CN111303633B - Method for preparing silicone rubber sponge heat-insulating material by taking in-situ graft modified mesoporous silica vesicle continuous aggregate as functional filler - Google Patents
Method for preparing silicone rubber sponge heat-insulating material by taking in-situ graft modified mesoporous silica vesicle continuous aggregate as functional filler Download PDFInfo
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Abstract
The invention discloses a method for preparing a premix by in-situ graft modification of a mesoporous silica vesicle continuous aggregate, and a method for preparing an addition type silicone rubber sponge heat insulation material by adopting the premix as a main raw material. (1) Under the action of an alkaline catalyst, vinyl-terminated silicone oil, water and vesicles undergo a chemical equilibrium reaction, and silicon hydroxyl generated in situ exists in three different forms: and the mixed blocked polysiloxane is grafted at the tail end of the polysiloxane on the surface of the vesicle, at both ends of the polysiloxane and at one end of a silicon hydroxyl group and one end of a vinyl group. The vesicle surface grafting rate, the content of the silicon hydroxyl terminated polysiloxane and the content of the vinyl terminated polysiloxane of the premix can be controlled by adjusting the raw material proportion and the like, so that the grafting modification of the in-situ vesicle and the synthesis of the active hydroxyl component are realized, the process links are few, no pollution is caused, and the odor is low; (2) the addition type silicone rubber sponge is prepared by adopting the premix as a main raw material, the liquid silicone rubber has low viscosity and high strength, and the heat conductivity coefficient of the liquid silicone rubber is reduced along with the increase of the addition proportion of the vesicles.
Description
Technical Field
The invention relates to a premix for enhancing the effect of in-situ graft modified mesoporous silica vesicle continuous aggregates (hereinafter referred to as vesicles) and a modification method, and also relates to a silicone rubber sponge heat-insulating material containing the premix for enhancing the effect of in-situ graft modified vesicles and a preparation method thereof.
Background
At present, the flexible heat-insulating material is generally a traditional polyurethane sponge, the heat conductivity coefficient is as low as 0.02W/(m.K), and the defects are that the temperature resistance is poor, the water absorption is high, the degradation is easy, and the toxicity of combustion smoke is high. The silicone rubber sponge, also called as silicone rubber foam, is a porous spongy polymer elastomer prepared from silicone rubber through a foam molding process, and has a series of advantages of low density, heat resistance, flame retardance, heat insulation, sound insulation, shock absorption, damping, water resistance, weather resistance, permanent low compression, good air tightness and the like. The silicone rubber sponge on the current market can resist the temperature of minus 55 ℃ to 200 ℃ for a long time, has good flame retardant FVO grade, anti-dripping property and smoke suppression property, has no toxicity in smoke and hydrophobic and damp insulation, but has the thermal conductivity coefficient of about 0.05W/(m.K) and unsatisfactory heat preservation effect. With the reduction of the cost of the silicon rubber and the maturity of the technology, the silicon rubber sponge is expected to become a flexible heat preservation and insulation material with great potential.
The key to further reducing the thermal conductivity of silicone rubber sponges is to reduce the apparent density and to reduce the cell diameter. As is well known, the thermal conductivity coefficients of the silicon dioxide aerogel, the glass beads, the air and the silicon rubber are respectively about 0.018W/(m.K), 0.030W/(m.K), 0.026W/(m.K), and the volume ratio of the air to the light filler is increased, so that the thermal conductivity coefficient is reduced by greatly foaming the silicon rubber. Patent document CN103130454A discloses that the thermal conductivity of a silicone rubber foam matrix with hollow glass beads added in a super-high proportion in a condensed liquid silicone rubber is 0.048W/(m · K), and the thermal conductivity of a product with aerogel added thereto is reduced to 0.02W/(m · K), but the foam inevitably loses resilience and toughness due to the addition of a non-reinforcing filler in a high proportion. Patent document
WO2018148290A1 adds 9.09/% by mass of glass hollow microspheres to conventional addition type liquid silicone rubber which is not foamed in the body, and the apparent density and the thermal conductivity of the glass hollow microspheres are respectively only 0.87g/cm3And 0.17W/(m.K), the effect is not significant.
