Summary of the invention
Technical problem to be solved by this invention is according to the Nuclear power plants needs, and a kind of two component siliconefoam seal gums of the anti-irradiation self cure of fire prevention that is used for Nuclear power plants and preparation technology thereof who meets the Nuclear power plants Application standard is provided.
It is as follows that the present invention solves the problems of the technologies described above the technical scheme that adopts:
The two component siliconefoam seal gums of the anti-irradiation self cure of a kind of fire prevention for Nuclear power plants comprise A component, B component, and described A component each component by weight constitutes:
560~700 parts of the hydroxy silicon oils of viscosity 1000~10000 mPa.s;
300~2000 purpose quartz sands: 210~300 parts
1~5 part of carbon black;
1~4 part of Pt catalyzer;
Described B component each component by weight constitutes:
230~340 parts of the high viscosity hydroxy silicon oils of viscosity 5000~15000mPa.s;
210~260 parts of the vinyl silicone oils of viscosity 1000~10000 mPa.s;
40~55 parts of the vinyl phenyl silicone oils of viscosity 200~2000 mPa.s;
90~120 parts of hydrogeneous 1.0~2.5% containing hydrogen silicone oils;
0~34 part of auxiliary blowing agent;
300~2,000 260~330 parts of purpose quartz sands;
When using, A component, B constituent mass are than being 1:0.9~1.1.
Further optimize, described A component each component by weight constitutes:
590~620 parts of the hydroxy silicon oils of viscosity 1000~10000 mPa.s;
300~2000 purpose quartz sands: 225~260 parts
1~3 part of carbon black;
2~3 parts of Pt catalyzer;
Described B component each component by weight constitutes:
270~290 parts of the high viscosity hydroxy silicon oils of viscosity 5000~15000;
225~250 parts of the vinyl silicone oils of viscosity 1000~10000 mPa.s;
50~55 parts of the vinyl phenyl silicone oils of viscosity 200~2000 mPa.s;
95~110 parts of hydrogeneous 1.0~2.5% containing hydrogen silicone oils;
8~20 parts of auxiliary blowing agents;
300~2,000 290~310 parts of purpose quartz sands.
In described A component, hydroxy silicon oil viscosity is 1000~5000 mPa.s, and in the B component, high viscosity hydroxy silicon oil viscosity is 10000~15000 mPa.s, vinyl silicone oil viscosity is 1000~5000 mPa.s, and the viscosity of vinyl phenyl silicone oil is 500~2000 mPa.s.
The best as said components is preferred, and described A component each component by weight constitutes:
600 parts of the hydroxy silicon oils of viscosity 1000~5000 mPa.s;
300~2,000 245 parts of purpose quartz sands;
3 parts of carbon blacks;
2 parts of Pt catalyzer;
Described B component each component by weight constitutes:
285 parts of the high viscosity hydroxy silicon oils of viscosity 10000~15000;
240 parts of the vinyl silicone oils of viscosity 1000~5000 mPa.s;
50 parts of the vinyl phenyl silicone oils of viscosity 500~2000 mPa.s;
100 parts of hydrogeneous 1.0~2.5% containing hydrogen silicone oils;
12 parts of auxiliary blowing agents;
300~2,000 297 parts of purpose quartz sands;
When using, A component, B constituent mass are than being 1:1.
Described auxiliary blowing agent is any one or the above-mentioned multiple mixture that consists of with arbitrary proportion in the low-molecular-weight hydroxyl silicone oil of glycerine, tetramethylolmethane, viscosity 1~200 mPa.s.
