CN109758794B - Preparation method of organic silicon composition - Google Patents
Preparation method of organic silicon composition Download PDFInfo
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- CN109758794B CN109758794B CN201910214371.2A CN201910214371A CN109758794B CN 109758794 B CN109758794 B CN 109758794B CN 201910214371 A CN201910214371 A CN 201910214371A CN 109758794 B CN109758794 B CN 109758794B
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Abstract
The invention relates to a preparation method of an organic silicon composition, which is prepared by mixing and stirring vinyl polysiloxane, hydrogen-containing polysiloxane, a structure control agent, a catalyst, silicon dioxide, inert organic silicon resin and water. By dripping the hydrogenous polysiloxane with a spatial structure and controlling the dripping speed, the problem of reaction implosion of vinyl polysiloxane and hydrogenous polysiloxane under the condition of no inert polysiloxane is solved, the foam control performance of the composition is improved, the obtained composition is stable to store, and the viscosity cannot be greatly increased in a storage period. The organic silicon composition prepared by the method can be used in the industries of textile printing and dyeing, sewage treatment, industrial cleaning and the like.
Description
Technical Field
The invention relates to a preparation method of an organic silicon composition, the composition prepared by the method can efficiently control the generation of foam in an anionic surfactant, and the invention belongs to the technical field of fine chemical preparations.
Background
Foam is a common phenomenon in daily life and industrial production processes, and it is further desirable in industrial systems to effectively control foam production. According to different industries, people have different requirements on the foam. For example, the washing industry requires that a certain amount of foam be present to carry away the soil; air bubbles can not exist in the papermaking industry, and the air bubbles can cause the formation of pinholes on the surface of paper and influence the appearance and tensile strength of the paper; the coating ink industry, especially high-grade coating ink, has unique requirements on the existence of foam, otherwise, the phenomena of shrinkage cavity, fish eyes and the like are caused.
Methods for eliminating or controlling foam are generally classified into "mechanical methods" and "chemical methods". The so-called mechanical method is to eliminate harmful foam by using methods such as high-pressure impact, temperature rise, vacuum pumping, mechanical stirring and the like, but the effect is not satisfactory; the so-called "chemical method" is to eliminate foam by using chemical agents, such as foam control agents, whose basic principle is to cause a change in the local thickness of the foam membrane by a change in surface tension, and the foam control agents do not eliminate foam by reducing the concentration of the foaming substance by a chemical reaction.
Foam control agents in industrial production are to be understood more as defoamers, and in practice it should be more appropriate to say that they are foam control agents. Depending on the actual industry, one may choose to control the foam to a specific range rather than eliminate it altogether. Currently, foam control agents have been widely used in paper making, coatings, chemical industry, printing and dyeing, medicine, water treatment, food processing, oil extraction and other processes.
The foam control agent may be classified into silicones, polyethers, fatty alcohols, mineral oils, polyether-modified silicones, and the like, depending on the active material that exerts the foam control function. The application range of the organosilicon foam control agent is widest, and the organosilicon foam control agent has a unique effect on the stable foam of the surfactant, mainly because the surface tension of the organosilicon foam control agent is lower and the organosilicon foam control agent is easy to spread on the surface of a bubble film, the dosage is small, and the cost is low; and secondly, the organosilicon foam control agent has low volatility, no toxicity and no side effect.