Patent document US9488311 uses a thermal decomposition foaming agent to increase the expansion ratio and has an apparent density of less than 0.080g/cm3The thermal conductivity is less than 0.04W/(m.K), but the cell diameter generated by thermal decomposition is coarse and uneven, and air convection is not favorable for reducing the thermal conductivity. Patent document US5010115 adopts addition type liquid silicone rubber system, under the action of platinum catalyst, long-chain alkyl alcohol and hydrogen-containing siloxane are dehydrogenated and foamed, and the lowest apparent density reaches 0.050g/cm 3However, the system has no reinforcing filler, and has poor strength, strong guiding significance and poor practicability. Generally, liquid silicone rubber has low surface tension, oleophylic and hydrophobic properties and low mechanical strength, and the surface-modified fumed silica with high specific surface area is an ideal reinforcing agent and has the reinforcing effect of about more than 50 times. Therefore, a small amount of aerogel, diatomite, montmorillonite, vermiculite and the like are added into the gas-phase-method-silica-reinforced addition-type foaming liquid silica gel as a thickening agent, and the thickening agent and the surfactant are used together to refine the diameter of water-in-oil droplets, so that the nucleation density can be improved, and the pore type, the cell density, the pore size distribution and the apparent density of foam cotton are obviously influenced, which is described in patent documents such as US20180057652A1, JPWO2017110565A1, US20110021649A1, US4460713, WO2005085357A1 and the like, but the addition amount of the thickening agent is too small, and the thickening agent per se has a great influence on the pore type, the cell density, the pore size distribution and the apparent density of the foam cottonThe thermal conductivity has a very limited effect. In addition, the thermal insulation performance of the aerogel is reduced after water absorption, so that the KR20090061301A and US 6475561B1 specially perform hydrophobic treatment on a large number of silicon hydroxyl groups on the surface of the aerogel, so that the water absorption of the aerogel is effectively reduced, and the thermal insulation performance of the aerogel is remarkably improved. Although the hydrophobic treatment of hydrophilic fillers such as aerogel, glass cenospheres, diatomite, montmorillonite and vermiculite can reduce the thickening property of the fillers, the reinforcing property of high-proportion addition is deviated, and the flexibility and resilience of rubber are lost to different degrees.
Research shows that when the pore diameter in the material is reduced to nanometer level, nanometer effects of 'zero convection', 'infinite heat shield', 'infinite long path' and the like can be generated, so that the heat transfer capacity of the material is reduced to be close to the limit, and the super heat-insulating material can be prepared. The vesicles are three-dimensional bulk networks formed by mutually combining nano-scale silicon dioxide hollow microspheres, the gas-phase method silicon dioxide is three-dimensional dendritic networks formed by mutually combining nano-scale solid silicon dioxide microspheres, the inner parts of single vesicles and the vesicles have nano-scale pore-size high gaps, and the solid particles of the gas-phase method silicon dioxide have nano-scale high gaps, so that the packing densities of the single vesicles and the solid particles are lower, and the gas-phase method silicon dioxide is suitable for preparing super heat-insulating materials. For example, patent documents CN106478053A, CN106747261A, and CN106699106A hydrolyze in situ in the fiber-added liquid phase to prepare mesoporous silica vesicles, and the thermal conductivity is at most 0.02W/(m · K). The product prepared by the patent document CN103922347B is a continuous vesicle with the size of 20-100 nm, the pore wall thickness is 4-6 nm, the pore size distribution is a hierarchical pore, the space between walls is 2-4 nm, the pore size of the vesicle is 20-40 nm, and the specific surface area is 600-1100 m2(ii)/g; the product has good uniformity and density of 40kg/m 3Left and right; the high temperature performance at 850 ℃ is stable, and the pore structure still keeps complete under the pressure of 10 MPa. Therefore, it can be expected that the surface hydrophobic modified light porous vesicles are added into the silicone rubber with high foaming ratio, the micron-scale void structure of the silicone rubber is combined with the nano-scale voids of the vesicles, and the thermal conductivity of the silicone rubber is greatly reduced along with the increase of the proportion of the vesicles.
Disclosure of Invention
The invention aims to provide a premix for enhancing the efficacy of in-situ grafting modified vesicles and a modification method of the premix. The invention also provides the silicone rubber sponge heat insulation material with low heat conductivity coefficient and the preparation method thereof.
In order to solve the technical problems, the invention takes vesicles with high porosity and low thermal conductivity as main fillers to prepare the silicon rubber with high foaming ratio, and the flexible silicon rubber formed by the gaps of the nano-scale vesicles and the gaps of the micron-scale silicon rubber together has the thermal conductivity of 0.034W/(m.K).
Firstly, hydrophobic treatment of surface hydrophilic vesicles by adopting in-situ surface chemical grafting modification is realized, the compatibility and the dispersibility of the vesicles in liquid silicone rubber are improved, the heat conductivity coefficient of the silicone rubber is obviously reduced along with the increase of the addition amount of low-thickening vesicles, and particularly, the silicone rubber is mutually rented with addition type silicone rubber with high foaming multiplying power, so that a remarkable synergistic gain effect is realized on the reduction of the heat conductivity coefficient; secondly, the hydrophilic inner cavity of the vesicle has selective adsorption effect on the active hydrogen-containing component of the addition type foaming silicone rubber, and the vesicle has large adsorption capacity on water and alcohol with small molecular weight and high polarity, and is not suitable for batch foaming multiplying power. The hydroxyl-terminated polysiloxane with low polarity and relatively large molecular weight is used as the active hydrogen-containing component, and the vesicle has low adsorbability to the active hydrogen-containing component, so that the stable foaming multiplying power of the foaming silicone rubber is ensured, and the product batch stability of the flexibility, resilience and heat conductivity coefficient of the silicone rubber is good.