The preparation technology of the two component siliconefoam seal gums of the anti-irradiation self cure of the described fire prevention for Nuclear power plants of a kind of above-mentioned any one is characterized in that, comprises the steps:
The preparation of A component:
(1) by metering, hydroxy silicon oil is joined in reactor, temperature remains on 10~50 ° of C;
(2) add quartz sand in the mixed solution of step (1), mix 60min;
(3) add Pt catalyzer, carbon black in step (2) gained solution, mix;
(4) with the degassed 30~60min of step (3) gained solution for vacuum;
(5) with step (4) gained solution with 100 purpose filtering net pressure filters, can namely gets the A component;
The preparation of B component:
(a) by metering, high viscosity hydroxy silicon oil, vinyl silicone oil, vinyl phenyl silicone oil, containing hydrogen silicone oil, auxiliary blowing agent are joined in reaction flask, stir 10min and make it be mixed to get mixing solutions fully at the temperature of 10~50 ° of C;
(b) add 300~2000 purpose quartz sands in step (a) gained mixing solutions, mix 60min;
(c) with the degassed 30~60min of step (b) gained solution for vacuum;
(d) with step (c) gained solution with 100 purpose filtering net pressure filters, can namely gets the B component.
In described step (1), the viscosity of mixed solution is 1000~2500 mPa.s.
In described step (2), the viscosity of mixed solution is 2500~5500 mPa.s, and in the maintenance reactor, mixeding liquid temperature is 10~50 ° of C.
In described step (a), the viscosity of mixed solution is 1000~2500 mPa.s.
In described step (b), the viscosity of mixed solution is 2500~5500 mPa.s, and in the maintenance reactor, mixeding liquid temperature is 10~50 ° of C.
The formula of the two component siliconefoam seal gums of the anti-irradiation self cure of fire prevention that compared with prior art, propose according to the present invention and the utilisation technology effect that the prepared seal gum of preparation technology has following advantage and essence thereof:
1, the two component siliconefoam seal gums of the anti-irradiation self cure of fire prevention provided by the invention have good radiation hardness effect;
2, the two component siliconefoam seal gum product preparation process of the anti-irradiation self cure of fire prevention of the present invention are fairly simple, and reaction conditions has no special requirements, and preparation time is short; Slow with respect to the ordinary method foaming, steep crackly shortcoming, the present invention adopts and contains polyhydric organic molecule as auxiliary blowing agent, and foaming is fast, and efficient is high;
3, after tested, the anti-irradiation sealing of the silicone fire prevention foam that is used for Nuclear power plants according to composition and engineering preparation provided by the invention, the various performances such as its fire prevention, radiation hardness, sealing property, intensity reach relevant criterion to the requirement of this series products, meet the Nuclear power plants Application standard.
Embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited by embodiment.
The bi-component silicone foam that is used for Nuclear power plants of the present embodiment comprises A component, B component, and wherein the concrete formation of each component is as shown in table 1 by weight for A component, B component.
The concrete proportioning of A component, B component in table 1 the present embodiment
The radiation hardness sealing foam of the present embodiment preparation is take hydroxy silicon oil as base-material, and is auxiliary with vinyl silicone oil, and take containing hydrogen silicone oil as whipping agent, a kind of spongy elastic foam with micropore that forms is vulcanized in foaming at ambient temperature.Its reaction formula is as follows:
Under the component proportion of above-mentioned table 1, study for each component of the present embodiment:
(1) basic glue: the two component siliconefoam seal gums of the anti-irradiation self cure of fire prevention of the present invention's preparation, or title room temperature vulcanization organosilicon foam, it is base mateiral that its basic glue is mainly selected hydroxy silicon oil (i.e. 107 silicon rubber) and the vinyl silicone oil ligand of different molecular weight (viscosity), and its molecular structure is respectively:
Compared the impact of 107 silica gel viscosity on the performance of room temperature vulcanization organosilicon foam by system experimentation.Along with the increase of 107 silica gel viscosity, the foaming coefficient of self cure silicon foam increases to some extent, and the abscess-size of foam reduces gradually, and the rate of closed hole of abscess increases, and it is evenly fine and closely woven that the distribution of abscess also is tending towards, lower hardness, and elasticity increases; But the viscosity of sizing material also increases simultaneously, mobility descends, when system viscosity surpasses 10000 mPas, in system, each component can't mix in whipping process, the two-pack product has been difficult to effectively mix before foamable reaction carries out fully, cause that the product abscess prepared is sparse and distributed pole is inhomogeneous, obvious atypical characteristic appears in product.When the viscosity of 107 silica gel that use is too low, foam is that the intensity of matrix own is low, the foaming coefficient is little, the gas that foamable reaction produces easily penetrates the bubble wall and overflows and run through into large abscess, form large perforate bubble, reduced the closed-cell foam-cell formation probability, the frostproof froth n. multiplying power that solidify to form is low, poor flexibility, intensity is low.Therefore, the present invention has prepared has appropriate viscosity silicone oil mixed system as the basic glue of foaming, be that 1000~5000 mPa.s, consumption are 590~620 parts in hydroxy silicon oil viscosity, vinyl silicone oil viscosity is 1000~5000 mPa.s, when consumption is 225~250 parts, adopt this proportioning and viscosity parameter, the component title of definite other couplings and physical and chemical parameter, consumption, adopt above-mentioned each component to match simultaneously, and finally prepd siliconefoam seal gum just can reach the radioprotective parameter request of Nuclear power plants.
