CN105131873A - Fireproof liquid of composite fireproof glass and preparation method thereof and composite fireproof glass - Google Patents

Abstract

The invention discloses a fireproof liquid of composite fireproof glass and a preparation method thereof and a composite fireproof glass, relates to a field of safety glass, and solves the problems that a fireproof glue-line has micro bubbles and bad flame resistance. The main method of the invention is as follows: polyol, a functional monomer, deionized water and an auxiliary agent are mixed for obtaining a first mixed emulsion, silica is added, and a silica dispension emulsion is obtained; styrene, methyl methacrylate and butyl acrylate monomer are mixed, a second mixed monomer emulsion is obtained, a cross-linking agent, deionized water, the silica dispersion emulsion and an initiator are added, a soap-free seeded emulsion is obtained after reaction; acrylic acid, styrene, methyl methacrylate and butyl acrylate monomer are mixed, a third mixed monomer emulsion is obtained, deionized water, the initiator, the cross-linking agent and the soap-free seeded emulsion are added, and a soap-free emulsion with core-shell structure is obtained after reaction; a potassium hydroxide solution and an auxiliary agent are added, after mixing, standing and refiltering, an obtained filtrate is the fireproof liquid of composite fireproof glass. The fireproof liquid provided by the invention can be solidified into a fireproof glue, which has good fireproof performance without micro bubbles.

Description

Fire-resistant fluid of composite fireproof glass and preparation method thereof and composite fireproof glass

Technical field

The present invention relates to shatter proof glass field, the composite fireproof glass particularly relating to fire-resistant fluid of a kind of composite fireproof glass and preparation method thereof and adopt this fire-resistant fluid to prepare.

Background technology

Shatter proof glass is a kind of important New Building Materials, is mainly divided into toughened glass, laminated glass, splinter-proof glass, burglar-proof glazing, flame resistant glass, wire glass, cover plate and pad pasting glass, flame resistant glass is a kind of external wall or windowpane with fire-proof function, it can keep the long period not burst under 1000 DEG C of flame impingements, thus effectively stop spreading of flame and smog, be conducive to the very first time discovery condition of a fire, ensure that disaster-stricken crowd has the sufficiently long time to withdraw scene, and striven for the time for disaster relief work, be the most effective safest fire prevention class glassy product at present, flame resistant glass is divided into composite fireproof glass and single-sheet fire-resistant glass, composite fireproof glass refers to the glass of the ordinary plate glass transparent fireproof adhesive bonds more than by two panels or two panels or the glass of spraying composite fireproof glass liquid, composite fireproof glass has fire integrity and fire insulation, also there is physical strength high, anti-folding, the superperformances such as resistance to compression, when composite fireproof glass runs into fire, its fire prevention glue-line can form the refractory heat-insulating foam layer of hard thermal insulation by rapid foaming and intumescing, the heat that a large amount of absorption fire produces, effective blocking-up flame, isolated high temperature and obnoxious flavour, glue-line of simultaneously preventing fires can also bond broken sheet glass, to keep overall integrity, the performance of fire prevention glue-line decides the performance of composite fireproof glass, and glue-line of preventing fires is solidified by fire-resistant fluid and forms, therefore whether fire-resistant fluid has good performance decides composite fireproof glass and whether have good fire resistance.

Domestic at present phase of basic research is in the work that the fire-resistant fluid of composite fireproof glass does, domestic widely used be inorganic fire liquid, as sodium silicate aqueous solution or potassium silicate aqueous solution, be commonly called as sodium silicate or potash water glass, and study less for the inorganic fire-resistant fluid prepared with organic composite material.

All there is many weak points in the Waterproof gum solidified by fire-resistant fluid in prior art in fire resistance, as water glass, its modulus is low, solid content is low, water content is large, and then result in composite fireproof glass and there is a large amount of microvesicle, directly affects the apparent mass of composite fireproof glass, optical property, hardness and toughness, the more important thing is that the existence of microvesicle greatly reduces the fire resistance of composite fireproof glass, it has had a strong impact on result of use and the work-ing life of composite fireproof glass.

Summary of the invention

In view of this, embodiments provide a kind of preparation method of fire-resistant fluid of composite fireproof glass, main purpose be to provide a kind of by the fire-resistant fluid of described composite fireproof glass solidify without microvesicle and the good Waterproof gum of fire resistance.

For achieving the above object, invention broadly provides following technical scheme:

On the one hand, the invention provides a kind of preparation method of fire-resistant fluid of composite fireproof glass, comprise the following steps:

(1) by weight, 15-35 part polyvalent alcohol, 15-50 part function monomer, 2-14 part heat-resisting stabilizing agent, 0.05-0.3 part solidifying agent, 2-8 part carbon forming agent and 8-20 part deionized water are mixed, through stirring obtained first mixed emulsion;

By weight, described for 30-40 part the first mixed emulsion is mixed with 20-40 part hydrophilic nano silica dioxide granule, through stirring obtained nanometer silicon dioxide particle dispersion emulsion;

(2) by weight, 10-30 part vinylbenzene, 15-40 part methyl methacrylate and 20-50 part butyl acrylate are mixed, through stirring obtained second mix monomer emulsion;

By weight, described for 1-8 part the second mix monomer emulsion, 0.1-0.7 part linking agent and 5-15 part deionized water are joined in the described nanometer silicon dioxide particle dispersion emulsion of 50-80 part, and be heated to 60 DEG C-65 DEG C, 0.01-0.05 part redox type initiator is added again, through being obtained by reacting soapless seed emulsion polymerization in described nanometer silicon dioxide particle dispersion emulsion;

(3) by weight, 10-30 part vinylformic acid, 15-40 part vinylbenzene, 25-50 part methyl methacrylate and 5-20 part butyl acrylate are mixed, through stirring obtained 3rd mix monomer emulsion;

By weight, described for 5-25 part the 3rd mix monomer emulsion, 5-25 part deionized water, 0.01-0.22 part redox type initiator and 0.1-0.7 part linking agent are joined in the described soapless seed emulsion polymerization of 55-105 part, obtains soap-free core-shell emulsion 60 DEG C-65 DEG C reactions after 3-5 hour;

(4) by weight, the potassium hydroxide aqueous solution being 50% by described for 70-75 part soap-free core-shell emulsion and 5-8 part mass percentage concentration mixes, add 1-5 part again and become carbon auxiliary agent, 0.05-0.1 part ion fixing agent, 0.01-0.05 part defoamer, 0.1-0.2 part flow agent and 0.05-0.2 part solidifying agent, through stirring, leave standstill, refilter, gained filtrate is the fire-resistant fluid of composite fireproof glass.

As preferably, described polyvalent alcohol is one or more in glycerine, Xylitol and tetramethylolmethane; Described function monomer is one or more in vinylformic acid, methacrylic acid and polyacrylamide.

As preferably, by weight, described first mixed emulsion is mixed obtained by 15-20 part glycerine, 2-4 part Xylitol, 2-4 part tetramethylolmethane, 10-15 part vinylformic acid, 10-15 part methacrylic acid, 5-10 part polyacrylamide, 3-5 part borax, 3-5 part boric acid, 3-6 part sucrose, 0.1-0.2 part Sodium Silicofluoride and 10-15 part deionized water.

As preferably, by weight, described second mix monomer emulsion be mixed by 15-20 part vinylbenzene, 20-30 part methyl methacrylate and 30-40 part butyl acrylate obtained.

As preferably, by weight, described 3rd mix monomer emulsion be mixed by 15-20 part vinylformic acid, 20-30 part vinylbenzene, 30-40 part methyl methacrylate and 10-15 part butyl acrylate obtained.