The in-situ grafting modified vesicle synergistic premix comprises the following components in parts by mass:
(A) vinyl-terminated silicone oil 1500.0-3000.0
(B) 10.0-50.0% of water
(C) 1.0-5.0 parts of basic catalyst
(D) 500-1000 vesicles.
(A) The vinyl-terminated silicone oil is vinyl-terminated polysiloxane, the viscosity is 5000-200000 mPa.s, and the side chain is methyl or the combination of methyl and phenyl. The preferable mass part of the vinyl-terminated silicone oil (A) is 1800-2000.0 parts.
(B) Water, tap water, purified water, distilled water, deionized water. The amount of the water (B) is preferably 20.0 to 30.0 parts.
(C) The basic catalyst is lithium hydroxide, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide or a balance of potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide and siloxane (known in the art as an alkali gum), preferably tetramethylammonium hydroxide. The methods of use of the different catalysts are well known in the art and will not be described here. The (C) basic catalyst is preferably 3.0-4.0 parts.
(D) The vesicles are mesoporous silica vesicle continuous aggregates, the size of the continuous vesicles is 20-100 nm, the thickness of pore walls is 4-6 nm, the pore size distribution is hierarchical pores, the gaps between walls are 2-4 nm, the pore size of the vesicles is 20-40 nm, and the specific surface area is 600-1100 m 2(ii)/g; the density is 40kg/m3Left and right; the high temperature performance at 850 ℃ is stable, and the pore structure still keeps complete under the pressure of 10 MPa. The preferable part of the vesicle (D) is 500.0-800 parts.
The silicone rubber sponge heat insulation material with the in-situ graft modified vesicle synergistic effect comprises the following components in parts by mass:
(E) 70.0-90.0 parts of premix
(F) 0.1-1.0% of platinum catalyst
(G) 0.02-0.05% of inhibitor
(H) 0.0-20.0 parts of vinyl-terminated silicone oil
(I) 10.0 to 20.0 parts of hydrogen-containing siloxane.
(E) The premix is the premix for the synergy of the in-situ grafting modified vesicles, and the addition amount of the premix needs to be adjusted according to a formula, so that the vesicle proportion is improved as much as possible.
(F) The platinum catalyst is chloroplatinic acid, triphenylphosphine platinum, alcohol or ether complex of chloroplatinic acid, and alkenyl complex of platinum. Polysiloxane-soluble platinum compounds, such as alkenyl complexes of platinum, are preferred. The alkenyl ligand in the alkenyl complex of platinum is an olefin, vinylsiloxane or tetramethyldivinyldisiloxane, and particularly preferably a divinyltetramethyldisiloxane platinum complex and a tetramethyltetravinylcyclotetrasiloxane platinum complex. The platinum group metal catalyst can promote hydrosilylation reaction between silicon hydrogen atoms and vinyl groups to form a cross-linked silicone rubber elastomer and can also promote reaction between silicon hydrogen and hydroxyl in a foaming agent to generate hydrogen gas for foaming. The addition amount of the platinum catalyst is 10-200 ppm, preferably 30-50 ppm, and the increase of the addition amount is beneficial from the aspects of cost performance and production efficiency.
(G) The inhibitor, the hydrosilylation inhibitor, retards the rate of crosslinking and the rate of foaming during the mixing operation. The inhibitor can be selected from vinyl siloxane, alkynol, phosphite, unsaturated amide or maleate, preferably vinyl siloxane or alkynol, such as tetramethyl divinyl disiloxane, tetramethyl tetravinylcyclotetrasiloxane, methyl butynol and ethynylcyclohexanol, etc.
(I) The hydrosiloxane, preferably the hydrosiloxane, is a cyclic, linear or branched hydrosiloxane. Hydrogen atoms directly connected with silicon atoms in the hydrogen-containing silane and vinyl are subjected to addition reaction, and the elastomer is formed by crosslinking and curing; the hydrogen atoms and the hydroxyl silicone oil containing active hydrogen have dehydrogenation condensation reaction, and not only foaming but also crosslinking effect. The hydrosilyl group of the hydrosilyl can be located anywhere in the molecular chain, and the other groups to which the silicon atom is attached can be any of alkane, alkene and arene, and most preferably all methyl.
The hydrogen-containing silicone of the present invention has a viscosity (25 ℃) of 10.0 to 50.0mPa.s, more preferably 20.0 to 30.0 mPa.s. The hydrogen content of the hydrogen-containing siloxane is 0.1 to 1.67%, and more preferably 1.5 to 1.6%. The hydrosiloxanes with various structures can be selected from one or more optimized combinations.