In order to improve the anti-radiation performance of product, the present invention has used a certain amount of phenyl-vinyl silicon oil in formula, and its molecular structural formula is as follows:
Use separately phenyl-vinyl silicon oil still can at room temperature foam and form spongy elastic foamed body.Phenyl-vinyl silicon oil with identical viscosities replaces common vinyl silicone oil, the frothing percentage that uses the room temperature vulcanization organosilicon foam that identical catalyzer and 107 silica gel systems make is more higher approximately 15% than the density of not using the phenyl-vinyl silicon oil system, and foam homogeneity and the rate of closed hole of system improve.Experiment is found, suitably introduce the radiation-resistant property that phenyl is expected to improve two component silicone seal glue materials in the siliconefoam seal gum, vinyl phenyl silicone oil viscosity is 500~2000 mPa.s, and when consumption was 50~55 parts, the siliconefoam seal gum radiation hardness effect of preparation was ideal.
(2) filler: the fire prevention room temperature vulcanization organosilicon of the anti-irradiation foam as shutoff is used, in order to reduce costs the raising resistance to elevated temperatures, still need to use the mineral filler of a great deal of, filler commonly used has: thermal silica, precipitated silica, quartz sand etc.According to purposes of the present invention, we have mainly carried out experiment relatively to thermal silica and quartz sand.
Thermal silica is to too obvious to the product thickening power before solidifying, to the use properties generation detrimentally affect of product.Therefore, the room temperature vulcanization organosilicon foam that the present invention describes has used quartz sand to do filler, has adopted simultaneously the relatively high hydroxy silicon oil of molecular weight and vinyl silicone oil as basic glue.The fineness of quartz sand product has larger impact to product performance, and the present invention compares by experiment, and the optimum size of having determined quartz sand in the room temperature vulcanization organosilicon foam is 300~2000 orders, and consumption is 290~310 parts.
(3) containing hydrogen silicone oil
The experiment discovery, along with the increase of active hydrogen massfraction in containing hydrogen silicone oil, the cross-linking density of foam materials improves.Having of high hydrogen richness containing hydrogen silicone oil can improve system viscosity fast in the system solidification process, reduce air-loss and improve foaming efficient.Therefore, having used the active hydrogen mass fraction in the room temperature vulcanization organosilicon foam is higher containing hydrogen silicone oil.
Silicon-hydrogen bond in containing hydrogen silicone oil and the terminal hydroxy group of basic glue carry out the condensation dehydrogenation reaction, the hydrogen that produces is gathered into bubble distribution in sealing agent, simultaneously, make the composition of sealing agent rubber molecule chain extension in catalyzer, the very fast skeleton that supports foam materials that forms in body, the gas that sulfuration is produced is unlikely to holes and subsides, and obtains the foam materials with satisfied apparent density and over-all properties.The consumption size of containing hydrogen silicone oil can affect the structure of speed of response and foams.Consumption too much can make foam surface that more perforate is arranged, and impels vulcanization rate to accelerate; Consumption hour, volumetric expansion is little, and the product apparent density increases.