As preferably, described char-forming agent is one or more in sucrose, fructose, glucose and granulated sugar; Described one-tenth charcoal auxiliary agent is one or more in potassium primary phosphate, potassium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC and sodium hydrogen phosphate; Described ion fixing agent is one or more in zinc oxide, aluminum oxide and starch; Described defoamer is organic silicon modified by polyether and/or polyurethanes auxiliary agent; Described flow agent is polyethers auxiliary agent; Described heat-resisting stabilizing agent is borax and/or boric acid; Described solidifying agent is one or more in Sodium Silicofluoride, potassium silicofluoride and aluminum fluoride; Described linking agent is 1,2-Vinylstyrene; Described redox type initiator is formed with the mixed in molar ratio of 1:1 by ammonium persulphate and sodium bisulfite; The granularity of described hydrophilic nano silica dioxide granule is 60nm-150nm.

On the other hand, the invention provides a kind of fire-resistant fluid of composite fireproof glass, the fire-resistant fluid of described composite fireproof glass is prepared from by the preparation method of the fire-resistant fluid of above-mentioned composite fireproof glass.

Another aspect, the invention provides a kind of composite fireproof glass, described composite fireproof glass comprises the first glass and the second glass, the Waterproof gum that described first glass and described second glass are solidified by fire-resistant fluid is combined layer by layer, described fire-resistant fluid is the fire-resistant fluid of above-mentioned composite fireproof glass, and the outside surface of described first glass has antireflection coatings.

As preferably, described second glass is combined by described fire prevention glue-line and the 3rd glass coating; The thickness of described first glass, described second glass and described 3rd glass is 4mm, and the thickness of described fire prevention glue-line is 1mm-2mm.

As preferably, described antireflection coatings is silicon dioxide layer film coating, titanium dioxide unitary film coating, earth silicon/titanic oxide duplicature coating, titania/silica duplicature coating or earth silicon/titanic oxide/silicon-dioxide MULTILAYER COMPOSITE film coating; The thickness of described silicon dioxide layer film coating or titanium dioxide unitary film coating is 0.0001mm-0.1mm.

Compared with prior art, the invention has the beneficial effects as follows:

The technique means of the fire-resistant fluid of composite fireproof glass is prepared by being mixed mutually with potassium hydroxide solution by soap-free core-shell emulsion, solve the technical problem that there is microvesicle and fire resistance difference in the fire prevention glue-line of the fire-resistant fluid solidification of composite fireproof glass, reach without microvesicle in the fire prevention glue-line of composite fireproof glass, the technique effect that fire resistance is good.

Accompanying drawing explanation

Fig. 1 is the structural representation of a kind of composite fireproof glass that the embodiment of the present invention provides;

Fig. 2 is the structural representation of the another kind of composite fireproof glass that the embodiment of the present invention provides.

Description of reference numerals:

1 antireflection coatings, 2 first glass, 21 second glass, 22 the 3rd glass, 23 the 4th glass, 24 the 5th glass, 3 fire prevention glue-lines.

Embodiment

For further setting forth the present invention for the technique means reaching predetermined goal of the invention and take and effect, below in conjunction with accompanying drawing with preferred embodiment, to according to the embodiment of the present patent application, technical scheme, feature and effect thereof, be described in detail as follows.Special characteristic, structure or feature in multiple embodiments in following explanation can be combined by any suitable form; The present invention is when describing the preparation method of fire-resistant fluid of composite fireproof glass, and sequence number (1) (2) (3) (4) that adopt, do not limit the sequence of steps of the inventive method; " one or more " that the present invention mentions, comprise by the situation of two kinds of material composition mixtures; In an embodiment, for the allied substances with same or similar character and performance same effect, only enumerate wherein moieties and be described, all do not enumerate, other materials do not enumerated have equally has enumerated effect that material possesses skills; When content for material has range of choice, the partial data only enumerated in range of choice is described, and does not all enumerate, and other data do not enumerated in range of choice have the technique effect that enumerated data has equally.

Embodiment 1

First accurately take 0.15kg glycerine, 0.15kg vinylformic acid, 0.02kg borax, 0.0005kg Sodium Silicofluoride, 0.02kg sucrose and 0.08kg deionized water, said components is mixed, by abundant stirring, obtained first mixed emulsion, stand-by;

Accurately take the hydrophilic nano silica dioxide granule that above-mentioned first mixed emulsion of 0.3kg and 0.2kg particle diameter are 60nm, hydrophilic nano silica dioxide granule is scattered in the first mixed emulsion respectively through ultrasonic disperse and high-speed stirring, forming weight by standing 5 hours froth breakings is stable nanometer silicon dioxide particle dispersion emulsion, stand-by;

Accurately take 0.1kg vinylbenzene, 0.15kg methyl methacrylate and 0.2kg butyl acrylate, said components is mixed, by abundant stirring, obtained second mix monomer emulsion, stand-by;

Be that 1:1 mixes by ammonium persulphate and sodium bisulfite with mol ratio, and as the redox type initiator of polyreaction, and it is stand-by to prepare 0.1kg in advance;

Accurately take the above-mentioned second mix monomer emulsion of 0.01kg, 0.001kg1, 2-Vinylstyrene and 0.05kg deionized water, above-mentioned nanometer silicon dioxide particle dispersion emulsion is at the uniform velocity stirred with the rotating speed of 250rpm/min, and in above-mentioned nanometer silicon dioxide particle dispersion emulsion, nitrogen protection is passed under whipped state, under whipped state, in above-mentioned nanometer silicon dioxide particle dispersion emulsion, add the above-mentioned second mix monomer emulsion of 0.01kg successively simultaneously, 0.001kg1, 2-Vinylstyrene and 0.05kg deionized water, by stirring abundant mixing, stir and be slowly heated to 60 DEG C simultaneously, accurately take the redox type initiator that 0.0001kg prepares in advance, again above-mentioned for 0.0001kg redox type initiator is joined in above-mentioned nanometer silicon dioxide particle dispersion emulsion, polymerization reaction take place under the condition of redox type initiator and 60 DEG C of temperature of reaction, prepare soapless seed emulsion polymerization, stand-by,

Accurately take 0.1kg vinylformic acid, 0.15kg vinylbenzene, 0.25kg methyl methacrylate and 0.05kg butyl acrylate, said components is mixed, by abundant stirring, obtained 3rd mix monomer emulsion, stand-by;

Accurately take the above-mentioned 3rd mix monomer emulsion of 0.05kg, 0.05kg deionized water, the above-mentioned redox type initiator of 0.0001kg and 0.001kg1,2-Vinylstyrene, and fully mix, be heated to 60 DEG C, join in above-mentioned soapless seed emulsion polymerization with constant speed, 60 DEG C of isothermal reactions 4 hours after dropping terminates, finally obtain soap-free core-shell emulsion;

Prepare weight to be in advance 0.1kg massfraction be the potassium hydroxide aqueous solution of 50%, accurately take the above-mentioned soap-free core-shell emulsion of 0.7kg, 0.05kg massfraction be 50% potassium hydroxide aqueous solution, 0.01kg potassium primary phosphate, 0.0005kg starch, 0.0001kg organic silicon modified by polyether BYK-024,0.001kg polyethers auxiliary agent RH-212 and 0.0005kg Sodium Silicofluoride, the potassium hydroxide aqueous solution being first 50% by above-mentioned for 0.7kg soap-free core-shell emulsion and 0.05kg massfraction fully mixes, and stir 10 minutes, add 0.01kg potassium primary phosphate successively again, 0.0005kg starch, 0.0001kg organic silicon modified by polyether BYK-024, 0.001kg polyethers auxiliary agent RH-212 and 0.0005kg Sodium Silicofluoride, and under the vacuum tightness of 20mbar stirring at low speed 20 minutes, after keeping being cooled to normal temperature under vacuum conditions, slowly rise to normal pressure again, froth breaking is left standstill under normal temperature and pressure, filtered by 100 eye mesh screens again, gained filtrate is the fire-resistant fluid of composite fireproof glass.

Embodiment 2

First accurately take 0.2kg tetramethylolmethane, 0.2kg methacrylic acid, 0.04kg boric acid, 0.001kg potassium silicofluoride, 0.03kg fructose and 0.12kg deionized water, said components is mixed, by abundant stirring, obtained first mixed emulsion, stand-by;

Accurately take the hydrophilic nano silica dioxide granule that above-mentioned first mixed emulsion of 0.32kg and 0.24kg particle diameter are 80nm, hydrophilic nano silica dioxide granule is scattered in the first mixed emulsion respectively through ultrasonic disperse and high-speed stirring, forming weight by standing 6 hours froth breakings is stable nanometer silicon dioxide particle dispersion emulsion, stand-by.