The foam control agent of silicone type is composed of several basic components of polysiloxane, hydrophobic particles and catalyst. US4639489 is the earliest foam control agent patent, which describes a foam control agent obtained by processing polydimethylsiloxane and silica at high temperature for a long time, but this type of foam control composition has a single structure and poor foam inhibition performance, and is still used in some industries so far; US4338217A1 is prepared by mixing alkoxy polysiloxane and white carbon black particles. The organosilicon active substance described in CN101120056 is characterized in that the viscosity of the composition treated by polysiloxane, white carbon black and catalyst is reduced by at least 50% compared with the viscosity before treatment; US5531929A describes the effect of the reaction product of a hydrogen-terminated polysiloxane and a vinyl-terminated polysiloxane in a strongly alkaline system; US5824739 directly mixing amino or carboxyl containing polysiloxane with white carbon black to obtain an organosilicon composition; US6521586B1 describes defoaming actives consisting of alkyl polysiloxane, white carbon and silicone, which have a good effect in the laundry industry. US2006160908a1 describes the addition of a small amount of water during the preparation of the active to enhance the effectiveness of the composition. US2008064806a1 investigated the difference between the viscosity and the foam suppressing effect of silicone compositions; US2014316015a1 mixes hydrophilic white carbon black, hydrophobic white carbon black, polysiloxane, silicone resin, and a catalyst to prepare a foam control composition, so that the defoaming composition is finally emulsified at a suitable viscosity, but a cross-linking structure formed by hydroxyl condensation is weak, and a good effect of inhibiting foam is difficult to play in an anionic system with strong foaming power. EP0163398A1 researches the preparation of silicon paste by mixing high and low viscosity polysiloxane and white carbon black. In conclusion, researches have been mainly made around the spatial structure of polysiloxane, the kind and amount of hydrophobic particles, the kind of silicone resin, and the process, and the researches have become more intensive.
One of the most important ways to obtain an excellent foam control composition is to change the steric structure of the polysiloxane, and US5153258 describes the introduction of a mixture of lightly crosslinked polysiloxane and silica into the system to improve the defoaming performance of the composition. US8053480B2 describes a high viscosity vinyl siloxane and a low viscosity hydrogen-containing polysiloxane crosslinked in the presence of a catalyst until partially gelled, and then the viscosity is reduced to a certain range by strong shearing action, which is believed to have relatively good foam suppressing properties in strong alkaline systems. Both US3455839 and CA2074060 describe a polysiloxane defoaming composition with a cross-linked structure formed by reacting vinyl polysiloxane and hydrogen-containing polysiloxane under the condition of chloroplatinic acid, which improves the capability of inhibiting foam in the later period, but how to control the difference between batches is not solved well.
The preparation of silicone foam control compositions by cross-linking techniques based on vinyl polysiloxanes and hydrogen containing polysiloxanes is an important form of foam control composition. However, many technical documents have attempted to control the reaction rate by using inert polysiloxanes as solvents for hydrosilylation reactions of vinylpolysiloxanes and hydrogenpolysiloxanes, which solvents on the one hand cannot be removed from the crosslinking system and on the other hand contribute much less to foam control than the crosslinked materials. Therefore, it becomes important to remove the solvent or to greatly reduce the amount of the solvent.
The inventor of the present invention obtains polysiloxane cross-linked product with controllable reaction by dripping hydrogenous polysiloxane at low temperature, and the viscosity will not further increase greatly in storage period.
Disclosure of Invention
The invention relates to a preparation method of an organic silicon composition, which is characterized by comprising the following steps of:
A. vinyl polysiloxane
The vinyl-containing polysiloxane comprises polysiloxane with vinyl at terminal position or lateral position, and the structural formula is as follows:
in the formula (I), subscriptaAndbis the degree of polymerization,bis 0 or an integer of 1 to 5;
R1is an alkyl or vinyl group having 1 to 8 carbon atoms, including methyl, ethyl, propyl, pentyl, hexyl, octyl and vinyl, preferably R1Is methyl and vinyl, R1The values are the same or different.
R2The aryl group is an alkyl group or an aryl group having 1 to 20 carbon atoms, and includes a methyl group, an ethyl group, a propyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an eicosyl group, a phenyl group, and a phenethyl group.
The dynamic viscosity of the vinyl polysiloxane at 25 ℃ is 500-80,000 mPas.
The usage amount of the vinyl polysiloxane is 75-95% of the total mass of the organic silicon composition.
Hydrogen-containing polysiloxane
The hydrogenpolysiloxane is polysiloxane with a spatial structure, is a cross-linking node for connecting different vinyl polysiloxane molecules, and has the following structural general formula:
(HMe2SiO1/2) c (R3 2SiO2/2) d (R4SiO3/2) e （Ⅱ）
abbreviated to: mH c D d T e
In formula (II), subscriptc、d、eRepresents the molar ratio between three segmentsThe ratio between them determines the molecular weight, morphology and activity of the polysiloxane of this steric structure,candethe ratio of (A) to (B) is 0.5 to 1.2.
