JP2022112544A - Method for treating hydrogen polysiloxane waste, and hydrogen polysiloxane treatment device - Google Patents

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 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 a hydrogenpolysiloxane treatment apparatus.

Hydrogenpolysiloxanes are often used in the process of producing organopolysiloxanes into which various organic groups have been introduced through addition reactions with organic unsaturated compounds having aliphatic unsaturated bonds in the presence of catalysts. The resulting organopolysiloxane is widely used in fields such as paints, molding materials, medical materials, various coating materials, cosmetics, personal care compositions, home care compositions, release agents, and fiber treatment agents.

Hydrogen polysiloxane is used not only in the state of oil as it is, but also in the state diluted with an arbitrary solvent, and in recent years, it is used in the form of an aqueous emulsion from the viewpoint of safety in the working environment and reduction of environmental load. is increasing.

When hydrogenpolysiloxane comes into contact with water or a substance having active hydrogen such as an amino group, it undergoes intermolecular dehydrogenation and releases hydrogen gas. Hydrogen gas has the danger of ignition and explosion, and must be handled with care. Emulsion-like hydrogenpolysiloxane coexists with water, which is a source of active hydrogen, and releases hydrogen gas over time due to a hydrolysis reaction, so safety is required in terms of storage and handling. Safety is required not only for products, but also for waste generated in the manufacturing process.

In a process for producing an emulsion of hydrogenpolysiloxane and a process for producing organopolysiloxane using the emulsion, waste emulsion of hydrogenpolysiloxane is generated for reasons such as pre-cutting, post-cutting, and cleaning of equipment. After such waste emulsion is stored until it reaches a certain amount, it is usually transported to an incineration facility and discarded by incineration.

However, hydrogen gas is gradually generated from the stored waste emulsion, and there is a risk that the storage container may burst or the hydrogen gas may catch fire.
Measures such as attaching a gas vent cap to prevent the container from bursting have been taken, but there is a danger that the hydrogen gas released from the container will ignite. It is also conceivable to reduce the amount of hydrogenpolysiloxane stored in the container to suppress the rise in the internal pressure of the container, but the volume of the container becomes larger than the amount of storage, and a vast storage area is required. There's a problem.
Therefore, unlike oily or solvent-diluted hydrogenpolysiloxanes that can be stably stored without the risk of generating hydrogen, it has been difficult to store hydrogenpolysiloxane emulsions safely until they are discarded.

As a countermeasure for suppressing hydrogen generation over time, it is conceivable to physically separate the active hydrogen source and the hydrogen polysiloxane.
However, in the case of hydrogenpolysiloxane containing water, for example, it is difficult to completely remove the water from the mixture.
The method of removing water by applying external energy such as heat accelerates the generation of hydrogen gas, and there is also a risk of ignition of the hydrogen gas, which raises safety concerns.
As another means for suppressing hydrogen generation over time, a method of reducing the amount of silicon-hydrogen bonds remaining in the hydrogenpolysiloxane is conceivable. For example, Patent Document 1 discloses a method of blowing ethylene gas into hydrogenpolysiloxane. However, since this method involves a reaction at the gas-liquid interface, it is difficult to increase the reaction efficiency, and the residual amount of hydrogen in the hydrogenpolysiloxane cannot be reduced sufficiently. In addition, advanced equipment capable of controlling pressure and temperature is required.

In addition, since the addition reaction between the hydrogenpolysiloxane and the organic unsaturated compound having an aliphatic unsaturated bond in the presence of a catalyst is an exothermic reaction, it is necessary to pay attention to the temperature rise of the system due to the heat of the addition reaction. A special reactor or the like may be required.

Patent Document 2 discloses a method for obtaining a silicone oil emulsion by mixing an emulsion of alkenylsiloxane having alkenyl groups at both ends and an emulsion of 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 cross-linking reaction at a ratio of 1:1, resulting in a silicon-hydrogen bond in the hydrogenpolysiloxane. The residual amount is reduced.
This method is safe in that it does not apply external energy (heat, pressure, etc.) to the system. However, as described above, the reaction ratio (hydrogen-silicon bond): (vinyl group) = 1:1, so the greater the number of functional groups (hydrogen-silicon bond) contained in the hydrogen polysiloxane, the more the corresponding alkenyl Similarly, a large amount of siloxane is required, and there is a problem that the amount of waste increases. In addition, silicone itself is expensive, and in the case of siloxane having a plurality of Si-H atoms in one molecule, there is a problem that the reaction rate becomes insufficient due to steric hindrance. Therefore, even with this method, it is difficult to reduce the residual amount of hydrogen in the hydrogenpolysiloxane to a safe level.

Japanese Patent Application Laid-Open No. 2001-114895 Japanese Patent Application Laid-Open No. 2020-12076

Therefore, there has been a demand for a treatment method that sufficiently reduces the residual amount of hydrogen in the discarded hydrogenpolysiloxane.
The present invention has been made in view of the above matters, and is a method for safely and highly efficiently reducing the residual amount of hydrogen in waste hydrogenpolysiloxane containing water, which can be realized by inexpensive equipment in the treatment process. The purpose is to provide a method with less load on Here, "safe" means not causing an excessive exothermic reaction, and "highly efficient" means not using excessive amounts of chemical substances (e.g., using theoretical amounts of chemical substances for hydrogen polysiloxane). 2) The remaining amount of hydrogen is sufficiently low, "inexpensive equipment" does not require equipment that can handle high temperatures and high pressures, or highly airtight equipment, and "low load on equipment" means that the equipment is This means that it is difficult for members such as pipes and valves to become clogged.
Another object of the present invention is to provide an apparatus for sufficiently reducing the residual amount of hydrogen in hydrogenpolysiloxane containing water with safe and inexpensive equipment.

As a result of intensive studies to achieve the above object, the present inventors 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, an inexpensive and safe process We found that the amount of Si-H can be reduced to a safe range.
In addition, according to a hybrid system that combines a batch type and a continuous type, it is possible to efficiently treat even if it includes a step of reducing the residual amount of hydrogen in the hydrogen polysiloxane, which takes a certain amount of time. Found it.

The method for reducing the amount of residual silicon-hydrogen bonds (also referred to as residual hydrogen) in waste hydrogenpolysiloxane according to the present invention comprises:
generated in the step of producing an emulsion containing hydrogenpolysiloxane, including a mixing step of obtaining an alkyl-modified silicone emulsified composition by mixing component (A) below with an emulsion containing component (B) below. A method for treating waste hydrogenpolysiloxane, comprising:
The component (A) is
(A) the waste hydrogen polysiloxane containing water and an organohydrogensiloxane having one or more silicon-bonded hydrogen atoms per molecule;
The component (B)-containing emulsion comprises (B) a hydrocarbon compound having only one carbon-carbon double bond in the molecule;
(C) water;
(D) a platinum group catalyst; and (E) an emulsifier.
Here, the water as the component (C) is water for emulsifying the component (B), and the water added at the initial stage of emulsification (hereinafter also referred to as initial water), Water added to dilute the mixture with (hereinafter also referred to as dilution water), and water added to adjust the temperature of the mixture containing component (B) and the initial water and dilution water (hereinafter referred to as temperature (also called adjusted water).