Accurately take 0.20kg vinylbenzene, 0.2kg methyl methacrylate and 0.3kg butyl acrylate, said components is mixed, by abundant stirring, obtained second mix monomer emulsion, stand-by;

Be that 1:1 carries out mixing the redox type initiator as polyreaction using ammonium persulphate and sodium bisulfite with mol ratio, and it is stand-by to prepare 0.1kg in advance;

Accurately take the above-mentioned second mix monomer emulsion of 0.03kg, 0.002kg1, 2-Vinylstyrene and 0.08kg deionized water, above-mentioned nanometer silicon dioxide particle dispersion emulsion is at the uniform velocity stirred with the rotating speed of 250rpm/min, and in above-mentioned nanometer silicon dioxide particle dispersion emulsion, nitrogen protection is passed under whipped state, under whipped state, in above-mentioned nanometer silicon dioxide particle dispersion emulsion, add the above-mentioned second mix monomer emulsion of 0.03kg successively simultaneously, 0.002kg1, 2-Vinylstyrene and 0.08kg deionized water, by stirring abundant mixing, stir and be slowly heated to 62 DEG C simultaneously, accurately take the redox type initiator that 0.00015kg prepares in advance, again above-mentioned for 0.0002kg redox type initiator is joined in above-mentioned nanometer silicon dioxide particle dispersion emulsion, polymerization reaction take place under the condition of redox type initiator and temperature of reaction, prepare soapless seed emulsion polymerization, stand-by.

Accurately take 0.15kg vinylformic acid, 0.20kg vinylbenzene, 0.30kg methyl methacrylate and 0.10kg butyl acrylate, said components is mixed, by abundant stirring, obtained 3rd mix monomer emulsion, stand-by;

Accurately take the above-mentioned 3rd mix monomer emulsion of 0.1kg, 0.08kg deionized water, the above-mentioned redox type initiator of 0.0005kg and 0.002kg1,2-Vinylstyrene, and fully mix, be heated to 62 DEG C, join in above-mentioned soapless seed emulsion polymerization with constant speed, 62 DEG C of isothermal reactions 4 hours after dropping terminates, finally obtain soap-free core-shell emulsion.

Prepare weight to be in advance 0.1kg massfraction be the potassium hydroxide aqueous solution of 50%, accurately take the above-mentioned soap-free core-shell emulsion of 0.71kg, 0.06kg massfraction be 50% potassium hydroxide aqueous solution, 0.02kg potassium hydrogen phosphate, 0.0006kg zinc oxide, 0.0002kg polyurethanes auxiliary agent 902W, 0.002kg polyethers auxiliary agent RH-212 and 0.0008kg Sodium Silicofluoride, the potassium hydroxide aqueous solution being first 50% by above-mentioned for 0.71kg soap-free core-shell emulsion and 0.06kg massfraction fully mixes, and stir 10 minutes, add 0.02kg potassium hydrogen phosphate successively again, 0.0006kg zinc oxide, 0.0002kg polyurethanes auxiliary agent 902W, 0.002kg polyethers auxiliary agent RH-212 and 0.0008kg Sodium Silicofluoride, and under the vacuum tightness of 25mbar stirring at low speed 20 minutes, remain on after vacuum state is cooled to normal temperature, slowly rise to normal pressure again, froth breaking is left standstill under normal temperature and pressure, filtered by 100 eye mesh screens again, gained filtrate is the fire-resistant fluid of composite fireproof glass.

Embodiment 3

First 0.23kg Xylitol, 0.25kg polyacrylamide, 0.03kg borax and 0.03kg boric acid, 0.0015kg aluminum fluoride, 0.04kg glucose and 0.16kg deionized water is accurately taken, said components is mixed, by abundant stirring, obtained first mixed emulsion, stand-by;

Above-mentioned first mixed emulsion of accurate measuring 0.34kg and 0.28kg particle diameter are the hydrophilic nano silica dioxide granule of 100nm, hydrophilic nano silica dioxide granule is scattered in the first mixed emulsion respectively through ultrasonic disperse and high-speed stirring, forming weight by standing 7 hours froth breakings is stable nanometer silicon dioxide particle dispersion emulsion, stand-by.

Accurately take 0.20kg vinylbenzene, 0.25kg methyl methacrylate and 0.35kg butyl acrylate, said components is mixed, by abundant stirring, obtained second mix monomer emulsion, stand-by;

Be that 1:1 carries out mixing the redox type initiator as polyreaction using ammonium persulphate and sodium bisulfite with mol ratio, and it is stand-by to prepare 0.1kg in advance;

Accurately take the above-mentioned second mix monomer emulsion of 0.05kg, 0.003kg1, 2-Vinylstyrene and 0.08kg deionized water, above-mentioned nanometer silicon dioxide particle dispersion emulsion is at the uniform velocity stirred with the rotating speed of 250rpm/min, and in above-mentioned nanometer silicon dioxide particle dispersion emulsion, nitrogen protection is passed under whipped state, under whipped state, in above-mentioned nanometer silicon dioxide particle dispersion emulsion, add the above-mentioned second mix monomer emulsion of 0.05kg successively simultaneously, 0.003kg1, 2-Vinylstyrene and 0.08kg deionized water, by stirring abundant mixing, stir and be slowly heated to 63 DEG C simultaneously, accurately take the redox type initiator that 0.0003kg prepares in advance, again above-mentioned for 0.0003kg redox type initiator is joined in above-mentioned nanometer silicon dioxide particle dispersion emulsion, polymerization reaction take place under the condition of redox type initiator and temperature of reaction, prepare soapless seed emulsion polymerization, stand-by.

Accurately take 0.20kg vinylformic acid, 0.25kg vinylbenzene, 0.35kg methyl methacrylate and 0.15kg butyl acrylate, said components is mixed, by abundant stirring, obtained 3rd mix monomer emulsion, stand-by;

Accurately take the above-mentioned 3rd mix monomer emulsion of 0.15kg, 0.08kg deionized water, the above-mentioned redox type initiator of 0.001kg and 0.003kg1,2-Vinylstyrene, and fully mix, be heated to 63 DEG C, join in above-mentioned soapless seed emulsion polymerization with constant speed, 63 DEG C of isothermal reactions 4 hours after dropping terminates, finally obtain soap-free core-shell emulsion.

Prepare weight to be in advance 0.1kg massfraction be the potassium hydroxide aqueous solution of 50%, accurately take the above-mentioned soap-free core-shell emulsion of 0.72kg, 0.07kg massfraction be 50% potassium hydroxide aqueous solution, 0.03kg SODIUM PHOSPHATE, MONOBASIC, 0.0014kg aluminum oxide, 0.0003kg polyurethanes auxiliary agent 902W, 0.0014kg polyethers auxiliary agent RH-212 and 0.0012kg aluminum fluoride, the potassium hydroxide aqueous solution being first 50% by above-mentioned for 0.72kg soap-free core-shell emulsion and 0.07kg massfraction fully mixes, and stir 10 minutes, add 0.03kg SODIUM PHOSPHATE, MONOBASIC successively again, 0.0007kg aluminum oxide, 0.0003kg polyurethanes auxiliary agent 902W, 0.0014kg polyethers auxiliary agent RH-212 and 0.0012kg aluminum fluoride, and under the vacuum tightness of 30mbar stirring at low speed 20 minutes, remain on after vacuum state is cooled to normal temperature, slowly rise to normal pressure again, froth breaking is left standstill under normal temperature and pressure, filtered by 100 eye mesh screens again, gained filtrate is the fire-resistant fluid of composite fireproof glass.