The in-situ grafting modification method of the vesicle comprises the following steps: taking (A) vinyl-terminated silicone oil, (B) water and (D) vesicles as raw materials, and forming a premix under the action of (C) an alkaline catalyst; in the premix, hydroxyl-terminated polysiloxane is generated in situ under the action of (C) an alkaline catalyst, and reactive hydroxyl groups of a part of the hydroxyl-terminated polysiloxane are condensed with silicon hydroxyl groups on the surface of the vesicle to form graft modification; the other part of the hydroxyl-terminated polysiloxane is dissolved in the premix; the premix comprises the following components in parts by mass:
(A) vinyl-terminated silicone oil 1500.0-3000.0
(B) 10.0-50.0% of water
(C) 1.0-5.0 parts of basic catalyst
(D) 500-1000 vesicles.
The surface-modified fumed silica with high specific surface area is an ideal reinforcing agent, and the reinforcing effect is about 50 times. Modification methods commonly used in the industry: silazane, water, silicone oil, fumed silica, hydroxyl-terminated polysiloxane and other raw materials are added into a kneader, and the silazane is hydrolyzed under the action of high shear and then reacts with silicon hydroxyl on the surface of the fumed silica to convert the surface of the fumed silica from hydrophilic to hydrophobic. Experiments show that the actual effects of adsorbing residual ammonia gas in the inner cavity of the vesicle treated by the method, increasing the temperature, increasing the vacuum degree and prolonging the dehydration time are not good. The catalyst platinum of the addition type liquid silicone rubber is easy to be poisoned and failed after being coordinated with ammonia gas. In addition, in the literature, the ethanol released by hydrolysis treatment with a silane treating agent is flammable and explosive, and has certain danger. According to the reverse thinking of the matching between the vesicle characteristics and the active hydrogen-containing substance components in the formula, the hydroxyl-terminated polysiloxane is found to be an active hydrogen substance for generating bubbles and a common auxiliary agent for treating a gas phase method, vinyl silicone oil, water, an alkaline catalyst and vesicles are used as raw materials, active hydroxyl generated in situ is condensed with the silicone hydroxyl on the surface of the vesicles, a silicone oil chain segment is grafted on the surface of the vesicles, the grafting amount can be controlled by adjusting the raw material proportion and process conditions, and the mixture is collectively called as premix.
The raw material proportion and the process parameters of the premix are adjusted, the vesicle grafting amount, the active hydroxyl content and the viscosity of the premix can be optimized, and the unique advantages of the reverse design of the patent can be understood by further verifying and comparing the formula of the addition type liquid foaming silicone rubber.
The preparation method of the silicone rubber sponge heat insulation material with the in-situ graft modification of the vesicle synergism comprises the following steps:
(1) and (E) carrying out in-situ grafting modification on the vesicle to obtain (E) premix. Vinyl-terminated silicone oil, water and vesicles are used as raw materials, hydroxyl-terminated polysiloxane is generated in situ under the action of a basic catalyst, reactive hydroxyl groups of a part of the hydroxyl-terminated polysiloxane are condensed with silicon hydroxyl groups on the surfaces of the vesicles to form graft modification, and the grafting amount can be controlled by adjusting the proportion of the raw materials and controlling process parameters; another portion of the hydroxyl terminated polysiloxane is dissolved in the mixture. Both of these two active hydrogen-containing hydroxyl-terminated polysiloxanes can react with the hydrogen-containing siloxane to produce a gas. The method has the advantages of few process steps, no pollution and low odor, and the mixture is called premix.
(2) Sequentially adding (E) premix, (F) platinum catalyst, (G) inhibitor, (H) terminal vinyl silicone oil and (I) hydrogen-containing siloxane, quickly stirring and defoaming, pouring into a mould to begin foaming until the surface is not sticky and the sponge volume is stable, wherein the (E) premix, (F) platinum catalyst, (G) inhibitor, (H) terminal vinyl silicone oil and (I) hydrogen-containing siloxane are as follows:
(E) 70.0-90.0 parts of premix
(F) 0.1-1.0% of platinum catalyst
(G) 0.02-0.05% of inhibitor
(H) 0.0-20.0 parts of vinyl-terminated silicone oil
(I) 10.0 to 20.0 parts of hydrogen-containing siloxane.
The silicon hydroxyl is generated in situ in the premix, and a substance component containing active hydroxyl does not need to be additionally added, and exists in three forms: the specificity of the composition of the polymer structure determines the specificity of the silicone rubber.
The addition type silicone rubber sponge generally consists of vinyl-containing polysiloxane, hydrogen-containing polysiloxane, filler, catalyst, inhibitor, foaming agent and various auxiliary agents. Vinyl polysiloxane, hydrogen-containing polysiloxane and foaming agent are subjected to hydrosilylation cross-linking reaction and hydrosilylation condensation reaction under the catalytic action, namely, cross-linking and foaming are carried out simultaneously, the rate ratio of the two reactions is controlled, and silicone rubber sponges with different cell types, cell densities, pore size distributions and apparent densities can be prepared. The chemical foaming process comprises three stages: the development degree of each stage is closely related to the crosslinking and curing degree. Ideally, the two processes are separated as much as possible, however, in reality, the two processes are inseparable, and both processes are sensitive to temperature anomaly, and how to control the equilibrium point is always a serious challenge.