In the process of producing an emulsion containing hydrogenpolysiloxane, waste containing hydrogenpolysiloxane and water (that is, waste hydrogenpolysiloxane) is generated due to pre-cutting, post-cutting, cleaning of equipment, and the like. This waste hydrogenpolysiloxane is typically in an emulsion or liquid crystal state.
The hydrogenpolysiloxane contained in the waste hydrogenpolysiloxane gradually reacts with the water contained in the waste hydrogenpolysiloxane to generate hydrogen gas.
Therefore, in the present invention, the waste hydrogen polysiloxane is reacted with a compound (B) having only one carbon-carbon double bond in the molecule to remove the silicon-hydrogen bond in the waste hydrogen polysiloxane molecule. Reduces the remaining amount and suppresses the generation of hydrogen gas.

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

A component (B) having only one carbon-carbon double bond in the molecule has a higher steric sensitivity during the addition reaction with component (A) compared to having two or more carbon-carbon double bonds. less obstacles. Therefore, the remaining amount of silicon-hydrogen bonds contained in component (A) can be reduced with higher efficiency.
Furthermore, when there is only one carbon-carbon double bond in the molecule, no gel-like or solid product is generated because no cross-linking reaction occurs. Therefore, there is little load on facilities such as clogging of pipes in treatment facilities, and maintenance is easy.

Component (E), which is a platinum group catalyst, is a catalyst necessary for the addition reaction of component (A) and component (B). Since this reaction is carried out at normal temperature and pressure and does not require high temperature and high pressure conditions, it is highly safe and can be carried out with simple equipment.

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

A very simple facility is required for the addition reaction of the component (a) containing water and hydrogenpolysiloxane and the component (b) containing a compound having only one carbon-carbon double bond in the molecule. can be used. For example, it can be processed by manually introducing component (a) and component (b) into a container having an opening. However, a certain degree of automation is required depending on the background, such as an increase in the amount of processing, a reduction in personnel, a request for reduction in processing man-hours, and the like. However, especially when the reaction of component (a) and component (b) takes a long time, it is difficult to fully automate the process by continuously adding both components, and the equipment becomes large-scale.
Therefore, in the present invention, a part of the treatment is continuously performed, and then the detection of the end point of the addition reaction and the discharge of the product are performed in a batch process, so that the treatment can be performed efficiently with a simple apparatus. Provide equipment.

In the processing apparatus of the present invention, component (a) and component (b) are each introduced into the reactor at a predetermined flow rate. Water can be introduced into the reactor at a predetermined flow rate. The flow rates of component (a), component (b) and water are adjusted according to the temperature in the reactor. As a result, it becomes possible to perform the treatment while automatically charging the component (a) and the component (b) into the reaction tank while suppressing rapid temperature changes. This automatic process ends when predetermined amounts of component (a) and component (b) are added to the reactor.

The reactor is further equipped with means for detecting the residual amount of silicon-hydrogen bonds in component (a). This allows detection of the endpoint of the addition reaction with component (b), indicating that the remaining silicon-hydrogen bonds in component (a) have been sufficiently reduced. After the end point of the reaction is detected, the reaction product is discharged from the reactor. This endpoint detection and discharge of reaction products is a batch process.

By using a processing apparatus capable of combining an automatic process and a batch process in this way, it is possible to perform processing at normal temperature and normal pressure even in a device with low airtightness. Therefore, there is no need to use a heat-resistant member that can withstand high temperatures, a device having high airtightness, a pressure adjusting device, or the like, and processing can be performed using inexpensive and simple processing equipment.

1 is a diagram showing a configuration example of a hydrogenpolysiloxane processing apparatus of the present invention; FIG. It is a figure which shows the structural example of the component (b) containing emulsion manufacturing apparatus of this invention.

The details of the method for reducing the amount of silicon-hydrogen bonds remaining in waste hydrogenpolysiloxane and the hydrogenpolysiloxane treatment apparatus according to the present invention will be described below.

The method for reducing the amount of residual silicon-hydrogen bonds in waste hydrogenpolysiloxane according to the present invention comprises:
generated in the step of producing an emulsion containing hydrogenpolysiloxane, including a mixing step of obtaining an alkyl-modified silicone emulsified composition by mixing component (A) below with an emulsion containing component (B) below. A method for treating waste hydrogenpolysiloxane, comprising:
The component (A) is
(A) the waste hydrogen polysiloxane containing water and an organohydrogensiloxane having one or more silicon-bonded hydrogen atoms per molecule;
The component (B)-containing emulsion comprises (B) a hydrocarbon compound having only one carbon-carbon double bond in the molecule;
(C) water;
(D) a platinum group catalyst; and (E) an emulsifier.

(About component (A))
Component (A) is a waste hydrogenpolysiloxane containing water and an organohydrogensiloxane having at least one silicon-bonded hydrogen atom per molecule. Waste hydrogenpolysiloxanes are generated in the process of making emulsions containing hydrogenpolysiloxanes.
The waste organohydrogensiloxane having one or more silicon-bonded hydrogen atoms in one molecule is represented by the following general formula (1).

R1aSiO _{(4-a)/2 (} ¹ )

(In formula (1), R ¹ may be the same or different in the molecule and is a substituted or unsubstituted saturated monovalent hydrocarbon group having 1 to 25 carbon atoms, a substituted or unsubstituted is a group selected from an aromatic group of up to 30, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or a hydrogen atom, and a is 1 to 3.)

The above R ¹ is specifically a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, 2-ethylhexyl group, heptyl group, Alkyl groups such as octyl group, nonyl group, decyl group and dodecyl group; Cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group; Aryl groups such as phenyl group, tolyl group, xylyl group, biphenyl group and naphthyl group; A benzyl group, a phenylethyl group, a phenylpropyl group, a chloromethyl group in which some or all of the hydrogen atoms in a hydrocarbon group are substituted with a halogen atom, a cyano group, etc., a 2-bromoethyl group, a 3,3,3-tri Substituted hydrocarbon groups such as fluoropropyl, 3-chloropropyl, chlorophenyl, dibromophenyl, tetrachlorophenyl, difluorophenyl, β-cyanoethyl, γ-cyanopropyl, β-cyanopropyl, methoxy groups, alkoxy groups such as ethoxy groups and propyl groups, hydroxyl groups, and hydrogen. A methyl group is particularly preferred.