Embodiment 4

First 0.2kg glycerine and 0.05kg tetramethylolmethane, 0.15kg vinylformic acid and 0.15kg methacrylic acid, 0.04kg borax and 0.04kg boric acid, 0.001kg Sodium Silicofluoride and 0.001kg potassium silicofluoride, 0.05kg granulated sugar and 0.18kg deionized water is accurately taken, said components is mixed, by abundant stirring, obtained first mixed emulsion, stand-by;

Accurately take the hydrophilic nano silica dioxide granule that above-mentioned first mixed emulsion of 0.36kg and 0.32kg particle diameter are 120nm, hydrophilic nano silica dioxide granule is scattered in the first mixed emulsion respectively through ultrasonic disperse and high-speed stirring, forming weight by standing 8 hours froth breakings is stable nanometer silicon dioxide particle dispersion emulsion, stand-by.

Accurately take 0.25kg vinylbenzene, 0.30kg methyl methacrylate and 0.40kg butyl acrylate, said components is mixed, by abundant stirring, obtained second mix monomer emulsion, stand-by;

Be that 1:1 carries out mixing the redox type initiator as polyreaction using ammonium persulphate and sodium bisulfite with mol ratio, and it is stand-by to prepare 0.1kg in advance;

Accurately take the above-mentioned second mix monomer emulsion of 0.08kg, 0.005kg1, 2-Vinylstyrene and 0.11kg deionized water, above-mentioned nanometer silicon dioxide particle dispersion emulsion is at the uniform velocity stirred with the rotating speed of 250rpm/min, and in above-mentioned nanometer silicon dioxide particle dispersion emulsion, nitrogen protection is passed under whipped state, under whipped state, in above-mentioned nanometer silicon dioxide particle dispersion emulsion, add the above-mentioned second mix monomer emulsion of 0.08kg successively simultaneously, 0.005kg1, 2-Vinylstyrene and 0.11kg deionized water, by stirring abundant mixing, stir and be slowly heated to 64 DEG C simultaneously, accurately take the redox type initiator that 0.0004kg prepares in advance, again above-mentioned for 0.0004kg redox type initiator is joined in above-mentioned nanometer silicon dioxide particle dispersion emulsion, polymerization reaction take place under the condition of redox type initiator and temperature of reaction, prepare soapless seed emulsion polymerization, stand-by.

Accurately take 0.25kg vinylformic acid, 0.30kg vinylbenzene, 0.40kg methyl methacrylate and 0.20kg butyl acrylate, said components is mixed, by abundant stirring, obtained 3rd mix monomer emulsion, stand-by;

Accurately take the above-mentioned 3rd mix monomer emulsion of 0.2kg, 0.12kg deionized water, the above-mentioned redox type initiator of 0.0015kg and 0.005kg1,2-Vinylstyrene, and fully mix, be heated to 64 DEG C, join in above-mentioned soapless seed emulsion polymerization with constant speed, 64 DEG C of isothermal reactions 4 hours after dropping terminates, finally obtain soap-free core-shell emulsion.

Prepare weight to be in advance 0.1kg massfraction be the potassium hydroxide aqueous solution of 50%, accurately take the above-mentioned soap-free core-shell emulsion of 0.73kg, 0.08kg massfraction be 50% potassium hydroxide aqueous solution, 0.04kg sodium hydrogen phosphate, 0.0004kg aluminum oxide and 0.0004kg starch, 0.0002kg organic silicon modified by polyether BYK-024 and 0.0002kg polyurethanes auxiliary agent 902W, 0.0016kg polyethers auxiliary agent RH-212 and 0.0008kg aluminum fluoride and 0.0008kg Sodium Silicofluoride, the potassium hydroxide aqueous solution being first 50% by above-mentioned for 0.73kg soap-free core-shell emulsion and 0.08kg massfraction fully mixes, and stir 10 minutes, add 0.04kg SODIUM PHOSPHATE, MONOBASIC successively again, 0.0004kg aluminum oxide and 0.0004kg starch, 0.0002kg organic silicon modified by polyether BYK-024 and 0.0002kg polyurethanes auxiliary agent 902W, 0.0016kg polyethers auxiliary agent RH-212 and 0.0008kg aluminum fluoride and 0.0008kg Sodium Silicofluoride, and under the vacuum tightness of 35mbar stirring at low speed 20 minutes, remain on after vacuum state is cooled to normal temperature, slowly rise to normal pressure again, froth breaking is left standstill under normal temperature and pressure, filtered by 100 eye mesh screens again, gained filtrate is the fire-resistant fluid of composite fireproof glass.

Embodiment 5

First 0.24kg glycerine and 0.04kg Xylitol, 0.18kg polyacrylamide and 0.17kg methacrylic acid, 0.05kg borax and 0.05kg boric acid, 0.0012kg Sodium Silicofluoride and 0.0013kg aluminum fluoride, 0.03kg sucrose and 0.03kg fructose and 0.2kg deionized water is accurately taken, said components is mixed, by abundant stirring, obtained first mixed emulsion, stand-by;

Accurately take the hydrophilic nano silica dioxide granule that above-mentioned first mixed emulsion of 0.38kg and 0.36kg particle diameter are 140nm, hydrophilic nano silica dioxide granule is scattered in the first mixed emulsion respectively through ultrasonic disperse and high-speed stirring, forming weight by standing 9 hours froth breakings is stable nanometer silicon dioxide particle dispersion emulsion, stand-by.

Accurately take 0.3kg vinylbenzene, 0.35kg methyl methacrylate and 0.45kg butyl acrylate, said components is mixed, by abundant stirring, obtained second mix monomer emulsion, stand-by;

Be that 1:1 carries out mixing the redox type initiator as polyreaction using ammonium persulphate and sodium bisulfite with mol ratio, and it is stand-by to prepare 0.1kg in advance;

The above-mentioned second mix monomer emulsion of accurate measuring 0.07kg, 0.007kg1, 2-Vinylstyrene and 0.15kg deionized water, above-mentioned nanometer silicon dioxide particle dispersion emulsion is at the uniform velocity stirred with the rotating speed of 250rpm/min, and in above-mentioned nanometer silicon dioxide particle dispersion emulsion, nitrogen protection is passed under whipped state, under whipped state, in above-mentioned nanometer silicon dioxide particle dispersion emulsion, add the above-mentioned second mix monomer emulsion of 0.07kg successively simultaneously, 0.007kg1, 2-Vinylstyrene and 0.15kg deionized water, by stirring abundant mixing, stir and be slowly heated to 65 DEG C simultaneously, accurately take the redox type initiator that 0.00025kg prepares in advance, again above-mentioned for 0.0005kg redox type initiator is joined in above-mentioned nanometer silicon dioxide particle dispersion emulsion, polymerization reaction take place under the condition of redox type initiator and temperature of reaction, prepare soapless seed emulsion polymerization, stand-by.

Accurately take 0.3kg vinylformic acid, 0.35kg vinylbenzene, 0.45kg methyl methacrylate and 0.20kg butyl acrylate, said components is mixed, by abundant stirring, obtained 3rd mix monomer emulsion, stand-by;

Accurately take the above-mentioned 3rd mix monomer emulsion of 0.25kg, 0.15kg deionized water, the above-mentioned redox type initiator of 0.002kg and 0.007kg1,2-Vinylstyrene, and fully mix, be heated to 65 DEG C, join in above-mentioned soapless seed emulsion polymerization with constant speed, 65 DEG C of isothermal reactions 4 hours after dropping terminates, finally obtain soap-free core-shell emulsion.