The size of the continuous vesicle is 20-100 nm, the thickness of the pore wall is 4-6 nm, the pore size distribution is a hierarchical pore, the space between walls is 2-4 nm, the pore size of the vesicle is 20-40 nm, and the specific surface area is 600-1100 m2(ii)/g; the product has good uniformity and density of 40kg/m3Left and right; the high temperature performance at 850 ℃ is stable, and the pore structure still keeps complete under the pressure of 10 MPa. The vesicle is a three-dimensional cluster network formed by combining nano-scale silicon dioxide hollow microspheres, the gas phase method silicon dioxide is a three-dimensional dendritic network formed by combining nano-scale solid silicon dioxide microspheres, the internal porosity of the nano-scale solid silicon dioxide microspheres is high, the inter-particle porosity of the nano-scale solid silicon dioxide microspheres is high, and the bulk density of the nano-scale solid silicon dioxide microspheres are low. Therefore, when the same mass parts of the liquid silicone rubber are added, the vesicle has high porosity and low density, and the volume ratio of the vesicle is obviously higher than that of the gas-phase method silicon dioxide in terms of the volume ratio of the filler to the polysiloxane polymer, so that the viscosity of the composition is much higher than that of the gas-silicon reinforced liquid silicone rubber.
The inner surface and the outer surface of the hydrophilic vesicle are both provided with a large number of silicon hydroxyl groups, so that a large number of water molecules can be adsorbed. The direct addition of unmodified hydrophilic vesicles in addition-type foamed liquid silicone rubbers can lead to serious problems: firstly, the water absorption of the vesicle is high, and the self heat conductivity coefficient is increased; secondly, the thickening property of the vesicles is high, the vesicles are difficult to add in a high proportion, and the overall contribution to reducing the heat conductivity coefficient is small; and thirdly, the silicon hydroxyl groups and the adsorbed water on the outer surface of the vesicle belong to substances containing active hydrogen, and both the silicon hydroxyl groups and the adsorbed water can perform dehydrogenation condensation reaction with hydrogen-containing siloxane under the action of a platinum catalyst, so that the foaming rate and the crosslinking rate of a system are influenced, the foaming ratio of the silicone rubber is unstable, and the thermal conductivity coefficient of a product fluctuates. In addition, the vesicles have an inner surface and an outer surface, which are different from the outer surface of fumed silica, and maintain hydrophilicity to the inner surface of the vesicles although the surface of the vesicles has nanometer-sized pores. The addition type foaming silicon rubber must be added with substances containing active hydrogen, which commonly comprise water, alkyl alcohol and hydroxyl silicone oil, and a part of the substances is absorbed by the vesicles to be not involved in the reaction outside the vesicles, so that the selection range of the substances containing active hydrogen is limited. The hydrophilic inner cavity of the vesicle has strong adsorption on water with small molecular weight and high polarity and alkyl alcohol, so that the water and the alkyl alcohol are unstable in percentage by mass, and the foaming multiplying power and the batch fluctuation of pore distribution are caused; the hydrophilic inner surface of the vesicle has weak adsorption effect on hydroxyl silicone oil with low polarity and relatively large molecular weight, and the hydroxyl silicone oil is used for providing active hydrogen, thereby being beneficial to improving the batch stability of products and reducing the heat conductivity coefficient.
The surface modified premix of the vesicle adopts vinyl silicone oil, water and the vesicle as raw materials, hydroxyl-terminated polysiloxane is generated in situ under the action of a basic catalyst, and reactive hydroxyl groups of part of the hydroxyl-terminated polysiloxane are condensed with silicon hydroxyl groups on the surface of the vesicle to form graft modification; another portion of the hydroxyl terminated polysiloxane is dissolved in the mixture. Both of these two active hydrogen-containing hydroxyl-terminated polysiloxanes can react with the hydrogen-containing siloxane to produce a gas. The modification method has the advantages of few process links, no pollution and low odor, and the mixture is called premix. The silicon hydroxyl is generated in situ in the premix, and a substance component containing active hydroxyl does not need to be additionally added, and exists in three forms: the specificity of the composition of the polymer structure determines the specificity of the silicone rubber. The addition type silicone rubber taking the premix as the main raw material has high foaming rate, the high proportion of added vesicles has obvious contribution to reducing the thermal conductivity coefficient, and the thermal conductivity coefficient reaches 0.034W/(m.K).
Detailed Description
The first step is as follows: and (3) carrying out hydrophobic treatment on the surface hydrophilic vesicles by adopting a surface chemical modification method.
