Summary of the invention
Technical problem to be solved by this invention is according to Nuclear power plants needs, provides a kind of Nuclear power plants that meets to use the two component siliconefoam seal gum of the resistance to irradiation of the fire prevention for the Nuclear power plants self cure of standard and preparation technology thereof.
It is as follows that the present invention solves the problems of the technologies described above adopted technical scheme:
The two component siliconefoam seal gum of the resistance to irradiation self cure of fire prevention for Nuclear power plants, comprise component A, B component, described component A by weight each component is configured to:
The hydroxy silicon oil of viscosity 1000 ~ 10000 mPa.s 560 ~ 700 parts;
300 ~ 2000 object quartz sands: 210 ~ 300 parts
Carbon black 1 ~ 5 part;
Pt catalyzer 1 ~ 4 part;
Described B component by weight each component is configured to:
The high viscosity hydroxy silicon oil of viscosity 5000 ~ 15000mPa.s 230 ~ 340 parts;
The vinyl silicone oil of viscosity 1000 ~ 10000 mPa.s 210 ~ 260 parts;
The vinyl phenyl silicone oil of viscosity 200 ~ 2000 mPa.s 40 ~ 55 parts;
The containing hydrogen silicone oil of hydrogeneous 1.0 ~ 2.5% 90 ~ 120 parts;
Auxiliary blowing agent 0 ~ 34 part;
300 ~ 2000 object quartz sands 260 ~ 330 parts;
During use, component A, B component mass ratio are 1:0.9 ~ 1.1.
Further optimization, described component A by weight each component is configured to:
The hydroxy silicon oil of viscosity 1000 ~ 10000 mPa.s 590 ~ 620 parts;
300 ~ 2000 object quartz sands: 225 ~ 260 parts
Carbon black 1 ~ 3 part;
Pt catalyzer 2 ~ 3 parts;
Described B component by weight each component is configured to:
The high viscosity hydroxy silicon oil of viscosity 5000 ~ 15,000 270 ~ 290 parts;
The vinyl silicone oil of viscosity 1000 ~ 10000 mPa.s 225 ~ 250 parts;
The vinyl phenyl silicone oil of viscosity 200 ~ 2000 mPa.s 50 ~ 55 parts;
The containing hydrogen silicone oil of hydrogeneous 1.0 ~ 2.5% 95 ~ 110 parts;
Auxiliary blowing agent 8 ~ 20 parts;
300 ~ 2000 object quartz sands 290 ~ 310 parts.
In described component A, hydroxy silicon oil viscosity is 1000 ~ 5000 mPa.s, and in 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 component A by weight each component is configured to:
The hydroxy silicon oil of viscosity 1000 ~ 5000 mPa.s 600 parts;
300 ~ 2000 object quartz sands 245 parts;
Carbon black 3 parts;
Pt catalyzer 2 parts;
Described B component by weight each component is configured to:
The high viscosity hydroxy silicon oil of viscosity 10000 ~ 15,000 285 parts;
The vinyl silicone oil of viscosity 1000 ~ 5000 mPa.s 240 parts;
The vinyl phenyl silicone oil of viscosity 500 ~ 2000 mPa.s 50 parts;
The containing hydrogen silicone oil of hydrogeneous 1.0 ~ 2.5% 100 parts;
Auxiliary blowing agent 12 parts;
300 ~ 2000 object quartz sands 297 parts;
During use, component A, B component mass ratio are 1:1.
Described auxiliary blowing agent is any one or the above-mentioned multiple mixture formed with arbitrary proportion in the low-molecular-weight hydroxyl silicone oil of glycerine, tetramethylolmethane, viscosity 1 ~ 200 mPa.s.
For a preparation technology for the two component siliconefoam seal gum of the resistance to irradiation self cure of the fire prevention of Nuclear power plants described in above-mentioned any one, it is characterized in that, comprise the steps:
The preparation of component A:
(1) join in reactor by metering by hydroxy silicon oil, temperature remains on 10 ~ 50 ° of C;
(2) in the mixed solution of step (1), add quartz sand, be uniformly mixed 60min;
(3) in step (2) gained solution, add Pt catalyzer, carbon black, be uniformly mixed;
(4) by the degassed 30 ~ 60min of step (3) gained solution for vacuum;
(5) by step (4) gained solution 100 object filtering net pressure filters, fillingly namely component A is obtained;
The preparation of B component:
A high viscosity hydroxy silicon oil, vinyl silicone oil, vinyl phenyl silicone oil, containing hydrogen silicone oil, auxiliary blowing agent join in reaction flask by metering by (), stir 10min and make it be mixed to get mixing solutions completely at the temperature of 10 ~ 50 ° of C;
B () adds 300 ~ 2000 object quartz sands in step (a) gained mixing solutions, be uniformly mixed 60min;
C () is by the degassed 30 ~ 60min of step (b) gained solution for vacuum;
D namely (), by step (c) gained solution 100 object filtering net pressure filters, fillingly obtain 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 keeps mixeding liquid temperature in reactor to be 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 keeps mixeding liquid temperature in reactor to be 10 ~ 50 ° of C.