Prepare weight to be in advance 0.1kg massfraction be the potassium hydroxide aqueous solution of 50%, accurately take the above-mentioned soap-free core-shell emulsion of 0.74kg, 0.065kg massfraction be 50% potassium hydroxide aqueous solution, 0.025kg potassium hydrogen phosphate and 0.025kg potassium primary phosphate, 0.00045kg zinc oxide and 0.00045kg starch, 0.0003kg organic silicon modified by polyether BYK-024 and 0.0002kg polyurethanes auxiliary agent 902W, 0.0018kg polyethers auxiliary agent RH-212 and 0.0009kg aluminum fluoride and 0.0009kg potassium silicofluoride, the potassium hydroxide aqueous solution being first 50% by above-mentioned for 0.74kg soap-free core-shell emulsion and 0.065kg massfraction fully mixes, and stir 10 minutes, add 0.025kg potassium hydrogen phosphate and 0.025kg potassium primary phosphate more successively, 0.00045kg zinc oxide and 0.00045kg starch, 0.0003kg organic silicon modified by polyether BYK-024 and 0.0002kg polyurethanes auxiliary agent 902W, 0.0018kg polyethers auxiliary agent RH-212 and 0.0009kg aluminum fluoride and 0.0009kg potassium silicofluoride, and under the vacuum tightness of 40mbar stirring at low speed 20 minutes, remain on after vacuum state is cooled to normal temperature, slowly rise to normal pressure again, froth breaking is left standstill under normal temperature and pressure, filtered by 100 eye mesh screens again, gained filtrate is the fire-resistant fluid of composite fireproof glass.

Embodiment 6

First 0.15kg tetramethylolmethane and 0.16kg Xylitol, 0.2kg polyacrylamide and 0.2kg vinylformic acid, 0.06kg borax and 0.06kg boric acid, 0.0015kg Sodium Silicofluoride and 0.0015kg potassium silicofluoride, 0.04kg glucose and 0.03kg granulated sugar and 0.17kg deionized water is accurately taken, said components is mixed, by abundant stirring, obtained first mixed emulsion, stand-by;

Accurately take the hydrophilic nano silica dioxide granule that above-mentioned first mixed emulsion of 0.4kg and 0.4kg particle diameter are 150nm, hydrophilic nano silica dioxide granule is scattered in the first mixed emulsion respectively through ultrasonic disperse and high-speed stirring, forming weight by standing 9 hours froth breakings is stable nanometer silicon dioxide particle dispersion emulsion, stand-by.

Accurately take 0.28kg vinylbenzene, 0.40kg methyl methacrylate and 0.50kg butyl acrylate, said components is mixed, by abundant stirring, obtained second mix monomer emulsion, stand-by;

Be that 1:1 carries out mixing the redox type initiator as polyreaction using ammonium persulphate and sodium bisulfite with mol ratio, and it is stand-by to prepare 0.1kg in advance;

Accurately take the above-mentioned second mix monomer emulsion of 0.08kg, 0.007kg1, 2-Vinylstyrene and 0.15kg deionized water, above-mentioned nanometer silicon dioxide particle dispersion emulsion is at the uniform velocity stirred with the rotating speed of 250rpm/min, and in above-mentioned nanometer silicon dioxide particle dispersion emulsion, nitrogen protection is passed under whipped state, under whipped state, in above-mentioned nanometer silicon dioxide particle dispersion emulsion, add the above-mentioned second mix monomer emulsion of 0.08kg successively simultaneously, 0.007kg1, 2-Vinylstyrene and 0.15kg deionized water, by stirring abundant mixing, stir and be slowly heated to 65 DEG C simultaneously, accurately take the redox type initiator that 0.00025kg prepares in advance, again above-mentioned for 0.00045kg redox type initiator is joined in above-mentioned nanometer silicon dioxide particle dispersion emulsion, polymerization reaction take place under the condition of redox type initiator and temperature of reaction, prepare soapless seed emulsion polymerization, stand-by.

Accurately take 0.3kg vinylformic acid, 0.35kg vinylbenzene, 0.45kg methyl methacrylate and 0.20kg butyl acrylate, said components is mixed, by abundant stirring, obtained 3rd mix monomer emulsion, stand-by;

Accurately take the above-mentioned 3rd mix monomer emulsion of 0.25kg, 0.25kg deionized water, the above-mentioned redox type initiator of 0.0022kg and 0.007kg1,2-Vinylstyrene, and fully mix, be heated to 65 DEG C, join in above-mentioned soapless seed emulsion polymerization with constant speed, 65 DEG C of isothermal reactions 4 hours after dropping terminates, finally obtain soap-free core-shell emulsion.

Prepare weight to be in advance 0.1kg massfraction be the potassium hydroxide aqueous solution of 50%, accurately take the above-mentioned soap-free core-shell emulsion of 0.75kg, 0.075kg massfraction be 50% potassium hydroxide aqueous solution, 0.020kg potassium hydrogen phosphate and 0.020kg potassium primary phosphate and 0.01kg sodium hydrogen phosphate, 0.00035kg zinc oxide and 0.00035kg starch and aluminum oxide, 0.0003kg organic silicon modified by polyether BYK-024 and 0.0002kg polyurethanes auxiliary agent 902W, 0.002kg polyethers auxiliary agent RH-212 and 0.0006kg aluminum fluoride and 0.0007kg potassium silicofluoride and 0.0007kg Sodium Silicofluoride, the potassium hydroxide aqueous solution being first 50% by above-mentioned for 0.75kg soap-free core-shell emulsion and 0.055kg massfraction fully mixes, and stir 10 minutes, add 0.020kg potassium hydrogen phosphate and 0.020kg potassium primary phosphate and 0.01kg sodium hydrogen phosphate more successively, 0.00035kg zinc oxide and 0.00035kg starch and aluminum oxide, 0.0003kg organic silicon modified by polyether BYK-024 and 0.0002kg polyurethanes auxiliary agent 902W, 0.002kg polyethers auxiliary agent RH-212 and 0.0006kg aluminum fluoride and 0.0007kg potassium silicofluoride and 0.0007kg Sodium Silicofluoride, and under the vacuum tightness of 35mbar stirring at low speed 20 minutes, remain on after vacuum state is cooled to normal temperature, slowly rise to normal pressure again, froth breaking is left standstill under normal temperature and pressure, filtered by 100 eye mesh screens again, gained filtrate is the fire-resistant fluid of composite fireproof glass.

Embodiment 7

First 0.18kg glycerine and 0.03kg tetramethylolmethane and 0.03kg Xylitol, 0.13kg vinylformic acid and 0.13kg methacrylic acid and 0.07kg polyacrylamide, 0.045kg borax and 0.045kg boric acid, 0.0005kg Sodium Silicofluoride and 0.0005kg potassium silicofluoride and 0.0005kg aluminum fluoride, 0.015kg sucrose and 0.015kg fructose and 0.01kg glucose and 0.005kg granulated sugar and 0.13kg deionized water is accurately taken, said components is mixed, by abundant stirring, obtained first mixed emulsion, stand-by;

Accurately take the hydrophilic nano silica dioxide granule that above-mentioned first mixed emulsion of 0.35kg and 0.3kg particle diameter are 105nm, hydrophilic nano silica dioxide granule is scattered in the first mixed emulsion respectively through ultrasonic disperse and high-speed stirring, forming weight by standing 7.5 hours froth breakings is stable nanometer silicon dioxide particle dispersion emulsion, stand-by.

Accurately take 0.275kg vinylbenzene, 0.35kg methyl methacrylate and 0.35kg butyl acrylate, said components is mixed, by abundant stirring, obtained second mix monomer emulsion, stand-by;

Be that 1:1 carries out mixing the redox type initiator as polyreaction using ammonium persulphate and sodium bisulfite with mol ratio, and it is stand-by to prepare 0.1kg in advance;

Accurately take the above-mentioned second mix monomer emulsion of 0.035kg, 0.0035kg1, 2-Vinylstyrene and 0.15kg deionized water, above-mentioned nanometer silicon dioxide particle dispersion emulsion is at the uniform velocity stirred with the rotating speed of 250rpm/min, and in above-mentioned nanometer silicon dioxide particle dispersion emulsion, nitrogen protection is passed under whipped state, under whipped state, in above-mentioned nanometer silicon dioxide particle dispersion emulsion, add the above-mentioned second mix monomer emulsion of 0.035kg successively simultaneously, 0.0035kg1, 2-Vinylstyrene and 0.075kg deionized water, by stirring abundant mixing, stir and be slowly heated to 63 DEG C simultaneously, accurately take the redox type initiator that 0.00025kg prepares in advance, again above-mentioned for 0.00025kg redox type initiator is joined in above-mentioned nanometer silicon dioxide particle dispersion emulsion, polymerization reaction take place under the condition of redox type initiator and temperature of reaction, prepare soapless seed emulsion polymerization, stand-by.