R3、R4Alkyl, alkenyl or aryl with 1-20 carbon atoms, including methyl, ethyl, propyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, vinyl, phenyl, styrene.
The method for synthesizing the hydrogenpolysiloxane comprises the following steps:
adding the M chain link, the acidic catalyst, deionized water and absolute ethyl alcohol, starting stirring, heating to 30-60 ℃, dropwise adding the mixture of the organic silicon monomers of the D chain link and the T chain link into the system, and controlling the dropwise adding speed to keep the temperature of the system between 60-80 ℃. And after the dropwise addition is finished, carrying out heat preservation reaction for 4-8 h. And extracting the reaction solution by hexamethyldisiloxane (MM), standing for layering, removing an acid water layer, washing an organic layer to be neutral by deionized water, and distilling under reduced pressure to remove residual water and MM to obtain the hydrogenpolysiloxane.
The hydrogen content of the hydrogenpolysiloxane is 0.5-3.0 mmol/g, and the dosage of the hydrogenpolysiloxane is 0.1-10% of the total mass of the organic silicon composition.
C. Structure control agent
The structure control agent is an alkynol substance selected from octynol, decylenol, 2-methyl-3-butyn-2-ol, methylbutylenol, methylpentylenol, 1-alkynylcyclohexanol, 1, 4-butynediol, 3,7, 11-trimethyldodecyn-3-ol, 4-pentyn-1-ol, 3, 5-dimethyl-1-hexyn-3-ol, 3, 6-dimethyl-4-octyn-3, -diol.
The dosage of the structure control agent is 0.1-5% of the total mass of the organic silicon composition.
D. Catalyst and process for preparing same
The catalyst is a noble metal catalyst for promoting hydrosilylation, and is selected from platinum-alcohol complex, platinum-olefin complex, platinum-alkoxide complex, platinum-ether complex, platinum-ketone complex, chloroplatinic acid isopropanol solution with chloroplatinic acid concentration of 1%, rhodium-alcohol complex and rhodium-alkoxide complex, and preferably chloroplatinic acid isopropanol solution with mass concentration of 1%. The amount of the catalyst is 3-15 ppm (calculated as platinum) of the total mass of the organosilicon composition.
E. Silicon dioxide
Silica is classified into precipitated silica and vapor-phase silica according to the manufacturing method, and hydrophilic silica and hydrophobic silica according to the surface properties. The silicon dioxide is hydrophobic silicon dioxide, comprises a gas phase method and a precipitation method, and has a specific surface area of 80-400 m2The precipitates and the fumed silica with different specific surface areas are used independently or in a mixed manner, and preferably at least one fumed silica and one precipitated silica are compounded for use; the using amount of the silicon dioxide is 3-8% of the total mass of the organic silicon composition.
F. Inert silicone resins
The inert organic silicon resin generally refers to a silicon resin which does not substantially react with other substances, wherein the silicon resin is MQ resin consisting of M chain links and Q chain links, and the molar ratio of the M chain links to the Q chain links is (0.5-1.2): 1.0.
the sum of the mass contents of hydroxyl and alkoxy on the surface of the inert organic silicon resin is less than or equal to 1 percent.
The inert organic silicon resin is added in the form of solution, and the diluting solvent is selected from toluene, hexamethyldisiloxane and isooctyl stearate.
The dosage of the inert organic silicon resin is 2-8% of the total mass of the organic silicon composition.
G. Water (W)
The water comprises tap water, process water and purified water, and the appearance forms of the water comprise liquid water and solid ice.
The amount of the water is 0.1-3% of the total mass of the organic silicon composition.
The preparation method of the organic silicon composition comprises the following steps:
adding part of vinyl polysiloxane A and silicon dioxide E into a container, grinding at a high speed to enable the dispersed particle size of the silicon dioxide in the container to be smaller than 1 mu m, adding a structure control agent C and an organic silicon resin F at a rotating speed of 200-1000 rpm, then adding a catalyst D, and mixing for 5-20 min to enable the catalyst D to be uniformly dispersed in the container to obtain a dispersion X;
maintaining the temperature of the dispersion X at 20-50 ℃, maintaining the rotating speed of 500-3000 rpm, and dropwise adding the dispersion X into the XComprises Hydropolysiloxane B/vinyl polysiloxane ASlowly stirring the mixture at room temperature for 8-24 h, keeping the negative pressure of-0.02 to-0.08 MPa, vacuumizing for 10-60 min to remove small molecules, finally adding water G, and uniformly mixing to obtain the organic silicon composition.