The above organohydrogensiloxanes are produced by methods known to those skilled in the art, and specific examples include methylhydrogenpolysiloxane, dimethylsiloxane/methylhydrogensiloxane copolymer, methylphenylsiloxane/methylhydrogensiloxane copolymer, and the like. exemplified. These may be used singly 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 terminal silicon atoms of the molecular chain of the organohydrogenpolysiloxane, and may be bonded to the terminal or non-terminal silicon atoms of the molecular chain. may be combined. The number of hydrogen atoms per organohydrogenpolysiloxane molecule is not particularly limited. The organohydrogenpolysiloxane is hereinafter also simply referred to as hydrogenpolysiloxane.

The step of producing an emulsion containing hydrogenpolysiloxane is a step of producing an emulsion of hydrogenpolysiloxane, which is an emulsion, from oily hydrogenpolysiloxane. The production method is not particularly limited, and known methods such as liquid crystal emulsification, mechanical emulsification, phase inversion emulsification, phase inversion temperature emulsification, and D phase emulsification may be used. The obtained emulsion is preferably oil-in-water type.

The liquid crystal emulsification method is a technique for producing fine emulsified particles that disperse and hold a dispersed phase (an oil phase in an O/W emulsion) in a liquid crystal formed by a surfactant.
The mechanical emulsification method is an emulsification method that utilizes physical convection and is performed using a homogenizer or a stirrer. A stirrer is a method of mixing substances by vigorously mixing them to cause physical convection, and a homogenizer is a method of mixing substances by causing physical convection using ultrasonic waves and high pressure.
Phase inversion emulsification is a method of dissolving a surfactant in an oil phase, then stirring while adding an aqueous phase, and inverting the continuous phase from the oil phase to the aqueous phase, thereby producing an O/W emulsion. is.
In the phase inversion temperature emulsification method, in a three-component system of nonionic surfactant, oil, and water, at a certain temperature, the nonionic surfactant infinitely associates and separates as a macroscopic phase containing a large amount of oil and water. However, when the temperature is further increased, the nonionic surfactant dissolves in the oil phase to form reverse micelles and water is solubilized, so this phase inversion temperature is used for emulsification.
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 form a fine O/W emulsion.

Waste hydrogen polysiloxane generated in the process of manufacturing an emulsion containing hydrogen polysiloxane refers to waste that is discarded during pre-cutting or post-cutting in the manufacturing process, or that is washed away due to reasons such as cleaning inside the equipment. This includes items extracted from the manufacturing process for inspection. The form of waste hydrogenpolysiloxane varies depending on the generation process and storage conditions after generation. There are forms such as an emulsion state, a liquid crystal state, an oil state containing a small amount of water, or a state in which an oil phase and an aqueous phase are separated. In either case, since hydrogenpolysiloxane and water coexist, hydrogen gas is gradually generated by the hydrolysis reaction.

A polyhydric alcohol can be added to component (A) when component (A) is in a liquid crystalline state. Polyhydric alcohols include ethylene glycol, polyethylene glycol, propylene glycol, glycerin, 1,3-butanediol, D-sorbitol and the like. By adding a polyhydric alcohol, the cohesive force of the surfactant can be relaxed and fluidity can be obtained. In the case of solid-liquid coexistence, the uniformity is poor, and when mixed with the component (B) and treated, uneven treatment may occur, and silicon-hydrogen bonds may remain. When there is fluidity (everything is liquid), it is excellent in uniformity, and treatment unevenness is less likely to occur.

These waste hydrogen polysiloxanes must be stored immediately after generation, or after a certain amount of hydrogen gas is stored, in a state in which the generation of hydrogen gas is suppressed. A state in which the generation of hydrogen gas is suppressed means a state in which the amount of silicon-hydrogen bonds remaining in the hydrogenpolysiloxane is small. For example, it is 0.001% by mass or less, 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, lowering safety.

保管後には、ケイ素－水素結合残留量が低下したハイドロジェンポリシロキサンは、他のポリシロキサン含有廃棄物と同様に廃棄物処理業者へ運搬され、処理される。 If the capacity of the container to be stored and the amount of hydrogenpolysiloxane enclosed in the container are limited in order 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 enclosed in a 200 L non-pressure resistant container up to 30% of the container capacity, the upper limit of the silicon-hydrogen bond residual amount is preferably 0.02% by mass. If 80% is enclosed, it is preferably 0.001% by mass or less. According to Charles' law, when the pressure is constant, the volume is proportional to the temperature. Therefore, if the temperature during storage is high, it is preferable to further lower the upper limit value.
If the mass parts of the waste hydrogenpolysiloxane and the amount of residual silicon-hydrogen bonds (% by mass) are known, the volume of hydrogen that can be generated can be estimated by Equation (2).

After storage, the hydrogenpolysiloxane with reduced residual silicon-hydrogen bond content is transported to a waste disposal company and treated in the same manner as other polysiloxane-containing wastes.

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

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

Component (A) may contain components other than hydrogenpolysiloxane and water, and if necessary, other optional components (such as surfactants, stabilizers, and preservatives) may be added. may

(About component (B))
Hydrocarbon compounds having only one carbon-carbon double bond in the molecule may be alkenes or cycloalkenes, or mixtures thereof. Alkenes are preferred.

When component (B) is an unsaturated hydrocarbon having only one carbon-carbon double bond in the molecule, it is preferable because it is readily available.

It is even more preferred if component (B) is an α-olefin having a terminal double bond. This is because the steric hindrance during the reaction is small and the reactivity is high. It is therefore preferably linear.

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

The amount of component (B) should be added according to the amount of silicon-hydrogen bonds remaining in component (A).
Specifically, the amount of component (B) is the amount required to make the silicon-hydrogen bond residual amount of component (A) detected by alkaline titration 0% or more and 0.001% or less. . Considering the reaction efficiency, it is preferable to adjust the amount so that the number of alkenyl groups in component (B) is 1.0 to 2.0 per silicon-bonded hydrogen atom contained in component (A) as a whole. .
The component (B)-containing emulsion is mixed with the component (A) after forming an emulsion together with the following components (C) to (E). Emulsions generally destabilize over time, causing separation, sedimentation, and the like to decrease. Therefore, it is more preferable to use the component (B) immediately after emulsification. The elapsed time after emulsification is preferably, for example, 1 to 10 days, depending on the properties, concentrations, etc. of components (B) to (E).

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

Water, which is component (C), can be divided into initial water, dilution water, and temperature adjustment water according to its role. The water added when emulsifying component (B) is initial water, the water added when diluting the emulsion of component (B) is diluted water, and the heat generated by the reaction between component (B) and component (A). When the temperature of the reaction system rises due to the above, water as a medium for maintaining the temperature of the reaction system below a certain level is referred to herein as temperature-adjusting water.