Accurately take 0.175kg vinylformic acid, 0.25kg vinylbenzene, 0.35kg methyl methacrylate and 0.125kg butyl acrylate, said components is mixed, by abundant stirring, obtained 3rd mix monomer emulsion, stand-by;

Accurately take the above-mentioned 3rd mix monomer emulsion of 0.15kg, 0.20kg deionized water, the above-mentioned redox type initiator of 0.00017kg and 0.0035kg1,2-Vinylstyrene, and fully mix, be heated to 63 DEG C, join in above-mentioned soapless seed emulsion polymerization with constant speed, 63 DEG C of isothermal reactions 4 hours after dropping terminates, finally obtain soap-free core-shell emulsion.

Prepare weight to be in advance 0.1kg massfraction be the potassium hydroxide aqueous solution of 50%, accurately take the above-mentioned soap-free core-shell emulsion of 0.725kg, 0.065kg massfraction is the potassium hydroxide aqueous solution of 50%, 0.01kg potassium hydrogen phosphate and 0.010kg potassium primary phosphate and 0.01kg sodium hydrogen phosphate and 0.005kg SODIUM PHOSPHATE, MONOBASIC, 0.0003kg zinc oxide and 0.0003kg starch and 0.0002kg aluminum oxide, 0.00015kg organic silicon modified by polyether BYK-024 and 0.00015kg polyurethanes auxiliary agent 902W, 0.0015kg polyethers auxiliary agent RH-212 and 0.0005kg aluminum fluoride and 0.0005kg potassium silicofluoride and 0.0005kg Sodium Silicofluoride, the potassium hydroxide aqueous solution being first 50% by above-mentioned for 0.725kg soap-free core-shell emulsion and 0.065kg massfraction fully mixes, and stir 10 minutes, add 0.01kg potassium hydrogen phosphate and 0.010kg potassium primary phosphate and 0.01kg sodium hydrogen phosphate and 0.005kg SODIUM PHOSPHATE, MONOBASIC more successively, 0.0003kg zinc oxide and 0.0003kg starch and 0.0002kg aluminum oxide, 0.00015kg organic silicon modified by polyether and 0.00015kg polyurethanes auxiliary agent 902W, 0.0015kg polyethers auxiliary agent RH-212 and 0.0005kg aluminum fluoride and 0.0005kg potassium silicofluoride and 0.0005kg Sodium Silicofluoride, and under the vacuum tightness of 30mbar stirring at low speed 20 minutes, remain on after vacuum state is cooled to normal temperature, slowly rise to normal pressure again, froth breaking is left standstill under normal temperature and pressure, filtered by 100 eye mesh screens again, gained filtrate is the fire-resistant fluid of composite fireproof glass.

In the fire-resistant fluid of above-mentioned composite fireproof glass, the effect of each auxiliary agent is as follows:

Polyvalent alcohol: refer to the alcohols containing more than three or three hydroxyls in molecule, such as glycerine, trihydroxy methyl ethane, tetramethylolmethane, Xylitol, sorbyl alcohol etc.; Every have stronger crystallinity and all can adopt compared with the polyvalent alcohol of high bond strength; The polyvalent alcohol that the present invention adopts is one or more in glycerine, Xylitol and tetramethylolmethane, by using above-mentioned polyvalent alcohol, improves agglutinating value(of coal) and the intensity of composite fireproof glass; Above-mentioned polyvalent alcohol is also hydrocarbon polymer simultaneously, also can be used as carbon forming agent, has the effect of tensio-active agent to a certain extent, and itself serve certain froth breaking and antifreezing effect.

Function monomer: refer to the monomer that specific function group can be provided, as agglutinating value(of coal), water tolerance, stability etc.; The function monomer of the every agglutinating value(of coal) and stability that can improve the fire-resistant fluid of composite fireproof glass all can adopt; The function monomer that the present invention adopts is one or more in vinylformic acid, methacrylic acid and polyacrylamide; Wherein, vinylformic acid and methacrylic acid are as water-soluble monomer, and can be used as emulsifying agent, synthetic polymer monomer, methyl methacrylate and vinylbenzene are as comonomer, the second-order transition temperature of each one polymer of the fire-resistant fluid of adjustable composite fireproof glass, increases its cohesive strength and stability.

Char-forming agent and one-tenth charcoal auxiliary agent: under enough heats, the hydroxyl in molecule ruptures from carbochain, and the carbochain losing hydroxyl forms gac, and gac forms insulation layer to stop heat trnasfer; Every char-forming agent that at high temperature can form long-chain charcoal insulation layer all can adopt; The carbon forming agent that the present invention adopts is one or more in sucrose, fructose, glucose and granulated sugar, becomes carbon auxiliary agent to be one or more in potassium primary phosphate, potassium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC and sodium hydrogen phosphate; When glue-line of preventing fires at high temperature foams generation hole, char-forming agent and the charing of one-tenth charcoal auxiliary agent form the carbide of long-chain, and be deposited in above-mentioned hole, the carbide of long-chain can absorb amount of heat, thus enhances the fire resistance of glass.

Defoamer: can suppress produce foam or eliminate the foam produced; The defoamer that the present invention adopts is organic silicon modified by polyether BYK-024 and/or polyurethanes auxiliary agent 902W; Because when preparing the fire-resistant fluid of composite fireproof glass, needs stirring just can make each material fully mix, and inevitably produce bubble while of stirring, when the fire-resistant fluid of composite fireproof glass is solidified into Waterproof gum and is overlying on composite fireproof glass surperficial, bubble can be present in fire prevention glue-line, what the apparent mass of composite fireproof glass was become is poor, and bubble in fire-resistant fluid can be eliminated by adding above-mentioned defoamer, namely eliminate the bubble in fire prevention glue-line, and then improve the apparent mass of composite fireproof glass.Heat-resisting stabilizing agent: the heat-resisting stabilizing agent that the present invention adopts is borax and/or boric acid, there is flame retardant resistance, heat-resisting and the properties of transparency of the fire prevention glue-line that the fire-resistant fluid that can improve composite fireproof glass is solidified into, control the coefficient of thermal expansion of above-mentioned fire prevention glue-line, and then the chemical stability of raising composite fireproof glass, resistance to mechanical impact capacity and thermal shocking ability.

Ion fixing agent: the ion fixing agent that the present invention adopts is one or more in zinc oxide, aluminum oxide and starch, in the fire prevention glue-line that its fire-resistant fluid that can change composite fireproof glass is solidified into, the activity of potassium oxide, can improve the water tolerance of above-mentioned fire prevention glue-line by adding above-mentioned ion fixing agent.

Flow agent: the flow agent that the present invention adopts is polyethers auxiliary agent RH-212, when preparing composite fireproof glass, the fire-resistant fluid coating overlaying on the composite fireproof glass on composite fireproof glass surface needs to dry, because composite fireproof glass has certain amount of deflection, in dry process, the fire prevention glue-line that the fire-resistant fluid of composite fireproof glass is solidified into inevitably produces thickness difference, by adding above-mentioned flow agent, make above-mentioned fire prevention glue-line still can form smooth, smooth and uniform glue-line after pressurized, to ensure that above-mentioned fire prevention glue-line evenly and bubble-free.

Solidifying agent: the solidifying agent that the present invention adopts is one or more in Sodium Silicofluoride, potassium silicofluoride and aluminum fluoride, soap-free core-shell emulsion and potassium hydroxide aqueous solution reaction generate the fire-resistant fluid of composite fireproof glass, namely the potash water glass that solid content is higher, utilize solidifying agent can accelerate both speed of response and curing speed, and the intensity of fire prevention glue-line that is solidified into of the fire-resistant fluid improving composite fireproof glass and the intensity of composite fireproof glass.

Linking agent: the linking agent that the present invention adopts is 1,2-Vinylstyrene, it can accelerate the sclerosis of the fire-resistant fluid of composite fireproof glass, improves the thermotolerance of the fire-resistant fluid of composite fireproof glass, improves physical strength and the weathering resistance of the Waterproof gum of composite fireproof glass solidification.