The organic silicon composition prepared by the invention is generally prepared into emulsion type, solid type or solution type products according to the actual use requirements, and is convenient for users to use.
Generally, the O/W type emulsion product is prepared by the organosilicon composition, the emulsifier, the thickener, the water and the preservative, and the specific emulsification process and method are well known to those skilled in the art and can be inquired on the general technical information.
The emulsifier required for preparing the emulsion is a nonionic surfactant and comprises nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, lauric acid polyoxyethylene ether, oleic acid polyoxyethylene ether, lauryl alcohol polyoxyethylene ether, octanol polyoxyethylene ether, isooctanol polyoxyethylene ether, isomeric decyl alcohol polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether, cetyl alcohol polyoxyethylene ether, stearyl alcohol polyoxyethylene ether, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tristearate, one or more of polyoxyethylene sorbitan trioleate, castor oil polyoxyethylene ether and polyether modified polysiloxane, preferably a plurality of mixtures.
The thickening agent required for preparing the emulsion is selected from polyacrylamide, polyvinyl alcohol, carbomer, xanthan gum, polyacrylate, cellulose ether, preferably xanthan gum and polyacrylate, and the addition amount is adjusted according to the requirement of the viscosity of the emulsion.
The preparation of solid products generally requires the composition of a carrier, a silicone composition, an adhesive and the like; the carrier includes inorganic carrier and organic carrier. The inorganic carrier comprises sodium sulfate, sodium tripolyphosphate, zeolite, diatomite, kaolin and sodium chloride; organic carriers include wheat starch, corn starch, sodium gluconate, and the like. The method is realized by the processes of mixing, stirring, drying, sieving and the like.
Detailed Description
Example 1:
the general structural formula of the vinyl polysiloxane A is as follows:
example 2: synthesis of hydrogenpolysiloxanes B-1
Adding 25 parts of 1,1,3, 3-tetramethyldisiloxane, 55 parts of hydrochloric acid catalyst, 50 parts of deionized water and 30 parts of absolute ethyl alcohol, stirring, heating to 35 ℃, and dropwise adding a mixture of 280 parts of dimethyldiethoxysilane and 250 parts of methyltrimethoxy into the system, wherein the dropwise adding speed is controlled so that the temperature of the system is kept between 65 ℃. After the dropwise addition, the reaction is carried out for 4 hours under the condition of heat preservation. And then, extracting the reaction solution by using MM, standing for layering, removing an acid water layer, washing an organic layer by using deionized water to be neutral, and distilling under reduced pressure to remove residual moisture and MM to obtain the hydrogenpolysiloxane B-1 with the hydrogen content of 2.93 mmol/g.
Example 3: synthesis of hydrogenpolysiloxanes B-2
Adding 3 parts of 1,1,3, 3-tetramethyldisiloxane, 30 parts of hydrochloric acid catalyst, 95 parts of deionized water and 50 parts of absolute ethyl alcohol, stirring, heating to 58 ℃, and dropwise adding a mixture of 50 parts of vinyl methyl diethoxysilane and 100 parts of phenyl triethoxysilane into the system, wherein the dropwise adding speed is controlled so that the temperature of the system is kept between 78 ℃. After the dropwise addition, the reaction is carried out for 7.5 hours under the condition of heat preservation. And then, extracting the reaction solution by using MM, standing for layering, removing an acid water layer, washing an organic layer by using deionized water to be neutral, and distilling under reduced pressure to remove residual moisture and MM to obtain hydrogen-containing polysiloxane B-2 with the hydrogen content of 0.67 mmol/g.