Compared with prior art, the formula of the two component siliconefoam seal gum of fire prevention resistance to irradiation self cure proposed according to the present invention and the seal gum prepared by preparation technology thereof have the utilisation technology effect of following advantage and essence:
1, the two component siliconefoam seal gum of fire prevention provided by the invention resistance to irradiation self cure has excellent radiation hardness effect;
2, the two component siliconefoam seal gum product preparation process of fire prevention of the present invention resistance to irradiation self cure is fairly simple, and reaction conditions has no special requirements, and preparation time is short; Slow relative to ordinary method foaming, steep crackly shortcoming, the present invention adopts containing polyhydric organic molecule as auxiliary blowing agent, and foaming is fast, and efficiency is high;
3, after tested, the silicone for Nuclear power plants prepared according to composition and engineering provided by the invention is prevented fires resistance to irradiation sealing foam, the various performances such as its fire prevention, radiation hardness, sealing property, intensity reach the requirement of relevant criterion to this series products, meet Nuclear power plants and use standard.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention does not limit by embodiment.
The bi-component silicone foam for Nuclear power plants of the present embodiment comprises component A, B component, wherein component A, B component by weight each component specifically form as shown in table 1.
The concrete proportioning of component A, B component in table 1 the present embodiment
Radiation hardness sealing foam prepared by the present embodiment take hydroxy silicon oil as base-material, and auxiliary take containing hydrogen silicone oil as whipping agent with vinyl silicone oil, a kind of spongy elastic foam with micropore of sulfuration of foaming at ambient temperature.Its reaction formula is as follows:
Under the component proportion of above-mentioned table 1, each component for the present embodiment is studied:
(1) base glue: the two component siliconefoam seal gum of the resistance to irradiation self cure of fire prevention prepared by the present invention, or claim room temperature vulcanization organosilicon foam, material based on the hydroxy silicon oil (i.e. 107 silicon rubber) of different molecular weight (viscosity) and vinyl silicone oil balanced constant mainly selected by its base glue, and its molecular structure is respectively:
107 silica gel viscosity are compared on the impact of 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 the distribution of abscess is also tending towards evenly fine and closely woven, and hardness reduces, and elasticity increases; But the viscosity of sizing material also increases simultaneously, mobility declines, when system viscosity is more than 10000 mPas, in whipping process, in system, each component cannot mix, two-pack product has been difficult to effectively mix before foamable reaction carries out completely, causing the product abscess prepared sparse and distributed pole is uneven, there is obvious atypical characteristic in product.When the viscosity of 107 silica gel used is too low, the intensity of foam system matrix own is low, foaming coefficient is little, the gas that foamable reaction produces easily penetrates bubble wall and overflows and run through into large abscess, form large perforate bubble, reduce closed-cell foam-cell formation probability, the frostproof froth n. multiplying power solidify to form is low, poor flexibility, intensity is low.Therefore, the present invention has prepared has appropriate viscosity silicone oil mixed system as foaming base glue, hydroxy silicon oil viscosity be 1000 ~ 5000 mPa.s, consumption is 590 ~ 620 parts, when vinyl silicone oil viscosity is 1000 ~ 5000 mPa.s, consumption is 225 ~ 250 parts, adopt this proportioning and viscosity parameter, determine other ingredient names mated and physical and chemical parameter, consumption, adopt above-mentioned each component to match, finally prepd siliconefoam seal gum just can reach the radioprotective parameter request of Nuclear power plants simultaneously.
In order to improve the anti-radiation performance of product, the present invention employs a certain amount of phenyl-vinyl silicon oil in formula, and its molecular structural formula is as follows:
Be used alone phenyl-vinyl silicon oil still can at room temperature foam formed spongy elastic foamed body.Common vinyl silicone oil is replaced with the phenyl-vinyl silicon oil of identical viscosities, the frothing percentage of the room temperature vulcanization organosilicon foam using identical catalyzer and 107 silica gel systems to obtain is not than using the density of phenyl-vinyl silicon oil system higher about 15%, and the foam homogeneity of system and rate of closed hole improve.Experiment finds, the radiation-resistant property that phenyl is expected to improve two component silicone seal glue material is suitably introduced in siliconefoam seal gum, vinyl phenyl silicone oil viscosity is 500 ~ 2000 mPa.s, and when consumption is 50 ~ 55 parts, the siliconefoam seal gum radiation hardness effect of preparation is ideal.