Initiator: it is that the mixture of the ammonium persulphate of 1:1 and sodium bisulfite is as redox initiator with mol ratio that the present invention adopts, it can carry out polyreaction by trigger monomer, be prepare the important integral part of above-mentioned soap-free core-shell emulsion, directly affect size of the polymerization rate of above-mentioned soap-free core-shell emulsion, the transformation efficiency of monomer and final particle etc.; Redox initiator systems be utilize the transfer transport between Oxidizing and Reducing Agents to generate free radical to cause the polyreaction of soap-free core-shell emulsion, because the reaction activity of redox initiation system is much smaller than the reaction activity of thermal initiation system, the kick off temperature of above-mentioned soap-free core-shell emulsion can be reduced, improve speed of reaction, reduce energy consumption of reaction, partial function monomer generation hydrolysis reaction at high temperature can also be avoided simultaneously.

Emulsifying agent: all need during traditional emulsion polymerization reaction take place to use emulsifying agent, to make polymerization system stablize, but brings into emulsifying agent in the finished product and goes, even if also cannot by complete for emulsifying agent Ex-all by washing process.Existence due to emulsifying agent can affect the optical property of emulsion polymer, electrical property, the compactness of film, water tolerance, scrub resistance and sticking power etc., limits the range of application of emulsion; Expensive emulsifying agent turn increases the production cost of emulsion simultaneously.In order to overcome the drawback because emulsifying agent brings, have developed new emulsion polymerization systems---emulsifier-free emulsion polymerization.This letex polymerization is the new technology grown up on conventional emulsion polymerizations basis, and so-called emulsifier-free emulsion polymerization refers to the emulsion polymerization process not adding emulsifying agent in reaction process completely, reduces the production cost of emulsion.

The fire-resistant fluid of composite fireproof glass of the present invention is soap-free emulsion: namely do not have emulsifying agent completely in emulsion, and latex particle is mainly able to stable by the various ionic group be combined on polymkeric substance long-chain or its end group.Introduce these groups mainly by carrying out copolymerization with water-soluble monomer, multipolymer is positioned at the surface of micelle owing to having wetting ability, these hydrophilic radicals can exist in the form of an ion under certain pH value, also can rely on the space steric effect between them thus make latex particle reach steady state; And vinylformic acid is due to containing hydrophilic radical-COOH, the effect of similar emulsifying agent can be played, reason is that vinylformic acid is water-soluble monomer, both containing hydrophilic radical-COOH, simultaneously again containing hydrophobic grouping-CH3, therefore in soap-free core-shell emulsion polymerization of the present invention, part propylene acid mono can be similar to the effect playing emulsifying agent, part acrylic acid can play again the effect of polymerization single polymerization monomer, and simultaneously acrylic acid second-order transition temperature is about 105 degree, similar to vinylbenzene, methyl methacrylate.

The fire-resistant fluid of composite fireproof glass prepared by the inventive method is the emulsion of nucleocapsid structure: mainly refer to two or more monomers under certain condition stage by stage or multi-stage polymeric, make inner side or the outside enrichment heterogeneity respectively of emulsion particle, i.e. hud typed emulsion particle, thus impart core and the variant function of shell, obtain the composite emulsion of different performance.

When preparing the second mix monomer emulsion in the inventive method, use vinylbenzene, methyl methacrylate and butyl acrylate to carry out reaction and obtain multipolymer, vinylbenzene is due to containing phenyl ring, and its second-order transition temperature is about 105 degree, be vitreous state at normal temperatures, the rigidity of multipolymer can be improved, simultaneously owing to adopting 1,2-Vinylstyrene is linking agent, it is easy to make vinylbenzene and other monomer copolymerizations, the second-order transition temperature of polymethylmethacrylate is similar to polystyrene, under the prerequisite of second-order transition temperature not affecting multipolymer, can reduce costs; The second-order transition temperature of butyl acrylate is-56 degree left and right, is rubbery state at normal temperatures, can improves the toughness of multipolymer, prevent multipolymer from use brittle rupture occurring.According to the multipolymer that the component proportion in the inventive method obtains, i.e. the second mix monomer emulsion, known according to the second-order transition temperature formulae discovery of multipolymer, the second-order transition temperature of the second mix monomer emulsion is at about 50 degree, be vitreous state under normal temperature condition, there is certain toughness; In the nucleocapsid structure of the second mix monomer emulsion, the particulate in the second mix monomer emulsion is wrapped in the nanometer silicon dioxide particle as core as the first shell.

When preparing the 3rd mix monomer emulsion in the inventive method, employ vinylbenzene, methyl methacrylate, vinylformic acid and butyl acrylate, according to the multipolymer that the component proportion of the inventive method obtains, i.e. the 3rd mix monomer emulsion, known according to the second-order transition temperature formulae discovery of multipolymer, owing to there is crosslinking structure in the 3rd mix monomer emulsion system, the second-order transition temperature of the 3rd mix monomer emulsion is at about 80 degree, improve the intensity of latex particle shell, the fire-resistant fluid of the composite fireproof glass finally obtained is made to become a kind of structure of hard outside soft inside, namely under the Waterproof gum be solidified at the fire-resistant fluid of guarantee composite fireproof glass has the condition of higher-strength, still there is certain toughness.In the nucleocapsid structure of the 3rd mix monomer emulsion, the particulate of the 3rd mix monomer emulsion is wrapped in the particulate of the second mix monomer emulsion as the first shell as the second shell.

The fire-resistant fluid of composite fireproof glass prepared by the inventive method, have employed the method preparing core-shell emulsion, core is the mixture based on silicon-dioxide, two-layer colloid shell has been wrapped up in outside, potassium hydroxide solution in the outside of two-layer colloid shell, two-layer colloid sheath polymers Absorbable rod ultraviolet, extend the work-ing life of composite fireproof glass, the more important thing is that silica dioxide granule and potassium hydroxide solution can be kept apart by certain thickness colloid shell under normal temperature or low temperature, when normal temperature or low temperature, silica dioxide granule cannot contact with potassium hydroxide solution, do not react, and when temperature is higher, during second-order transition temperature namely higher than colloid shell, colloid shell becomes rubbery state from vitreous state, potassium hydroxide solution infiltrates in colloid shell, react with silica dioxide granule and obtain potassium silicate solution, namely water content is obtained very little, modulus is the potash water glass of 4-6, and the Sodium Silicofluoride added, the curing speed of potash water glass can be accelerated, improve the intensity after potash water glass solidification, the silica network skeleton formed after potash water glass sclerosis, at high temperature hardness declines very little, and have good flame retardant resistance, can high temperature resistantly prevent fires, hardness is higher, enhances hardness and the resistance toheat of composite fireproof glass, simultaneously because containing vinylformic acid and methacrylic acid in colloid, vinylformic acid and methacrylic acid all have wetting ability, and containing some water in colloid, when meeting fire, water will ooze out, and also play certain fire extinguishing function, the fire-resistant fluid of the composite fireproof glass that the inventive method adopts nucleocapsid structure to prepare, the soap-free core-shell emulsion of 70%-75% and potassium hydroxide solution are mixed, generate potassium silicate at a certain temperature, its water content is few, modulus high (modulus refers to molecular ratio or the mol ratio of silicon oxide and alkalimetal oxide in water glass), larger effect can be played when preventing fires, simultaneously because water content is few, the Waterproof gum of the fire-resistant fluid solidification of above-mentioned composite fireproof glass, without microvesicle, substantially increases apparent property and the fireproofing and heat resistant of composite fireproof glass.

On the other hand, the invention provides a kind of fire-resistant fluid of composite fireproof glass; The fire-resistant fluid of above-mentioned composite fireproof glass is prepared from by above-mentioned preparation method.