Adding vinyl silicone oil, water and an alkaline catalyst into a kneader in sequence, closing a cover, opening the kneader, setting the temperature to 90 ℃, reacting for 60min, and generating hydroxyl-terminated polysiloxane in situ. The cap was opened, the vesicles were added in portions and kneaded for 5.0 hours. Setting the temperature at 180 ℃, continuing kneading for 2.0 hours, then starting a vacuum pump, kneading for 3 hours under negative pressure, and removing volatile matters. Stopping heating, stopping kneading, turning off the vacuum pump, relieving vacuum, and discharging when the temperature of the material is reduced to below 40 deg.C for use.
According to the above method, the corresponding raw materials were added in each example.
TABLE 1 Effect of the viscosity of vinyl terminated Silicone oils in different examples
In the table, E represents examples, as follows.
Theoretically one molecule of water gives two molecules of reactive silicon hydroxyl groups and 10g of water gives more than at least 1000mmol of silicon hydroxyl groups, well above 2000g of 120mmol of vinyl groups contained in 5000mpa.s of vinyl terminated silicone oil. Under the action of an alkaline catalyst, a series of hydrolysis, condensation, termination, cyclization, ring opening and the like occur to the terminal vinyl silicone oil, and the actually obtained silicon hydroxyl group is probably far lower than 1000 mmol. The viscosity of the premix increases with increasing silicone oil, while the process remains consistent.
TABLE 2 Effect of water amount on premix viscosity
In Table 2, in the different examples E-6, E-7, E-8, E-9 and E-10, the water is tap water, purified water, distilled water and deionized water, respectively.
The water quantity is increased, the viscosity is reduced, and the reaction principle is met. The vesicle has water absorption, and the viscosity of the premix with 20g of water has good batch stability.
TABLE 3 influence of the amount of silicone oil added on the viscosity of the premix
The more silicone oil is added, the lower the premix viscosity. E-1 and E-2 are too viscous and E-3, E-4, E-5 are gradually reduced, preferably E-3, with a vesicle content of 20.0%.
TABLE 4 influence of catalyst addition on premix viscosity
In Table 4, the catalysts in examples E-16, E-17, E-18, E-19 and E-20 were tetramethylammonium hydroxide, lithium hydroxide, potassium hydroxide, sodium hydroxide and tetramethylammonium hydroxide, respectively.
The catalyst is large in addition amount and high in treatment speed, but the post-treatment consumes time and energy, the equipment effect is comprehensively considered, and the E-3 effect is good.
In the embodiment, the vesicle is a mesoporous silica vesicle continuous aggregate, the size of the continuous vesicle is 20-I00 nm, the thickness of the pore wall is 4-6 nm, the pore size distribution is hierarchical pores, the gap between the walls is 2-4 nm, the pore size of the vesicle is 20-40 nm, and the specific surface area is 600-1100 m 2/g; the density is about 40kg/m 3; the high temperature performance at 850 ℃ is stable, and the pore structure still keeps complete under the pressure of 10 MPa.
A second part: and (3) optimally designing the formula of the addition type liquid foaming silicone rubber.
In the second group of embodiments, as represented by embodiments E-18, the remaining groups are also distinguished and will not be described again.
Adding the premix, the platinum catalyst, the inhibitor and the hydrogen-containing silicone oil into a stirrer in sequence, quickly stirring and defoaming, pouring into a mould, and standing and observing at room temperature. Foaming was started until the surface was not sticky and the sponge volume was stable.
The corresponding components were added separately in the following examples according to the above-described method.
TABLE 5 influence of premix and platinum addition on expansion ratio and thermal conductivity
Note that: the concentration of the platinum catalyst is 5000 ppm; the inhibitor is methylbutynol concentration 1.0%.
In Table 5, for the different examples E-19, E-20, E-21, E-22, E-23, E-24, E-25, E-26, E-27, the platinum catalysts are: chloroplatinic acid; the inhibitors are respectively: tetramethyldivinyldisiloxane, tetramethyltetravinylcyclotetrasiloxane, methylbutynol, tetramethyldivinyldisiloxane, ethynylcyclohexanol, phosphite, unsaturated amide, maleate, methylbutynol.
The proportion of the premix and the platinum is improved, the proportion of the vesicles is increased, the foaming ratio is increased, and the heat conductivity coefficient is favorably reduced.
TABLE 6 Effect of premix and hydrogenosiloxane addition on expansion ratio and thermal conductivity
Note that: the concentration of the platinum catalyst is 5000 ppm; the inhibitor is methylbutynol concentration 1.0%.
The proportion of the hydrogen-containing siloxane is improved, the active hydroxyl of the premix has sufficient reaction and large gas evolution, the foaming ratio of the silicon rubber body is increased, and the heat conduction coefficient is favorably reduced to 0.34 w/m.k.
In the above examples, the component units are parts by mass except for the viscosity unit.