The consumption of containing hydrogen silicone oil not only affects the foaming coefficient of foam silicone rubber, but also affects the curability of foam silicone rubber.Along with the increase of containing hydrogen silicone oil consumption, the foaming coefficient of foam silicone rubber increases; But after its consumption reached certain value, the foaming index variation was not obvious.When the containing hydrogen silicone oil consumption was too low, the coefficient that not only foams was little, and sulfuration is also incomplete, the surfaces of tacky of foam silicone rubber.Show after deliberation, adopt 95~110 parts of hydrogeneous 1.0~2.5% containing hydrogen silicone oils, can make the siliconefoam seal gum of preparation have good physicochemical property.Hydrogen content described here refers to the hydrogen activity hydrogen massfraction in containing hydrogen silicone oil.
(4) auxiliary blowing agent
When preparation siliconefoam seal gum, the cross-linked speed of resin should adapt with the rate of decomposition of foaming system, too early or begin crosslinked after late, rate of crosslinking all is unfavorable for improving the effect that foam expands too slowly, because of liquid phase and to deposit be generally to be in unsteady state, the untimely solidifying and setting of bubble just easily merges or subsides, and affects expansion ratio.
In order to regulate expansion ratio effectively, easily, this formula has been introduced auxiliary blowing agent.Mainly some low molecular compounds that contain hydroxyl.Systematic comparison different auxiliary blowing agents, the foaming effect of the low-molecular-weight hydroxy silicon oil of glycerine, tetramethylolmethane and viscosity 1~200 mPa.s.The frothing aid tetramethylolmethane is effective frothing aid, can significantly promote expansion rate, but the consistency of tetramethylolmethane and system is very poor, therefore can only use on a small quantity.
Studies show that low-molecular-weight hydroxy silicon oil is a kind of extraordinary auxiliary blowing agent: one, it is also a kind of organosilicon molecule, colorless and odorless, and suitability for industrialized production, conveniently be easy to get.Two, one of siliconefoam raw material is hydroxy silicon oil, and it is full-bodied hydroxy silicon oil, plays main foaming effect, and is good with low-molecular-weight hydroxy silicon oil consistency.The hydroxy radical content of low-molecular-weight hydroxyl silicone oil is high, and only needing can effectively increase expansion ratio on a small quantity.Experiment showed, that the auxiliary blowing agent consumption is that 8~20 parts of its auxiliary foaming effects are better.
(5) the two component siliconefoam seal gums of the self cure of catalyzer the present invention research adopt active higher, the Platinic chloride complex compound that can be dissolved in organopolysiloxane, as the alkene complex of Platinic chloride: double-seal head Pt complex compound.
Platinum group catalyst is higher to the catalytic activity of foam silicone rubber.Under its katalysis, silicon rubber in minutes can be completed and vulcanizes and foam.Along with the increase of platinum catalyst consumption, expansion rate is obviously accelerated, and the foaming coefficient increases, and the abscess of the foam of generation diminishes, and distributes also to be tending towards evenly fine and closely woven.When the platinum catalyst consumption was too low, expansion rate and vulcanization rate were not mated, and expansion rate is faster than vulcanization rate, and the gas that reaction generates is overflowed from sizing material prematurely, causes the abscess-size of foam large, and the foaming coefficient is little; When the platinum catalyst consumption was excessive, foaming and vulcanization rate were exceedingly fast, and foaming and sulfuration can be completed in moment, and the usage period is too short, operational difficulty, and foam surface unfairness.Test by systematic comparison, we have determined the optimum amount of catalyzer.Its consumption is good catalytic activity in the time of 2~3 parts.
(6) expansion rate
The two component siliconefoam seal gums of self cure mix in rear front 30 seconds when foaming, substantially can foaming and intumescing.This is due to initial reaction stage, and system viscosity is high not enough, is difficult to keep reacting the gas of generation, after the 1min clock, begins rapid expansion, namely reaches the maximum value of expansion ratio after mixing 4min, and the expansion ratio maximum value can reach 3.5.The rate of decomposition of the two component siliconefoam seal gum foaming systems of the anti-irradiation self cure of the fire prevention that the present invention relates to can be better with the crosslinking curing rate-matched of silicone resin cross-linking system, can reach the maximum value of expansion ratio and make the expansion that foam is even, fit speed, obtain the even fine and closely woven silicon foam material of abscess preferably.