Example 4: synthesis of hydrogenpolysiloxanes B-3
25 parts of 1,1,3, 3-tetramethyldisiloxane, 20 parts of a double-vinyl end-capping agent, 40 parts of a hydrochloric acid catalyst, 75 parts of deionized water and 76 parts of absolute ethyl alcohol are added, stirring is started, and when the temperature is raised to 48 ℃, a mixture of 38 parts of vinylmethyldiethoxysilane, 187 parts of diphenyldiethoxysilane and 250 parts of octyltrimethoxysilane is added dropwise into the system, and the dropping speed is controlled so that the temperature of the system is kept between 72 ℃. After the dropwise addition, the reaction is carried out for 5 hours under the condition of heat preservation. And then, extracting the reaction solution by using MM, standing for layering, removing an acid water layer, washing an organic layer by using deionized water to be neutral, and distilling under reduced pressure to remove residual moisture and MM to obtain hydrogen-containing polysiloxane B-3 with the hydrogen content of 1.24 mmol/g.
Example 5: synthesis of hydrogenpolysiloxanes B-4
To the system were added 50 parts of 1,1,3, 3-tetramethyldisiloxane, 20 parts of hexamethyldisiloxane, 45 parts of hydrochloric acid catalyst, 80 parts of deionized water and 88 parts of anhydrous ethanol, and a mixture of 98 parts of methylphenyldimethoxysilane, 176 parts of diisobutyldimethoxysilane and 230 parts of dodecyltrimethoxysilane was added dropwise while stirring and warming to 56 ℃, with the dropping speed being controlled so that the temperature of the system was maintained between 75 ℃. After the dropwise addition, the reaction is carried out for 6 hours under the condition of heat preservation. And then, extracting the reaction solution by using MM, standing for layering, removing an acid water layer, washing an organic layer by using deionized water to be neutral, and distilling under reduced pressure to remove residual moisture and MM to obtain hydrogen-containing polysiloxane B-4 with the hydrogen content of 2.1 mmol/g.
Example 6
Adding 50 parts of vinyl polysiloxane A-1, 5 parts of hydrophobic precipitated silica D10 (provided by winning) and 2 parts of hydrophobic fumed silica R202 (provided by winning) into a container, grinding at high speed to enable the dispersed particle size of the silica in the container to be less than 1 mu M, adding 0.2 part of structure control agent 1-alkynyl cyclohexanol C and 5 parts of organic silicon resin F (the M/Q ratio is 0.66, the sum of the mass contents of hydroxyl and alkoxy is 0.6%, the mass concentration is 50% by taking toluene as a solvent) at the rotating speed of 200rpm, then adding 4ppm (calculated by platinum) of chloroplatinic acid catalyst D, and mixing for 5min to enable the catalyst D to be uniformly dispersed in the container to obtain a dispersion X;
while maintaining the temperature of the dispersion X at 20 ℃ and maintaining the rotation speed at 550rpm, 9 parts of the dispersion X was added dropwiseHydrogen-containing polysilica Siloxane B-1/30 parts of vinyl polysiloxane A-1And slowly stirring the mixture at room temperature for 8 hours, keeping negative pressure of-0.06 MPa, vacuumizing for 60 minutes to remove small molecules, finally adding 0.3 part of water G, and uniformly mixing to obtain the organic silicon composition SC-1 with the viscosity of 34800 mPas at 25 ℃.
Example 7
80 parts of vinylpolysiloxane A-2 and 2 parts of hydrophobic precipitated silica (specific surface area 90 m)2Per g, self-treating), 1 part of hydrophobic fumed silica (specific surface area 380 m)2(g, self-treatment), by high-speed grinding, so that the dispersed particle diameter of the silica therein is less than 1 μ M, 0.5 part of a structure-controlling agent 3, 5-dimethyl-1-hexyn-3-ol C, 1 part of a silicone resin F (M/Q ratio of 0.75, sum of hydroxyl and alkoxy contents of 0.8% by mass, toluene as a solvent, mass concentration of 50%) are added at a rotation speed of 400rpm, then 7ppm (in terms of platinum) of chloroplatinic acid catalyst D is added and mixed for 10min, so that the catalyst D is uniformly dispersed therein, to obtain dispersion X;
while maintaining the temperature of the dispersion X at 35 ℃ and maintaining the rotation speed at 800rpm, 0.5 part by weight of a dispersant was added dropwise to XContaining hydrogen Polysiloxane B-3/14.5 parts vinyl polysiloxane A-2And slowly stirring the mixture at room temperature for 12 hours, keeping negative pressure of-0.06 MPa, vacuumizing for 30 minutes to remove small molecules, finally adding 0.5 part of water G, and uniformly mixing to obtain the organic silicon composition SC-2, wherein the viscosity is 54760mPa & s at 25 ℃.