The above embodiments do not limit the present invention in any way, and all technical solutions obtained by means of equivalent substitution or equivalent transformation fall within the protection scope of the present invention.
Claims (17)
1. The premix for the in-situ graft modification of the mesoporous silicon dioxide vesicle continuous aggregate synergism is characterized by comprising the following components in parts by mass:
(A) vinyl-terminated silicone oil 1500.0-3000.0
(B) 10.0-50.0% of water
(C) 1.0-5.0 parts of basic catalyst
(D) 500-1000 parts of vesicles;
the alkaline catalyst (C) is lithium hydroxide, potassium hydroxide, sodium hydroxide or tetramethyl ammonium hydroxide;
the (D) vesicles are mesoporous silica vesicle continuous aggregates;
the mesoporous silicon dioxide vesicle continuous aggregate in-situ grafting modification method adopts (A) vinyl-terminated silicone oil, (B) water and (D) vesicles as raw materials, and forms a premix under the action of (C) an alkaline catalyst; in the premix, hydroxyl-terminated polysiloxane is generated in situ under the action of (C) an alkaline catalyst, and reactive hydroxyl groups of a part of the hydroxyl-terminated polysiloxane are condensed with silicon hydroxyl groups on the surface of the vesicle to form graft modification; the other part of the hydroxyl-terminated polysiloxane is dissolved in the premix;
The silicon hydroxyl group is generated in situ in the premix and exists in three forms: the polysiloxane end grafted on the surface of the vesicle, two ends of the polysiloxane, and the mixed end-blocked polysiloxane with one end silicon hydroxyl and one end vinyl.
2. The in-situ grafting modified mesoporous silica vesicle continuous aggregate synergistic premix as claimed in claim 1, wherein: the vinyl-terminated silicone oil (A) is vinyl-terminated polysiloxane, the viscosity is 5000-200000 mPa.s, and the side chain is methyl or the combination of methyl and phenyl.
3. The in-situ grafting modified mesoporous silica vesicle continuous aggregate synergistic premix as claimed in claim 1, wherein: the mass part of the vinyl-terminated silicone oil (A) is 2000.0.
4. The in-situ grafting modified mesoporous silica vesicle continuous aggregate synergistic premix as claimed in claim 1, wherein: the (C) alkaline catalyst is tetramethyl ammonium hydroxide.
5. The silicone rubber sponge heat-insulating material with the synergistic effect of the in-situ graft modified mesoporous silica vesicle continuous aggregates, which adopts the premix compound of any one of claims 1 to 4, is characterized by comprising the following components in parts by mass:
(E) 70.0-90.0 parts of premix
(F) 0.1-1.0% of platinum catalyst
(G) 0.02-0.05% of inhibitor
(H) 0.0-20.0 parts of vinyl-terminated silicone oil
(I) 10.0 to 20.0 parts of hydrogen-containing siloxane.
6. The in-situ grafting modified mesoporous silica vesicle continuous aggregate synergistic silicone rubber sponge thermal insulation material as claimed in claim 5, wherein: the platinum catalyst (F) is chloroplatinic acid, triphenylphosphine platinum, alcohol or ether complex of chloroplatinic acid and alkenyl complex of platinum.
7. The in-situ grafting modified mesoporous silica vesicle continuous aggregate synergistic silicone rubber sponge thermal insulation material as claimed in claim 6, is characterized in that: the platinum catalyst (F) is an alkenyl complex of platinum.
8. The in-situ graft modified mesoporous silica vesicle continuous aggregate synergistic silicone rubber sponge thermal insulation material as claimed in claim 6 or 7, wherein: the alkenyl ligand in the alkenyl complex of the platinum is olefin and vinyl siloxane.
9. The in-situ graft modified mesoporous silica vesicle continuous aggregate synergistic silicone rubber sponge thermal insulation material as claimed in claim 6 or 7, wherein: the alkenyl complexes of the platinum are divinyl tetramethyl disiloxane platinum complexes and tetramethyl tetravinylcyclotetrasiloxane platinum complexes.
10. The in-situ grafting modified mesoporous silica vesicle continuous aggregate synergistic silicone rubber sponge thermal insulation material as claimed in claim 5, wherein: the (G) inhibitor is vinyl siloxane, alkynol, phosphite ester, unsaturated amide or maleate.
11. The in-situ graft modified mesoporous silica vesicle continuous aggregate synergistic silicone rubber sponge thermal insulation material as claimed in claim 10, wherein: the (G) inhibitor is vinyl siloxane or alkynol.
12. The in-situ grafting modified mesoporous silica vesicle continuous aggregate synergistic silicone rubber sponge thermal insulation material as claimed in claim 5, wherein: the hydrosiloxane (I) is cyclic, linear or branched hydrosiloxane.