(2) filler: as the fire prevention room temperature vulcanization organosilicon of the resistance to irradiation foam of shutoff, in order to reduce costs raising resistance to elevated temperatures, still need the mineral filler using a great deal of, conventional filler has: thermal silica, precipitated silica, quartz sand etc.According to purposes of the present invention, we have mainly carried out testing comparing to thermal silica and quartz sand.
Thermal silica, to too obvious to the product thickening power before solidification, produces detrimentally affect to the use properties of product.Therefore, the room temperature vulcanization organosilicon foam that the present invention describes employs quartz sand and does filler, have employed the relatively high hydroxy silicon oil of molecular weight and vinyl silicone oil as base glue simultaneously.The fineness of quartz sand product has larger impact to product performance, and the present invention compares by experiment, and the optimum size determining quartz sand in room temperature vulcanization organosilicon foam is 300 ~ 2000 orders, and consumption is 290 ~ 310 parts.
(3) containing hydrogen silicone oil
Experiment finds, 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 system solidification process, reduces air-loss and improves bubbling efficiency.Therefore, in room temperature vulcanization organosilicon foam, employing active hydrogen mass fraction is higher containing hydrogen silicone oil.
Silicon-hydrogen bond in containing hydrogen silicone oil and the terminal hydroxy group of base glue carry out condensation dehydrogenation reaction, the hydrogen produced is gathered into bubble distribution in the encapsulant, simultaneously, the composition of sealing agent rubber molecule chain extension is made in catalyzer, the very fast skeleton forming support foam materials in body, the gas that sulfuration is produced is unlikely to holes and subsides, and obtains and has satisfied apparent density and the foam materials of 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 have more perforate, impels vulcanization rate to accelerate; Consumption hour, volumetric expansion is little, and 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 reaches certain value, foaming index variation is not obvious.When containing hydrogen silicone oil consumption is too low, the coefficient that not only foams is little, and sulfuration is also incomplete, the surfaces of tacky of foam silicone rubber.Show after deliberation, adopt the containing hydrogen silicone oil 95 ~ 110 parts of hydrogeneous 1.0 ~ 2.5%, the siliconefoam seal gum of preparation can be made to have good physicochemical property.Hydrogen content described here refers to the active hydrogen massfraction in containing hydrogen silicone oil.
(4) auxiliary blowing agent
When preparing siliconefoam seal gum, the cross-linked speed of resin should adapt with the rate of decomposition of foaming system, start to be cross-linked too early or after late, rate of crosslinking is all unfavorable for the effect improving foam expansion too slowly, because of liquid phase and to deposit be generally be in unsteady state, bubble not in time solidifying and setting just easily merges or subsides, and affects expansion ratio.
In order to effectively, easily regulate expansion ratio, this formula introduces auxiliary blowing agent.More mainly contain the low molecular compound of hydroxyl.The different auxiliary blowing agent of systematic comparison, glycerine, tetramethylolmethane and viscosity 1 ~ 200 foaming effect of low-molecular-weight hydroxy silicon oil of mPa.s.Frothing aid tetramethylolmethane is effective frothing aid, significantly can promote expansion rate, but the consistency of tetramethylolmethane and system is very poor, therefore can only use on a small quantity.
Research shows that low-molecular-weight hydroxy silicon oil is a kind of extraordinary auxiliary blowing agent: one, it is also a kind of silicone molecules, and colorless and odorless, suitability for industrialized production, be conveniently 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, good with low-molecular-weight hydroxy silicon oil consistency.The hydroxy radical content of low-molecular-weight hydroxyl silicone oil is high, only needs effectively to increase expansion ratio on a small quantity.Experiment proves, auxiliary blowing agent consumption is that 8 ~ 20 parts of its auxiliary foaming effects are better.
(5) the two component siliconefoam seal gum of the self cure of catalyzer the present invention research adopts the Platinic chloride complex compound that activity is higher, can be dissolved in organopolysiloxane, the alkene complex as Platinic chloride: double-seal head Pt complex compound.