Example 8
A vessel was charged with 44.5 parts of vinylpolysiloxane A-5, 3 parts of hydrophobic precipitated silica (specific surface area 90 m)2Per g, self-treatment), 3 parts of hydrophobic fumed silica R974 (provided by winning), grinding at high speed to ensure that the dispersed particle diameter of the silica in the silica is less than 1 micron, adding 4 parts of a structure control agent 3,7, 11-trimethyldodecyn-3-ol C and 3 parts of an organic silicon resin F (the M/Q ratio is 0.75, the sum of the mass contents of hydroxyl and alkoxy is 0.8 percent, MM is used as a solvent, the mass concentration is 50 percent) at the rotating speed of 1000rpm, then adding 15ppm (calculated by platinum) of chloroplatinic acid catalyst D, and mixing for 20min to ensure that the catalyst D is uniformly dispersed in the catalyst D to obtain a dispersion X;
while maintaining the temperature of the dispersion X at 50 ℃,5 parts by weight of the dispersion X was added dropwise to the dispersion X while maintaining the rotation speed at 3000rpmHydrogen-containing polymers Siloxane B-4/35 parts of vinyl polysiloxane A-5And slowly stirring the mixture for 24 hours at room temperature, keeping the negative pressure of-0.08 MPa, vacuumizing for 30 minutes to remove small molecules, finally adding 2.5 parts of ice water G, and uniformly mixing to obtain the organic silicon composition SC-3, wherein the viscosity is 220400mPa & s at 25 ℃.
Example 9
60 parts of vinylpolysiloxane A-4, 3 parts of hydrophobic precipitated silica (specific surface area 90 m)2Per g, supplied by Cambot), 2 parts of hydrophobic fumed silica R106 (supplied by winning creativity), 2 parts of hydrophobic fumed silica (R669, specific surface area 140 m)2(g) by high-speed grinding so that the particle diameter of the silica dispersed therein is less than 1 μ M, adding 0.5 part of a structure-controlling agent methylpentylenol C, 4 parts of a silicone resin F (M/Q ratio of 1.2, total of hydroxyl and alkoxy mass contents of 0.75%, MM as a solvent, mass concentration of 50%) at a rotation speed of 800rpm, then adding 12ppm (in terms of platinum) of a chloroplatinic acid catalyst D, and mixing for 15min so that the catalyst D is uniformly dispersed therein to obtain a dispersion X;
while maintaining the temperature of the dispersion X at 35 ℃ and maintaining the rotation speed at 2000rpm, 1 part of the dispersion X was added dropwiseHydrogen-containing polymers Siloxane B-4/25 parts of vinyl polysiloxane A-4Slowly stirring the mixture at room temperature for 16h, keeping the negative pressure of-0.08 MPa, vacuumizing for 25min to remove small molecules, finally adding 2.5 parts of water G, and uniformly mixing to obtain the productThe silicone composition SC-4 had a viscosity of 134680 mPas when measured at 25 ℃.
Example 10
A container was charged with 55 parts of vinylpolysiloxane A-3, 1 part of hydrophobic precipitated silica (specific surface area 90 m)2Per g, supplied by cabot), 3 parts of hydrophobic precipitated silica (D10, supplied by winning authors), 2 parts of hydrophobic fumed silica (specific surface area 150 m)2(g, supplied by wacker corporation), by high-speed grinding to make the dispersed particle diameter of silica therein less than 1 μ M, adding 1 part of a structure-controlling agent 3, 5-dimethyl-1-hexyn-3-ol C, 4 parts of a silicone resin F (M/Q ratio of 1.0, sum of hydroxyl and alkoxy contents of 0.3% by mass, isooctyl stearate as a solvent, mass concentration of 50%) at a rotation speed of 600rpm, then adding 8ppm (in terms of platinum) of chloroplatinic acid catalyst D, and mixing for 20min to make the catalyst D uniformly dispersed therein to obtain dispersion X;
while maintaining the temperature of the dispersion X at 28 ℃ and maintaining the rotation speed at 2000rpm, 3 parts of the dispersion X was added dropwiseHydrogen-containing polymers Siloxane B-2/30 parts of vinyl polysiloxane A-1Slowly stirring the mixture at room temperature for 18h, keeping the negative pressure of-0.03 MPa, vacuumizing for 10min to remove small molecules, finally adding 1 part of water G, and uniformly mixing to obtain the organic silicon composition SC-5, wherein the viscosity is 124650mPa & s at 25 ℃.