13. The in-situ grafting modified mesoporous silica vesicle continuous aggregate synergistic silicone rubber sponge thermal insulation material as claimed in claim 5, wherein: the hydrogen-containing siloxane (I) has a viscosity of 10.0 to 50.0mPa.s at 25 ℃.
14. The in-situ grafting modified mesoporous silica vesicle continuous aggregate synergistic silicone rubber sponge thermal insulation material as claimed in claim 13, wherein: the hydrogen-containing siloxane (I) has a viscosity of 20.0 to 30.0mPa.s at 25 ℃.
15. The in-situ grafting modified mesoporous silica vesicle continuous aggregate synergistic silicone rubber sponge thermal insulation material as claimed in claim 5, wherein: the hydrogen content of the hydrogen-containing siloxane (I) is 0.1-1.67%.
16. The in-situ graft modified mesoporous silica vesicle continuous aggregate synergistic silicone rubber sponge thermal insulation material as claimed in claim 15, wherein: the hydrogen content of the hydrogen-containing siloxane (I) is 1.5-1.6%.
17. The preparation method of the silicone rubber sponge heat insulation material with the in-situ graft modification mesoporous silica vesicle continuous aggregate synergism is characterized by comprising the following steps:
(1) taking (A) vinyl-terminated silicone oil, (B) water and (D) vesicles as raw materials, and forming (E) premix under the action of (C) an alkaline catalyst; (E) in the premix, hydroxyl-terminated polysiloxane is generated in situ under the action of (C) an alkaline catalyst, and reactive hydroxyl groups of a part of the hydroxyl-terminated polysiloxane are condensed with silicon hydroxyl groups on the surface of the vesicle to form graft modification; another part of the hydroxyl-terminated polysiloxane is dissolved in the (E) premix; the premix (E) comprises the following components in parts by mass:
(A) Vinyl-terminated silicone oil 1500.0-3000.0
(B) 10.0-50.0% of water
(C) 1.0-5.0 parts of basic catalyst
(D) Vesicle 500-1000
The alkaline catalyst (C) is lithium hydroxide, potassium hydroxide, sodium hydroxide or tetramethyl ammonium hydroxide; the (D) vesicles are mesoporous silica vesicle continuous aggregates;
(2) sequentially adding (E) premix, (F) platinum catalyst, (G) inhibitor, (H) terminal vinyl silicone oil and (I) hydrogen-containing siloxane, quickly stirring and defoaming, pouring into a mould to begin foaming until the surface is not sticky and the sponge volume is stable, wherein the (E) premix, (F) platinum catalyst, (G) inhibitor, (H) terminal vinyl silicone oil and (I) hydrogen-containing siloxane are as follows:
(E) 70.0-90.0 parts of premix
(F) 0.1-1.0% of platinum catalyst
(G) 0.02-0.05% of inhibitor
(H) 0.0-20.0 parts of vinyl-terminated silicone oil
(I) 10.0 to 20.0 parts of hydrogen-containing siloxane.
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| PCT/CN2020/079262 WO2021179298A1 (en) | 2020-03-12 | 2020-03-13 | Method for preparing silicone rubber sponge thermal insulation material by adopting in-situ graft modified mesoporous silica vesicle continuous aggregate as functional filler |
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| CN113576058A (en) * | 2021-08-27 | 2021-11-02 | 杜成平 | Foamed silica gel bra mold cup and preparation method thereof |
| CN113844135A (en) * | 2021-09-17 | 2021-12-28 | 新华盛节能科技股份有限公司 | Mesoporous silica heat-insulating wrapping material and preparation method thereof |
| CN114106394A (en) * | 2021-11-23 | 2022-03-01 | 清华大学 | Benzene ring bridged organosilicon continuous aggregate vesicle material and preparation method thereof |
| CN114211770A (en) * | 2021-12-24 | 2022-03-22 | 新华盛节能科技股份有限公司 | Preparation method of vesicle composite rock wool material and vesicle composite paste spraying system used for same |
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| JP5392274B2 (en) * | 2011-01-25 | 2014-01-22 | 信越化学工業株式会社 | Method for producing high thermal conductive silicone rubber sponge composition |
| JP6688803B2 (en) * | 2015-02-16 | 2020-04-28 | ダウ・東レ株式会社 | Sponge forming silicone rubber composition and silicone rubber sponge |
| CN105647189B (en) * | 2016-01-29 | 2018-11-02 | 浙江凌志新材料有限公司 | A kind of organic foamed silastic |
| JP6894523B2 (en) * | 2017-02-08 | 2021-06-30 | エルケム・シリコーンズ・ユーエスエイ・コーポレーションＥｌｋｅｍ Ｓｉｌｉｃｏｎｅｓ Ｕｓａ Ｃｏｒｐ． | Silicone rubber syntactic foam |
| CN109054392A (en) * | 2018-05-28 | 2018-12-21 | 佛山市三水铠潮材料科技有限公司 | A kind of high thermal conductive silicon rubber composition |
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