The initial water and dilution water used to emulsify component (B) also function as temperature controls for the system. Therefore, the amount of temperature adjustment water required to maintain the temperature of the reaction system below a certain level is the amount of initial water and dilution water required for emulsification of component (B), the total amount derived from equation (3) is the amount subtracted from

c_water :水の比熱 （ｋＪ／ｋｇ）
ΔT :

（℃）
ΔrH :付加反応熱（kJ/mol）
c :比熱（kJ/kg・℃）
w :質量（ｋｇ）

：水以外の成分の熱容量の総和（ｋＪ／ｋｇ）
The amount of temperature-adjusting water required to maintain the temperature of the reaction system depends on the substance amount (g/mol) of component (B) or component (A) and the upper limit of temperature rise (arbitrary temperature). It can be obtained using the following formula (3) and parameters.

c _water : Specific heat of water (kJ/kg)
ΔT:

(°C)
ΔrH: Heat of addition reaction (kJ/mol)
c: Specific heat (kJ/kg・°C)
w: mass (kg)

: Total heat capacity of components other than water (kJ/kg)

と、成分（Ｃ）の必要最低限量は計算で導かれる。 For example, 10 parts by mass of n-octene emulsion (50% solid content) as component (B), 7 parts by mass (40% solid content) of CROSSLINKER V 72 JP manufactured by Asahi Kasei Wacker Silicone Co., Ltd. as component (A), When the allowable temperature rise range is 20°C from 25°C (upper limit temperature 45°C), the amount of component (C) required is 4.18 [kJ] for the specific heat of water, n-octene, and silicone. /kg·°C], 2.18 [kJ/kg·°C], 1.51 [kJ/kg·°C], and the heat of addition reaction as 168 kJ/mol. Since the amount of reactants = hydrogen content, and the hydrogen content in 7 parts by mass of CROSSLINKER V 72 JP (40% solid content) is 20.22 mol,

and the minimum necessary amount of component (C) is calculated.

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 the emulsification of component (B) is 5 parts by mass. 20.7 parts by mass of component (C) to be additionally added to the mixed system.

(About component (D))
Component D is a catalyst for reacting component (A) and component (B), and is not particularly limited as long as it is a platinum group catalyst, and known addition reaction catalysts can be used. Examples thereof include platinum-based, palladium-based, rhodium-based, and ruthenium-based catalysts, among which platinum-based catalysts are particularly preferred. Examples of the platinum-based catalyst include chloroplatinic acid, alcohol solutions or aldehyde solutions of chloroplatinic acid, and complexes of chloroplatinic acid with various olefins or vinyl siloxanes. The amount of these platinum group metal catalysts to be added is a catalytic amount, and the platinum group metal amount may be in the range of 1 to 50 ppm, 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.

(About 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 the component (B). It may be a nonionic surfactant. A nonionic surfactant and an anionic surfactant are more preferably used because compounds containing amines may inhibit the action of the platinum group catalyst.
For example, nonionic surfactants include 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; The total H L B (hydrophile/lipophile balance) of the nonionic surfactant used is preferably in the range of 8-17, more preferably in the range of 10-16.
Examples of anionic surfactants include alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, polyoxyethylene alkyl ether sulfate salts, polyoxyethylene alkylphenyl ether sulfate salts, and fatty acid alkylolamide sulfates. Salts, alkylbenzenesulfonates, polyoxyethylene alkylphenyl ether sulfonates, α-olefinsulfonates, α-sulfo fatty acid ester salts, alkylnaphthalenesulfonic acids, alkyldiphenylether disulfonates, alkanesulfonates, N-acyl Taurates, dialkyl sulfosuccinates, monoalkyl sulfosuccinates, polyoxyethylene alkyl ether sulfosuccinates, fatty acid salts, polyoxyethylene alkyl ether carboxylates, N-acyl amino acid salts, monoalkyl phosphate ester salts, dialkyl Phosphate ester salts, polyoxyethylene alkyl ether phosphate ester salts and the like can be mentioned.

The blending amount of component (E) is 1 to 10 parts by mass based on 100 parts by mass of component (B). If the amount is less than 1 part by mass, dispersion is difficult, and if the amount exceeds 10 parts by mass, the viscosity of the composition increases and the handleability deteriorates. More preferably, it is 3 to 6 parts by mass.

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 hydrophobized portion and a silanol group on the surface have a moderate affinity for both the oil phase and the water phase, so they are arranged at the oil phase / water phase interface to make the water phase continuous. Phased oil-in-water emulsions can be provided.

The silica particles have a hydrophobized portion and a silanol group on the surface, and can be arranged at the oil phase/aqueous phase interface of the component (A) organopolysiloxane oil droplets in the aqueous emulsion phase. . Such silica particles have a hydrophilic silanol group and a hydrophobized silanol group present on the surface within a predetermined ratio, so that the hydrophilicity-hydrophobicity balance of the particles is controlled. , is placed at the oil phase/aqueous phase interface composed of the organopolysiloxane of component (A), and exhibits an emulsifying function similar to that of conventional organic surfactants.

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 obtained by a dry method such as fumed silica, pyrogenic silica and fused silica, and precipitated silica or colloidal silica obtained by a wet method. These are known to those skilled in the art. Among these, calcined silica, precipitated silica and colloidal silica are preferably used. The silica particles may be hydrophilic silica with residual silanol groups on the surface, or hydrophobic silica with silylated silanol groups on the surface. Hydrophobic silica can be produced by a known method of treating hydrophilic silica with organosilicon halides such as methyltrichlorosilane, alkoxysilanes such as dimethyldialkoxysilane, silazane, and low-molecular-weight methylpolysiloxane. can be done.

When using silica having a hydrophobized portion and a silanol group on the surface of the silica particles, the surface tension of the silica particles is set in a region necessary for surface activity, so that a normal surfactant is not present. can be stabilized by being placed at the oil/aqueous phase interface of the oil droplets. The ratio of silanol groups remaining after silylation to silanol groups before silylation is preferably in the range of 50 to 95%. If the silanol residual rate is less than 50% or more than 95%, the function corresponding to the surfactant at the oil phase/aqueous phase interface cannot be exhibited. Silylation or residual silanol can be determined by measuring the carbon content by elemental analysis or by measuring the residual amount of reactive silanol groups on the silica surface. The silica particles used for the preparation may contain particles whose entire surface is silylated or particles whose entire surface is not silylated. However, if the overall silylation rate is within the above range and the necessary emulsifying function can be exhibited, it can be used.

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 can be achieved. 0.1 to 10% is preferred. A stable emulsion cannot be obtained at less than 0.1% or more than 10%. More preferably, it is within the range of 0.1 to 10%.

A method for treating waste hydrogenpolysiloxane, in which components (A) to (E) are mixed,
A B emulsification step of blending component (B) with 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 and the emulsified component (A) to obtain an alkyl-modified silicone emulsified composition.

The component (B) emulsification step is a step of turning the oily component (B) into an emulsion, and the production method is not particularly limited, and includes mechanical emulsification, phase inversion emulsification, D phase emulsification, phase inversion temperature emulsification, and gel emulsification. , a known method such as liquid crystal emulsification. An oil-in-water type is particularly preferred.