Comparative example 1:
a silicone composition CSC-1 was prepared according to the method of example 1 of US2015119509A1 and had a viscosity of 85650 mPas at 25 ℃.
Comparative example 2:
silicone composition CSC-2 was prepared according to CN101454061A example 2, having a viscosity of 34760 mPas, measured at 25 ℃.
Testing of foam control performance:
preparation of test samples: diluting foam control composition with cyclohexane as diluting medium
Test medium: 1% aqueous solution of sodium dodecylbenzenesulfonate
The test method comprises the following steps: testing by the Shake flask method
The test method comprises the following steps: 50mL of the foaming medium is added into a 100mL measuring cylinder with a plug, then 0.010g of a test sample is added, the test sample is shaken for 50 times at the amplitude of 30-40 cm at the frequency of 100-120 times/min in the vertical direction, then the test sample is kept stand, the time of foam elimination until the liquid level appears is recorded as defoaming time, the defoaming time is recorded by shaking for 50 times, and the shorter the time is until the total shaking times reach 400 times, the better the defoaming effect of the defoaming composition is.
The foam control performance test results for the silicone compositions are shown in table 1:
and (3) stability testing:
the initial viscosity was compared to the change in viscosity after one month at room temperature and the results are shown in table 2:
as can be seen from the data in table 1: the foam control capability of SC 1-5 is good; comparing the results of CSC1-2 with the results of the remaining examples, it can be seen that the compositions of the patented invention have significant advantages in foam inhibition.
As can be seen from the data in table 2: the viscosity change of the compositions of examples 1-5 after being placed for one month is within 20%, and the subsequent emulsification application is not influenced; the viscosity of the comparative example varied up to about 200%.
Claims (7)
1. A silicone composition comprising a vinyl polysiloxane, a hydrogen-containing polysiloxane, a structure-controlling agent, a catalyst, silica, an inert silicone resin, and water:
A. vinyl polysiloxane, wherein the vinyl polysiloxane comprises polysiloxane with vinyl at a terminal position or a side position, and the using amount of the vinyl polysiloxane is 75-95% of the total mass of the organosilicon composition;
B. the hydrogenpolysiloxane is a polysiloxane with a spatial structure and has the following structural formula:
(HMe2SiO1/2) c (R3 2SiO2/2) d (R4SiO3/2) e （Ⅱ）
abbreviated to: mH c D d T e
In formula (II), subscriptc、d、eRepresents the molar ratio of three chain links, the ratio of the three determines the molecular weight, the shape and the activity of the polysiloxane with the space structure,candethe ratio of (A) to (B) is 0.5-1.2;
R3、R4alkyl, alkenyl or aryl with 1-20 carbon atoms, including methyl, ethyl, propyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, vinyl, phenyl, styrene;
the hydrogen content of the hydrogenpolysiloxane is 0.5-3.0 mmol/g;
the dosage of the hydrogen-containing polysiloxane is 0.1-10% of the total mass of the organic silicon composition;
C. the structure control agent is an alkynol substance, and the using amount of the structure control agent is 0.1-5% of the total mass of the organic silicon composition;
D. a catalyst selected from the group consisting of platinum-alcohol complexes, platinum-olefin complexes, platinum-alkoxide complexes, platinum-ether complexes, platinum-ketone complexes, chloroplatinic acid isopropanol solution with a chloroplatinic acid concentration of 1%, rhodium-alcohol complexes, rhodium-alkoxide complexes; the dosage of platinum is 3-15 ppm of the total mass of the organic silicon composition;
E. the silicon dioxide is hydrophobic silicon dioxide, and the specific surface area of the silicon dioxide is 80-400 m2The/g is selected from precipitated silica and fumed silica with different specific surface areas to be used independently or mixed; the using amount of the organic silicon composition is 3-8% of the total mass of the organic silicon composition;
