to any one of claims 1 to 10, wherein the amount of component (B) is an amount such that there are 1.0 to 2.0 alkenyl groups in component (B) per hydrogen atom bonded to a silicon atom contained in the entire component (A).

12. An apparatus for treating component (a) containing water and an organohydrogensiloxane having one or more hydrogen atoms bonded to silicon atoms in each molecule with component (b) containing an unsaturated hydrocarbon compound having 10 to 14 carbon atoms and only one carbon-carbon double bond in the molecule, comprising: The amount of the component (b) is an amount such that the number of alkenyl groups in the component (b) is 1.0 or more per one hydrogen atom bonded to a silicon atom contained in the entire component (a), A component (a) storage tank for storing the component (a); The component (a) outlet flow rate control mechanism; An apparatus for producing an emulsion containing the component (b), A component (b) flow rate control mechanism; A reaction vessel for receiving the component (a) and an emulsion containing the component (b); A water line equipped with a flow rate control mechanism for introducing water into the reaction tank; A temperature measuring means for measuring the internal temperature of the reaction vessel; a control means for controlling an amount of at least one of the component (a), the component (b)-containing emulsion, and water introduced into the reaction tank based on the temperature measured by the temperature measuring means; and and a detection means for detecting the amount of SiH remaining in the product stored in the reaction tank. Hydrogen polysiloxane processing equipment.

13. The component (b)-containing emulsion producing apparatus comprises: A receiving tank for receiving at least the component (b) and the component (e); an initial water introduction line equipped with a flow rate control mechanism for introducing initial water into the mixture discharged from the receiving tank; a first emulsifier and a second emulsifier for mixing the mixture discharged from the receiving tank and the mixture of the initial water by shear force; a component (b)-containing initial dispersion discharge line for discharging the component (b)-containing initial dispersion from the component (b)-containing initial dispersion storage tank; a water addition line having one or more flow rate control mechanisms connected to the component (b)-containing initial dispersion discharge line; The processing device of claim 12 , comprising:

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