The component (B) emulsifying step can be carried out by a known method once an emulsion (also referred to as an emulsion) of component (B) is obtained. For example, a method of mixing and emulsifying the components using a homogenizer, colloid mill, homogenizer, high-speed stator rotor stirring device, or the like can be employed. Specifically, initial water is added to components (B) and (E) and stirred to form a water-in-oil type, and then diluted water is added to form an oil-in-water type. Dispersion is facilitated and emulsion stability is improved. Moreover, it is preferable to provide the following steps for controlling the particle size (reducing the particle size).
In the component (B) emulsifying step, an amount of component (B) corresponding to component (A), component (E), and a predetermined amount of water (initial water) are mixed by shearing action to obtain an initial dispersion containing component B. a first step of forming an object;
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, a fourth step of adding component (D), which is an emulsion, to the emulsion containing component (B) obtained in the third step.

The first step is part of the emulsification step of component (B). The component (B), which is the oil phase, is added to the mixed system of the component (E) surfactant and the initial water, and a stirring device such as a homogenizer, colloid mill, homomixer, high-speed stator rotor stirring device, etc. is used. to prepare a water-in-oil dispersion system. By going through this first step, it is possible to reduce the particle size. The amount of component (E) to be blended is preferably 3 to 6 parts by mass based on 100 parts by mass of component (B).
The amount of initial water must be sufficient to form this coexisting phase, and is determined by the amount of component (E) emulsifier. It is added in an amount of 1 to 100 parts by weight, preferably 40 to 70 parts by weight, per 100 parts by weight of the emulsifier.
As for the order of addition, it is preferable to add 0.5 to 3 parts of the initial water to 3 to 15 parts of the emulsifier, and then add the oil phase.

The second step is the step of optionally adding component (D) during the emulsification step of component (B) and emulsifying at the same time.
This step is preferred when component (D) is oily. Emulsification together with component (B) facilitates dispersion in water. This step can be omitted when the material is already emulsified, such as an emulsion, and can be easily dispersed in water. The amount of component (D) to be added is such that platinum is 1 to 100 ppm, preferably 2 to 20 ppm.

The third step is part of the emulsifying step of component (B), and is a step of adding dilution water to the mixture obtained in the first and second steps to disperse and dilute the mixture in water. The dilution water added in the third step is water as a dispersion medium (water that becomes a continuous phase). The amount to be added can be set arbitrarily, and the amount 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.

The fourth step is to optionally add component (D) to the emulsion containing component (B). This step may be carried out when the component (D) is water-soluble such as an emulsion, and this step may be omitted when the component (D) is added in the second step.

The mixing step is a step of mixing an emulsion containing component (B) and an emulsified component (A) to obtain an alkyl-modified silicone emulsified composition,
A fifth step of blending the component (A) with the emulsion containing the component (B);
optionally a sixth step of adding temperature conditioned water to the mixture obtained in the fifth step;
optionally, a seventh step of adding component (D) to the mixture obtained in the fifth or sixth step.

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

The fifth step is part of the step of mixing component (A) and component (B) to obtain an adduct. The order of addition does not matter. The container material for mixing is not particularly limited as long as it is a commonly used material, and plastics, metals, and the like can be used. PTFE is particularly preferred.

The sixth step is the step of optionally adding water for the purpose of suppressing the heat of reaction generated when component (A) and component (B) are mixed. Materials that can be applied in this process are not specified as long as they can suppress (absorb) the heat of reaction. Based on this, water is the most preferred. The temperature of the water to be applied is normal temperature or lower, preferably 4 to 20°C.
This step can be omitted if the heat of reaction is not considered.

The seventh step is mixing components (A) and (B) and optionally adding component (D) to the mixture of component (B). This step may be carried out when the component (D) is water-soluble such as an emulsion, and when the component (D) is added in the second step or the fourth step, this step is omitted. may

The platinum group component (D) is added in at least one of the second step, fourth step, or seventh step.
Component (D) has a function as a catalyst that promotes the addition reaction of component (A) and component (B). good.

The total amount of water added in the first step, the third step and the sixth step depends on the silicon-hydrogen bond content in the component (A) and the arbitrarily set target reaction temperature. can do. The arbitrarily set target reaction temperature is a temperature that is determined in consideration of process safety, heat resistance of equipment, etc. For example, 0° C. or higher and 80° C. or lower is even better. If the temperature is below 0°C, it will be lower than the melting point of water, which is expected to cause problems in the process. More preferably, the temperature is 10°C or higher and 60°C or lower.

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 described method.
Assuming that all the heat of reaction is used to change the temperature of the system, the following formula (5) holds.

c_water:水の比熱
ΔT :

ΔrH ：付加反応熱
c : 比熱
w : 質量

： 各成分（水以外）の熱容量の総和

パラメータは付加反応熱ΔrH: [kJ/mol]、成分（Ｂ）の比熱c_olefine [kJ/kg・℃]、シリコーンオイルの比熱c_silicone[kJ/kg・℃]、水の比熱c_water [kJ/kg・℃]、成分（Ａ）の重量[kg]、成分（Ｂ）の重量[kg]、成分（Ａ）のケイ素‐水素結合残留量[mol]である。 Here the amount of reactants is equivalent to the amount of residual silicon-hydrogen bonds in component (A). Formula (6) for setting the target temperature after the reaction and determining the necessary amount of water to be added can be derived from the above formula (5).

c _water : Specific heat of water ΔT :

ΔrH : Heat of addition reaction
c : specific heat
w : mass

: Total heat capacity of each component (other than water)

The parameters are heat of addition reaction ΔrH: [kJ/mol], specific heat of component (B) c _olefine [kJ/kg・℃], specific heat of silicone oil c _silicone [kJ/kg・℃], specific heat of water c _water [kJ /kg·°C], the weight of component (A) [kg], the weight of component (B) [kg], and the silicon-hydrogen bond residual amount of component (A) [mol].

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

The required time depends on the reaction rate. To control (adjust) the reaction rate, the contact area between component (A) and component (B) should be increased. In other words, by reducing the emulsion particle size, it is possible to increase the specific surface area and increase the contact area.

The emulsion particle size may be adjusted by adjusting the size of the shear force during emulsification. It is preferable to adjust the amount.

The mixing step can further include an eighth step of measuring the temperature of the mixture containing the component (B)-containing emulsion (mixture temperature). The total amount of water added in the first step, the third step, and the sixth step is controlled by measuring the temperature when the calculation formula described in Equation 6 above is not used. , the temperature can be controlled.
For example, when the temperature detected in the eighth step is higher than the target temperature, the sixth step is performed again. The eighth and sixth steps may be repeated until the mixture temperature reaches the target reaction temperature. By repeating this process, the temperature of the system can be controlled and the safety of the process can be achieved. The end point of the repetition is the point at which the temperature falls below the target temperature and the temperature begins to drop.