(7) foam structure characterizes
We carry out foam structure to the silicon foam material of preparing and characterize, and result shows, distribution of cells is even, size is little, is unicellular structure, and the abscess mean diameter is 0.8~1.0 mm as calculated.
According to said ratio and preparation technology, have the described radiation resistance of table 2 and other physicochemical property parameters by the two component siliconefoam seal gums of the anti-irradiation self cure of the prepared fire prevention of table 1 proportioning.In each component proportion of table 1, adopted hydroxy silicon oil and the vinyl silicone oil of different molecular weight (being different viscosity) to coordinate system, be sulfuration and whipping agent with the containing hydrogen silicone oil that can produce gas molecules in sulfidation, hydroxy silicon oil by different molecular weight is adjusted system viscosity, contain polyhydric auxiliary blowing agent and effectively control hydrogen generation speed and crosslinked foaming speed, the active balance product expansion rate, expansion ratio, relation between viscosity has obtained good foaming effect.In the A component of table 1, hydroxy silicon oil viscosity is 1000~10000 mPa.s, in the B component, high viscosity hydroxy silicon oil viscosity is 5000~15000 mPa.s, vinyl silicone oil viscosity is 1000~10000 mPa.s, the viscosity of vinyl phenyl silicone oil is 200~2000 mPa.s, and in above-mentioned range of viscosities, the prepared fire prevention room temperature vulcanization organosilicon of anti-irradiation foam all can satisfy the radiotolerant requirement of Nuclear power plants.In the A component, hydroxy silicon oil viscosity is 1000~5000 mPa.s, in the B component, high viscosity hydroxy silicon oil viscosity is 10000~15000 mPa.s, vinyl silicone oil viscosity is 1000~5000 mPa.s, the viscosity of vinyl phenyl silicone oil is 500~2000 mPa.s, and the preparation fire prevention this moment room temperature vulcanization organosilicon of anti-irradiation foaming properties is better, and radiation-resistant property significantly improves.
The detection method of each parameter in table 2, the test basis of radiation-resistant property: with reference to the requirement of the program B in " technical specification book-10.21(B.T.S-10.21) other shutoff and special fire prevention " appendix E4 and EJ/T1111-2000 " test method of compressed water reactor nuclear power station-service coating lacquer film gamma-ray irradiation impact ".Carry out irradiation test by the two component siliconefoam sealant specimen of the anti-irradiation self cure of the prepared fire prevention of table 1 proportioning according to test basis, as through 5 * 10
5Dimensional contraction do not occur after Gy integral dose irradiation, peel off, the phenomenons such as crackle, swelling, foaming, efflorescence, color and luster is unchanged, mechanical property also has no considerable change, after pre-irradiation, the sealing property of test specimen all meets the demands, and the radiation-resistant property of this product satisfies the related request of stipulating in test basis; Otherwise radiation-resistant property belongs to and does not satisfy the related request of stipulating in test basis.
Thermal conductivity test basis: detect the thermal conductivity of test sample under the condition of 20 ℃ of medial temperatures according to the standard of GB/T10295-2008.
The performance perameter of the table 2 fire prevention room temperature vulcanization organosilicon of anti-irradiation foam
According to the detected result of table 2 as can be known, the two component siliconefoam seal gums of the anti-irradiation self cure of fire prevention provided by the invention have good radiation hardness effect after tested; And other physical and chemical parameters all can reach relevant criterion to the requirement of this series products, and suitable with the same kind of products at abroad performance; The component of sequence number 1 particularly, its anti-irradiation particular significant effect, product prepared according to the methods of the invention, 1.2 times in irradiation in " compressed water reactor nuclear power station-service coating lacquer film gamma-ray irradiation impact test method " during use are carried out irradiation test, and its radiation-resistant property still meets the demands.
According to above-described embodiment, just can realize well the present invention.Above-described embodiment is only most preferred embodiment of the present invention, but embodiments of the present invention are not limited in this.