The catalytic activity of platinum group catalyst to foam silicone rubber is higher.Under its katalysis, silicon rubber in minutes can complete sulfuration and foam.Along with the increase of platinum catalyst consumption, expansion rate is obviously accelerated, and foaming coefficient increases, and the abscess of the foam of generation diminishes, and distribution is also tending towards evenly fine and closely woven.When platinum catalyst consumption is too low, expansion rate does not mate with vulcanization rate, and expansion rate is faster than vulcanization rate, and the gas that reaction generates is overflowed prematurely from sizing material, and cause the abscess-size of foam large, foaming coefficient is little; When platinum catalyst consumption is excessive, foaming and vulcanization rate are exceedingly fast, and foaming and sulfuration can complete instantaneously, and the usage period is too short, operational difficulty, and foam surface unfairness.Tested by systematic comparison, we determine the optimum amount of catalyzer.Its consumption is good catalytic activity 2 ~ 3 parts time.
(6) expansion rate
The two component siliconefoam seal gum of self cure, when foaming, mixes in latter first 30 seconds, substantially can not foaming and intumescing.This is due to initial reaction stage, and system viscosity is high not enough, is difficult to the gas keeping reaction to produce, and after 1min clock, starts rapid expansion, and after mixing 4min, namely reach the maximum value of expansion ratio, expansion ratio maximum value can reach 3.5.The rate of decomposition of the two component siliconefoam seal gum foaming system of the fire prevention that the present invention relates to resistance to irradiation self cure can be better with the crosslinking curing rate-matched of silicone resin cross-linking system, the maximum value of expansion ratio can be reached and make even, the suitable fast expansion of foam, obtaining the silicon foam material that good uniform foam cell is fine and closely woven.
(7) foam structure characterizes
We carry out foam structure sign to the silicon foam material prepared, and result shows, distribution of cells is even, size is little, are unicellular structure, and abscess mean diameter is 0.8 ~ 1.0 mm as calculated.
According to said ratio and preparation technology, by the two component siliconefoam seal gum of the resistance to irradiation self cure of the fire prevention prepared by table 1 proportioning, there is radiation resistance described in table 2 and other physicochemical property parameters.In each component proportion of table 1, have employed hydroxy silicon oil and the vinyl silicone oil balanced constant of different molecular weight (i.e. different viscosity), be sulfuration and whipping agent with the containing hydrogen silicone oil that can produce gas molecules in sulfidation, system viscosity is adjusted by the hydroxy silicon oil of different molecular weight, effectively control hydrogen containing polyhydric auxiliary blowing agent and produce speed and crosslinked foaming speed, active balance product expansion rate, expansion ratio, relation between viscosity, achieves good foaming effect.In the component A of table 1, hydroxy silicon oil viscosity is 1000 ~ 10000 mPa.s, in 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 resistance to irradiation foam all can meet the radiotolerant requirement of Nuclear power plants.In component A, hydroxy silicon oil viscosity is 1000 ~ 5000 mPa.s, in 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 now preparation fire prevention room temperature vulcanization organosilicon of resistance to 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-10.21(B.T.S-10.21) other shutoff and special fire prevention " annex E4 and EJ/T1111-2000 " test method of compressed water reactor nuclear power station-service coating lacquer film gamma-ray irradiation impact ".Irradiation test is carried out according to test basis, as through 5 × 10 by the two component siliconefoam sealant specimen of the resistance to irradiation self cure of the fire prevention prepared by table 1 proportioning
5there is not the phenomenons such as dimensional contraction, stripping, crackle, swelling, foaming, efflorescence in Gy integral dose after irradiating, 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, then the radiation-resistant property of this product meets the related request specified in test basis; Otherwise radiation-resistant property then belongs to the related request not meeting and specify in test basis.
Thermal conductivity test basis: the standard according to GB/T10295-2008 detects, detects the thermal conductivity of sample under the condition of medial temperature 20 DEG C.
Table 2 is prevented fires the performance perameter of the room temperature vulcanization organosilicon of resistance to irradiation foam
According to the detected result of table 2, the two component siliconefoam seal gum of the resistance to irradiation self cure of fire prevention provided by the invention after tested, has excellent radiation hardness effect; And other physical and chemical parameters all can reach the requirement of relevant criterion to this series products, and suitable with same kind of products at abroad performance; The particularly component of sequence number 1, its resistance to irradiation particular significant effect, product prepared according to the methods of the invention, carrying out irradiation test according to 1.2 times of " test method of compressed water reactor nuclear power station-service coating lacquer film gamma-ray irradiation impact " middle irradiation during use, its radiation-resistant property still meets the demands.
According to above-described embodiment, just the present invention can be realized well.Above-described embodiment is only most preferred embodiment of the present invention, but embodiments of the present invention are not limited in this.