The alkyl-modified silicone emulsified composition produced by the method for treating waste hydrogenpolysiloxane described above may be discarded, but is used as a release agent, antifoaming agent, car polish, fiber treatment agent, or antistatic agent. is also possible.

Next, the component (a) containing water and an organohydrogensiloxane having one or more silicon-bonded hydrogen atoms in one molecule is a compound having only one carbon-carbon double bond in the molecule. An apparatus for treating with component (b) comprising
The embodiments described below describe examples of the present invention. The present invention is by no means limited to the following embodiments, and includes various modifications implemented within the scope of the present invention. Note that not all of the configurations described below are essential configurations of the present invention.

The hydrogenpolysiloxane treatment apparatus 1 of the present invention shown in FIG.
Component (a) containing water and an organohydrogensiloxane having one or more silicon-bonded hydrogen atoms per molecule, including compounds having only one carbon-carbon double bond in the molecule An apparatus for treating with component (b), 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 manufacturing apparatus 200 for manufacturing the component (b)-containing emulsion;
the component (b) flow rate adjustment mechanism 121;
a reaction vessel 140 for receiving the component (a) and the emulsion containing the component (b);
a water line 131 equipped with a water flow rate adjustment mechanism 132 for introducing water into the reaction vessel 140;
a temperature measuring means 150 for measuring the internal temperature of the reaction vessel 140;
a control means 160 for controlling the introduction amount of at least one of the component (a), the component (b)-containing emulsion, or water into the reaction vessel based on the temperature measured by the temperature measurement means 150; ,
A detection means 170 (not shown) for detecting the remaining amount of SiH in the product stored in the reaction tank,
Hydrogen polysiloxane processing equipment.

Component (a) has the same composition as component (A), and may be a mixture containing water and hydrogenpolysiloxane, and does not necessarily have to be waste hydrogenpolysiloxane. Organohydrogensiloxane having one or more silicon-bonded hydrogen atoms in one molecule is represented by the following general formula (1).
R1aSiO _{(4-a)/2 (} ¹ )
(In formula (1), R ¹ may be the same or different in the molecule and is a substituted or unsubstituted saturated monovalent hydrocarbon group having 1 to 25 carbon atoms, a substituted or unsubstituted is a group selected from an aromatic group of up to 30, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or a hydrogen atom, and a is 1 to 3.)
Component (a) may be in an emulsion state or a liquid crystal state, or may be in a state in which hydrogenpolysiloxane and water are separated.
Component (a) may be a composition prepared in advance, and the waste discharged in the process of producing the emulsion containing hydrogenpolysiloxane is collected in a waste container. good too.

The component (a) storage tank 110 may be a container capable of storing component (a) containing water and an organohydrogensiloxane having one or more silicon-bonded hydrogen atoms per molecule. , it may be a sealable container, but it may also be an open reservoir.

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 manual opening/closing valve, or a combination of a flow meter and an adjustable valve. Alternatively, it may be a flow rate control valve that automatically controls the flow rate to a predetermined flow rate. For example, the flow rate can be 0.01 m ³ /h or more and 1 m ³ /h or less.

Component (b) is the same as component (B) above. 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 manual opening/closing valve, or a combination of a flow meter and an adjustable valve. Alternatively, it may be a flow rate control valve that automatically controls the flow rate to a predetermined flow rate. For example, the flow rate can be 0.01 m ³ /h or more and 1 m ³ /h or less.

Component (c) is equivalent to component (C) above. A component (c) lead-out line 131 for leading the component (c) to the reaction tank 140 has a flow rate adjusting mechanism 132 for adjusting the flow rate of the 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 the component (c), and may be a manual opening/closing valve, or a combination of a flow meter and a valve whose opening degree can be adjusted. Alternatively, it may be a flow rate control valve that automatically controls the flow rate to a predetermined flow rate. For example, the flow rate can be 0.01 m ³ /h or more and 1 m ³ /h or less.

A reaction vessel 140 that receives component (a), component (b)-containing emulsion, and component (c) from each lead-out line can be provided with temperature measuring means 150 and detecting means 170 for detecting the residual amount of SiH. The detection means 170 can also be provided outside the reaction tank 140 (for example, an analysis device installed in a separate room from the hydrogenpolysiloxane treatment device). In this case, the sample to be supplied to the detection means 170 is withdrawn from the reaction vessel 140 . It also has a feedback control mechanism that transmits the results measured by the temperature measuring means 150 to the control device 160 and controls each component flow rate adjustment mechanism (111, 121, 132) based on the measurement results. This feedback control is applied when the temperature inside the reaction vessel 140 is higher or lower than an arbitrarily set target temperature, and operation at an arbitrarily set temperature is possible.
For example, when the temperature in the reaction vessel is higher than the target temperature, the flow rate adjusting mechanisms 111 and 121 decrease the flow rate, and the flow rate adjusting mechanism 132 increases the flow rate of component (c). This control is continued until the reaction temperature measured by the temperature measuring means 150 falls below the target reaction temperature.

The component (b)-containing emulsion manufacturing apparatus 200 shown in FIG. In addition, two component (c) lead-out lines are provided, each with a predetermined amount of water lead-out line 221 and an emulsion dilution water lead-out line 222 . Flow control mechanisms 231 and 232 are provided on each outlet line. The flow rate adjusting mechanisms 231 and 232 are not particularly limited as long as they are means capable of adjusting the flow rate of the component (c). Alternatively, it may be a flow rate control valve that automatically controls the flow rate to a predetermined flow rate.
Further, if the component (b) emulsion can be supplied in an amount corresponding to the amount of the component (a), the component (b) containing emulsion manufacturing apparatus 200 can be operated alone, and the component (b) containing emulsion storage tank 120 Alternatively, it may be linked to the operation of the reaction tank 140 .
The first emulsifier 211 and the second emulsifier 212 have different roles, the first emulsifier 211 emulsifying, and the second emulsifying machine 212 assisting in dilution with the dispersion medium (water). The first emulsifier 211 and the second emulsifier 212 work simultaneously and never work alone.

EXAMPLES Hereinafter, the present invention will be specifically described by showing Examples and Comparative Examples, but the present invention is not limited thereto. In the examples below, the physical properties in the tables were measured by the following test methods.

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

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

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

(Emulsification Example 4)
As component (E), 5 parts by weight of silica particles manufactured by Wacker Chemie AG, and as component (C), 44.95 parts of water are added, and an ULTRA-TURRAX (registered trademark) T50 basic shaft generator G45M manufactured by IKA is used. , 2000 rpm to obtain a silica dispersion.
As component (B), 50 parts by weight of Linearene 12 (1-dodecene>95%, specific gravity at 20° C.) manufactured by Idemitsu Kosan Co., Ltd., and Wacker Chemie AG as component (D). 0.05 parts by weight of Wacker (registered trademark) Catalyst OL (a mixture of platinum complex dispersed in polyorganosiloxane) manufactured by IKA Co., Ltd., using an ULTRA-TURRAX (registered trademark) T50 basic shaft generator G45M manufactured by IKA, at 2000 rpm. Stir and mix to obtain an emulsion.