F. the inert organic silicon resin is MQ resin consisting of M chain links and Q chain links, and the molar ratio of the M chain links to the Q chain links is (0.5-1.2): 1.0; the using amount of the organic silicon composition is 2-8% of the total mass of the organic silicon composition;
G. the water comprises tap water, process water and purified water, and the appearance forms of the water comprise liquid water and solid ice; the using amount of the organic silicon composition is 0.1-3% of the total mass of the organic silicon composition;
the sum of the mass of the components A to G is 100 percent;
the method for synthesizing the hydrogenpolysiloxane comprises the following steps:
adding M chain links, an acidic catalyst, deionized water and absolute ethyl alcohol, starting stirring, heating to 30-60 ℃, dropwise adding a mixture of organic silicon monomers of the D chain links and the T chain links into the system, and controlling the dropwise adding speed to keep the temperature of the system between 60-80 ℃; after the dropwise addition is finished, carrying out heat preservation reaction for 4-8 h; then extracting the reaction solution by hexamethyldisiloxane, standing for layering, removing an acid water layer, washing an organic layer to be neutral by deionized water, and removing residual moisture and hexamethyldisiloxane by reduced pressure distillation to obtain hydrogen-containing polysiloxane;
the preparation method of the organic silicon composition comprises the following steps:
adding part of vinyl polysiloxane A and silicon dioxide E into a container, grinding at a high speed to enable the dispersed particle size of the silicon dioxide E in the container to be smaller than 1 mu m, adding a structure control agent C and an inert organic silicon resin F at a rotating speed of 200-1000 rpm, then adding a catalyst D, and mixing for 5-20 min to enable the catalyst D to be uniformly dispersed in the container to obtain a dispersion X;
keeping the temperature of the dispersion X at 20-50 ℃, keeping the rotation speed of 500-3000 rpm, dropwise adding a mixture of hydrogenpolysiloxane B and vinyl polysiloxane A into the dispersion X, slowly stirring for 8-24 h at room temperature, keeping negative pressure of-0.02 to-0.08 MPa, vacuumizing for 10-60 min to remove small molecules, finally adding water G, and uniformly mixing to obtain the organic silicon composition.
2. The silicone composition according to claim 1, wherein the vinyl polysiloxane has the following general structural formula:
（Ⅰ）
in the formula (I), subscriptaAndbis the degree of polymerization,bis 0 or an integer of 1 to 5;
R1is an alkyl or vinyl group having 1 to 8 carbon atoms, including methyl, ethyl, propyl, pentyl, hexyl, octyl and vinyl, R1The values are the same or different;
R2alkyl or aryl with 1-20 carbon atoms, including methyl, ethyl, propyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, phenyl, phenethyl;
the dynamic viscosity of the vinyl polysiloxane at 25 ℃ is 500-80,000 mPas.
3. The silicone composition of claim 2, wherein substituent R is1Are methyl and vinyl.
4. The silicone composition of claim 1, wherein the structural control agent is selected from the group consisting of octynol, decylenol, 2-methyl-3-butyn-2-ol, methylbutynol, methylpentylenol, 1-alkynylcyclohexanol, 1, 4-butynediol, 3,7, 11-trimethyldodecyn-3-ol, 4-pentyn-1-ol, 3, 5-dimethyl-1-hexyn-3-ol, 3, 6-dimethyl-4-octyn-3, 6-diol.
5. The silicone composition according to claim 1, wherein the silica is selected from at least one fumed silica and one precipitated silica.
6. The silicone composition according to claim 1, wherein the sum of the mass contents of hydroxyl groups and alkoxy groups on the surface of the inert silicone resin is 1% or less.
7. The silicone composition of claim 1, wherein the diluent solvent for the inert silicone resin is selected from the group consisting of toluene, hexamethyldisiloxane, and isooctyl stearate.
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| CN111592764B (en) * | 2020-05-29 | 2021-08-31 | 浙江新安化工集团股份有限公司 | Silicone resin reinforced organosilicon elastomer aqueous dispersion liquid and preparation method and application thereof |
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