<Mixing process>
The target upper limit temperature in the mixing step was set to 60°C. The temperature at the start of the reaction is 25°C.

よって、成分（Ｃ）２０重量部は、目標反応温度以下となるのに十分な量である。
以下実施例２～６、比較例１～３も同様に、目標反応温度以下となるのに十分な成分（Ｃ）の量を添加している。 (Example 1)
As the component (A), 10 parts by weight of Wacker (registered trademark) CROSSLINKER V 72 JP manufactured by Asahi Kasei Wacker Silicone Co., Ltd., and as the emulsion of the component (B), 11.1 parts by weight of the linearene 12 emulsion produced in Emulsification Example 1. Part, as component (C), 20 parts by weight of water are added and mixed by hand stirring for 10 minutes.
The amount of this component (C) was set based on the following calculation results.

Therefore, 20 parts by weight of component (C) is an amount sufficient to bring the reaction temperature below the target reaction temperature.
Similarly, in Examples 2 to 6 and Comparative Examples 1 to 3, the amount of component (C) sufficient to lower the target reaction temperature or lower was added.

(Example 2)
As the component (A), 10 parts by weight of Wacker (registered trademark) CROSSLINKER V 72 JP manufactured by Asahi Kasei Wacker Silicone Co., Ltd., and as the emulsion of the component (B), 22.2 parts by weight of the linearene 12 emulsion produced in Emulsification Example 1. 20 parts by weight of water are added and mixed by hand stirring for 10 minutes.

(Example 3)
As the component (A), 10 parts by weight of Wacker (registered trademark) CROSSLINKER V 72 JP manufactured by Asahi Kasei Wacker Silicone Co., Ltd., and as the emulsion of the component (B), 11.1 parts by weight of the linearene 12 emulsion produced in Emulsification Example 2. 20 parts by weight of water are added and mixed by hand stirring for 10 minutes.

(Example 4)
As the component (A), 10 parts by weight of Wacker (registered trademark) CROSSLINKER V 72 JP manufactured by Asahi Kasei Wacker Silicone Co., Ltd., and as the emulsion of the component (B), 11.1 parts by weight of the linearene 12 emulsion produced in Emulsification Example 3. 20 parts by weight of water are added and mixed by hand stirring for 10 minutes.

(Example 5)
As the component (A), 10 parts by mass of Wacker (registered trademark) CROSSLINKER V 72 JP manufactured by Asahi Kasei Wacker Silicone Co., Ltd., and as the emulsion of the component (B), 11.1 parts by mass of the linearene 12 emulsion produced in Emulsification Example 4. and 20 parts by mass of water are added and mixed by hand stirring for 10 minutes.

(Example 6)
As component (A), 10 parts by mass of hydrogen siloxane-containing waste (solid) generated in the manufacturing process of Wacker (registered trademark) CROSSLINKER V 72 JP manufactured by Asahi Kasei Wacker Silicone Co., Ltd., and PEG400 manufactured by Toho Co., Ltd. as an additive. 2 parts by mass, 29.1 parts by mass of the emulsion of linearene 12 prepared in Emulsification 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

(Comparative example 1)
As component (A), 10 parts by mass of Wacker (registered trademark) CROSSLINKER V 72 JP manufactured by Asahi Kasei Wacker Silicone Co., Ltd., 5.5 parts by mass of linearene 12 as component (B), and 25 parts by mass of water were added, and 10 parts by mass were manually stirred. Mix for a minute.

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

(Comparative Example 3)
As the component (A), 10 parts by mass of Wacker (registered trademark) CROSSLINKER V 72 JP manufactured by Asahi Kasei Wacker Silicone Co., Ltd., and as the emulsion of the component (B), 5.5 parts by mass of the linearene 12 emulsion prepared in Emulsification Example 1. and 20 parts by mass of water are added and mixed by hand stirring for 10 minutes.

<Measurement of silicon-hydrogen bond residual amount>
The amount of silicon-hydrogen bonds remaining in the mixture of component (A) and component (B) was determined by alkaline titration. On one side of the twin flask, 0.1 to 15 parts by mass of the substance to be measured, 5 parts by mass of ethanol (95) special grade manufactured by Kanto Chemical Co., Ltd. as a solvent, and 5 parts by mass of ethanol (95) special grade manufactured by Kanto Chemical Co., Ltd. on the other side After connecting a double-ended flask containing 2 parts by mass of sodium hydroxide manufactured by Kanto Chemical Co., Ltd. to a glass tube filled with water, the hydrolysis reaction is started by mixing the solution. is determined from the water level in the glass tube, and the silicon-hydrogen bond residual amount is calculated by the following formula.

The above P is the vapor pressure of ethanol and is calculated from the Antoine formula (logP = A-(B/(C+T)).
Here, A = 8.21337, B = 1652.05, C = 231.48, and T = room temperature [°C].

As an example, Table 1 below shows the calculation results of the ethanol vapor pressure P when the room temperature is 18 to 26°C.

<Evaluation Criteria for Residual Silicon-Hydrogen Bond Amount>
If the silicon-hydrogen bond residue was 0.001% or less, it was determined that the silicon-hydrogen bond residue was effectively reduced.

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

In Examples 1 and 2, the number of alkenyl groups in the emulsion of linearene 12 of component (B) per silicon-bonded hydrogen atom in the entire composition was 1.0 and 2.0, respectively. This is an example of adding an amount that becomes one.

In Examples 1 and 2, 90 days after mixing, the silicon-hydrogen bond residual amount residual rate was 0.0001% or less, and the silicon-hydrogen bond residual amount was effectively reduced. The obtained composition is represented by the following general formula (5).
R1aSiO _(4-a)/2 ⁽ ₅ )
(In formula (5), R ¹ may be the same or different in the molecule and is a substituted or unsubstituted saturated monovalent hydrocarbon group having 1 to 25 carbon atoms, a substituted or unsubstituted A group selected from an aromatic group of up to 30, a hydroxyl group, and an alkoxy group having 1 to 6 carbon atoms, and a is 1 to 3.)

In Examples 3 and 4, the amount of alkenyl groups in the linearene 12 emulsion of component (B) per silicon-bonded hydrogen atom in the entire composition was 1.0. For example.

In Examples 3 and 4, the silicon-hydrogen bond residual amount residual rate was 0.0001% or less 90 days after mixing, and the silicon-hydrogen bond residual amount was effectively reduced. The obtained composition is represented by the following general formula (5).
R1aSiO _(4-a)/2 ⁽ ₅ )
(In formula (5), R ¹ may be the same or different in the molecule and is a substituted or unsubstituted saturated monovalent hydrocarbon group having 1 to 25 carbon atoms, a substituted or unsubstituted A group selected from an aromatic group of up to 30, a hydroxyl group, and an alkoxy group having 1 to 6 carbon atoms, and a is 1 to 3.)

In Examples 1, 3, and 4, the ingredients prepared in Examples 1, 2, and 3 were added as the component (B). The smaller the particle size, the greater the reduction rate 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.

Example 5 is an example in which the number of alkenyl groups in the linearene 12 emulsion of component (B) per silicon-bonded hydrogen atom in the entire composition was 1.0. (B) is an example using silica particles for emulsification.

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

Example 6 is an example in which the number of alkenyl groups in the linearene 12 emulsion of component (B) per silicon-bonded hydrogen atom in the entire composition is 1.0. This is an example in which a polyhydric alcohol is added as an agent.

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

Comparative Example 1 used Linearene 12 as component (B) without emulsification.

In Comparative Example 1, 90 days after mixing, the silicon-hydrogen bond residual amount residual rate was 0.17% by mass, and the silicon-hydrogen bond residual amount did not decrease to the allowable value.

Comparative Example 2 is an example in which the number of alkenyl groups in the linearene 12 emulsion of component (B) is 0.3 per silicon-bonded hydrogen atom in the entire composition.

In Comparative Example 2, 90 days after mixing, the silicon-hydrogen bond residual amount residual rate was 0.11% by mass, and the silicon-hydrogen bond residual amount did not decrease to the allowable value.

Comparative Example 3 is an example in which the number of alkenyl groups in the linearene 12 emulsion of component (B) is 0.5 per silicon-bonded hydrogen atom in the entire composition.

In Comparative Example 3, 90 days after mixing, the silicon-hydrogen bond residual amount residual rate was 0.04% by mass, and the silicon-hydrogen bond residual amount did not decrease to the allowable value.

1. Hydrogen polysiloxane processing unit 110 . Component (a) reservoir 121 . Component (b) flow control mechanism 131 . water line 132 . Water flow adjustment mechanism 140. Reaction tank 150 . temperature measuring means 160 . control means 200 . Component (b) containing emulsion manufacturing device 210 . Receiving tank 211 . First emulsifier 212 . Second emulsifier

Claims (13)

Waste generated in the process of producing an emulsion containing hydrogenpolysiloxane, including a mixing step of mixing component (A) and an emulsion containing component (B) below to obtain an alkyl-modified silicone emulsified composition A method for treating hydrogenpolysiloxane, comprising:
The component (A) is the waste hydrogen polysiloxane containing (A) water and an organohydrogensiloxane having one or more silicon-bonded hydrogen atoms in one molecule,
The component (B)-containing emulsion comprises (B) a hydrocarbon compound having only one carbon-carbon double bond in the molecule;
(C) water (initial water, dilution water, temperature adjustment water);
(D) a platinum group catalyst; and (E) an emulsifier.
The component (B) emulsifying step is
a first step of mixing the component (B), the component (E), and the initial water in amounts corresponding to the component (A) by shearing 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) When,
Optionally, a fourth step of adding the (D) component, which is an emulsion, to the emulsion containing the component (B) obtained in the third step,
The mixing step includes
A fifth step of blending the component (A) with the emulsion containing the component (B);
optionally a sixth step of adding temperature conditioned water to the mixture obtained in said fifth step;
optionally, a seventh step of adding said component (D) to the mixture obtained in said fifth step or said sixth step;
The component (D) is added in at least one step of the second step, the third step, or the fifth step,
The total amount of water added in the first step, the third step, and the sixth step depends on the silicon-hydrogen bond content in the component (A) and the arbitrarily set target reaction temperature. 3. The method of claim 2, wherein the amount is responsive. 4. The method according to claim 3, wherein the total amount of water added in the first step, the third step and the sixth step is given by the following formula (1).

The magnitude of the shear force in the first step, the amount of the component (E) in the first step, the amount of water added in the third step, or from the end of the first step or the second step 5. The method according to claim 3 or 4, wherein the duration of the mixing step is adjusted by adjusting at least one of , the time until the start of the third step. The mixing step further includes an eighth step of measuring the temperature of the mixture containing the emulsion containing the component (B) (mixture temperature), and when the mixture temperature is higher than the target reaction temperature, the sixth 6. A method according to any one of claims 3 to 5, wherein the steps are performed and the eighth step and the sixth step are repeated until the mixture temperature reaches the target reaction temperature. The component (E) is at least one of an ionic surfactant, a nonionic surfactant, or silica particles having a hydrophobized portion and a silanol group on the surface. Item 7. The method according to any one of Item 6. 8. The method according to any one of claims 2 to 7, further comprising adding a polyhydric alcohol in the mixing step when component (A) is in a liquid crystalline state. 9. The method according to any one of claims 1 to 8, wherein said component (B) is an unsaturated hydrocarbon having a double bond. 10. The method according to any one of claims 1 to 9, wherein the component (B) is an α-olefin having a terminal double bond. A process according to any one of claims 1 to 10, wherein component (B) is an α-olefin having 10 to 14 carbon atoms. Claims 1 to 4, wherein the amount of olefin contained in component (B) is an amount required to make the residual amount of silicon-hydrogen bonds in component (A) 0% to 0.001%. 12. The method of any one of 11. Component (a) containing water and an organohydrogensiloxane having one or more silicon-bonded hydrogen atoms per molecule, and a component containing a compound having one carbon-carbon double bond in the molecule An apparatus for processing according to (b), comprising:
a component (a) storage tank for storing the component (a);
the component (a) outlet flow rate adjustment mechanism;
a component (b)-containing emulsion manufacturing apparatus for manufacturing the component (b)-containing emulsion;
the component (b) flow rate adjustment mechanism;
a reactor for receiving the component (a) and an emulsion containing the component (b);
a water line equipped with a flow control mechanism for introducing water into the reaction vessel;
temperature measuring means for measuring the internal temperature of the reaction vessel;
control means for controlling the introduction amount of at least one of the component (a), the component (b)-containing emulsion, or water into the reaction vessel based on the temperature measured by the temperature measurement means;
A detection means for detecting the amount of SiH remaining in the product stored in the reaction vessel,
Hydrogen polysiloxane processing equipment. The component (b)-containing emulsion manufacturing apparatus includes:
a receiving vessel for receiving at least said component (b) and said component (e);
an initial water introduction line with a flow 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 of the mixture discharged from the receiving tank and the initial water by shear force;
a component (b)-containing initial dispersion lead-out line for leading out the component (b)-containing initial dispersion from the component (b)-containing initial dispersion storage tank;
one or more moisture addition lines equipped with a flow control mechanism, connected on the component (b)-containing initial dispersion lead-out line;
13. The processing device of claim 12, comprising:

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