Embodiment 8

As shown in Figure 1, the present invention has prepared a kind of composite fireproof glass, be made up of the first glass 2 and the second glass 21, first glass 2 and the second glass 21 are laminated together by the agglutinating value(of coal) of glue-line 3 of preventing fires, fire prevention glue-line 3 is that the fire-resistant fluid solidification of the composite fireproof glass prepared by embodiment 1 forms, and the outside surface of the first glass 2 has antireflection coatings 1, and antireflection coatings 1 is silicon dioxide layer film coating, the thickness of fire prevention glue-line 3 is 1mm, and the thickness of antireflection coatings 1 is 0.0001mm.

Embodiment 9

As shown in Figure 2, the present invention has prepared a kind of composite fireproof glass, be made up of the first glass 2, second glass 21, the 3rd glass 22, the 4th glass 23 and the 5th glass 24, above-mentioned 5 sheet glass are laminated together by the agglutinating value(of coal) of glue-line 3 of preventing fires, fire prevention glue-line 3 is that the fire-resistant fluid solidification of the composite fireproof glass prepared by embodiment 1 forms, the outside surface of the first glass 2 has antireflection coatings 1, the thickness of fire prevention glue-line 3 is 2mm, antireflection coatings 1 is titanium dioxide unitary film coating, and the thickness of antireflection coatings 1 is 0.1mm.

Preferred as above-described embodiment, at the outside surface of the second glass 21 by fire prevention glue-line 3 laminated divided glass, such as, second glass 21 by fire prevention glue-line 3 and the 3rd glass 22 laminated, 3rd glass 22 by fire prevention glue-line 3 and the 4th glass 23 laminated, 4th glass 23 is laminated with the 5th glass 24 by fire prevention glue-line 3, the 5th glass 24 by prevent fires glue-line 3 and the 6th glass laminated etc.

Execute the preferred of example as above-mentioned, the thickness of fire prevention glue-line 3 is 1mm-2mm, and the thickness of the first glass 2, second glass 21, the 3rd glass 22, the 4th glass 23 and the 5th glass 24 is 4mm.

Execute the preferred of example as above-mentioned, above-mentioned antireflection coatings is silicon dioxide layer film coating, titanium dioxide unitary film coating, earth silicon/titanic oxide duplicature coating, titania/silica duplicature coating or earth silicon/titanic oxide/silicon-dioxide MULTILAYER COMPOSITE film coating; The thickness of above-mentioned silicon dioxide layer film coating or titanium dioxide unitary film coating is 0.0001mm-0.1mm; Wherein, when the antireflection coatings of composite fireproof glass is MULTILAYER COMPOSITE film coating, better can reduce the reflected light of composite fireproof glass, improve transmittance.

The method preparing above-mentioned composite fireproof glass is:

A, prepare the thick glass of 5 4mm, wherein 4 is chemically toughened glass, and 1 is non-chemically toughened glass;

B, by the fire-resistant fluid of the above-mentioned composite fireproof glass prepared, be overlying on above-mentioned 4 chemically toughened glass surfaces respectively by sheet form of drying in the air, and be 80 DEG C in temperature, humidity is 60%, condition under to dry in the air system 12 hours, obtain 4 chemically toughened glass with the thick fire prevention glue-line of 1.5mm; Wherein, temperature processed of drying in the air can be 75 DEG C-85 DEG C, and humidity can be 50%-70%, and the thickness of fire prevention glue-line can be 1-2mm; Above-mentioned 4 chemically toughened glass are labeled as the second glass glass, the 3rd glass, the 4th glass and the 5th glass, by remaining 1 non-chemically toughened glass be labeled as the first glass, and the first glass preparation is become the glass with thick individual layer silicon-dioxide (SiO2) antireflection coatings of 0.0005mm, make composite fireproof glass be about 1.13-1.40 in the specific refractory power of 300nm-2500nm scope; Wherein, the thickness of above-mentioned individual layer silicon-dioxide (SiO2) antireflection coatings can be 0.0001mm-0.1mm, above-mentioned antireflection coatings can also be titanium dioxide (TiO2) film of individual layer, also can be SiO2/TiO2 or TiO2/SiO2 duplicature, can also be SiO2/TiO2/SiO2 multilayer complex films;

C, by the gland of the 4th glass not with fire prevention glue-line in the one side of the 5th glass ribbon fire prevention glue-line, two blocks of glass are adhered to each other by middle stickiness of preventing fires glue-line;

D, with the way identical with step c successively by the 3rd glass not with fire prevention glue-line a gland the 4th glass ribbon fire prevention glue-line one side on, by the second glass not with fire prevention glue-line a gland the 3rd glass ribbon fire prevention glue-line one side on;

E, by the gland of the first glass not with antireflection coatings in the one side of the second glass ribbon fire prevention glue-line, one of first glass ribbon antireflection coatings faces up, namely the one side of the first glass ribbon antireflection coatings is in the outer surface of composite fireproof glass, as shown in Figure 2;

F, above-mentioned laminated good composite fire-proof glass is put into autoclave be forced into 0.5Mpa, pressurization is warming up to about 80 DEG C and steam pressure 30min simultaneously, takes out after being cooled to room temperature, namely obtains tool and to be of five storeys the composite fireproof glass of 4 layers, glass fire prevention glue-line; Wherein, above-mentioned fire prevention glue-line is solidified by the fire-resistant fluid of above-mentioned composite fireproof glass to form.

Embodiment 1-7 is adopted to prepare the method for the fire-resistant fluid of composite fireproof glass, prepare the fire-resistant fluid of 7 kinds of composite fireproof glass, accordingly, adopt the fire-resistant fluid of above-mentioned 7 kinds of composite fireproof glass, by the above-mentioned method preparing composite fireproof glass, 7 composite fireproof glass identical with the composite fireproof glass structure of embodiment 9 are obtained.

Comparative example 1

Adopt pure potash water glass as the fire-resistant fluid of composite fireproof glass, by the above-mentioned method preparing composite fireproof glass, prepare the composite fireproof glass identical with embodiment 9 structure.

Comparative example 2

Get 1kg water, 1kg modulus is the potash water glass of 2.9-3.4, mixes formation potash water glass; Adopt potash water glass as the fire-resistant fluid of composite fireproof glass, by the above-mentioned method preparing composite fireproof glass, prepare the composite fireproof glass identical with embodiment 9 structure.

Carry out fire performance test experience according to GB/T12513-2006 national standard to above-mentioned 9 pieces of composite fireproof glass, obtain the fire prevention time of each composite fireproof glass, parallel sample 4 is got in experiment, gets its statistical average as experimental result; Apparent mass is obtained by macroscopic form; The performance perameter of 2 pieces of composite fireproof glass that the 7 pieces of composite fireproof glass adopting the fire-resistant fluid of the composite fireproof glass of embodiment 1-7 to prepare and comparative example 1-2 provide refers to table 1:

The fire resistance parameter list of table 1.9 piece composite fireproof glass

Embodiment glass	Transmitance	Fire prevention time/min	Apparent mass
				Embodiment 1 glass	79％	69	Without microvesicle, antireflection layer is not corroded
Embodiment 2 glass	81％	77	Without microvesicle, antireflection layer is not corroded
				Embodiment 3 glass	82％	79	Without microvesicle, antireflection layer is not corroded
Embodiment 4 glass	84％	81	Without microvesicle, antireflection layer is not corroded
				Embodiment 5 glass	83％	82	Without microvesicle, antireflection layer is not corroded
Embodiment 6 glass	83％	81	Without microvesicle, antireflection layer is not corroded
				Embodiment 7 glass	85％	84	Without microvesicle, antireflection layer is not corroded
Comparative example 1 glass	58％	41	Have microvesicle, antireflection layer has white point
				Comparative example 2 glass	61％	49	Have microvesicle, antireflection layer has white point

Note: above-mentioned glass refers to the composite fireproof glass utilizing the fire-resistant fluid of the composite fireproof glass of embodiment 1-7 to prepare.

Drawn by above-mentioned detection method and test data, adopt potash water glass or pure potash water glass as the fire-resistant fluid of composite fireproof glass in comparative example 1 or 2 and the composite fireproof glass prepared, there is a large amount of microvesicle in its inside, antireflection coatings is corroded by potash water glass and occurs white point, and the fire prevention time is shorter; Have microvesicle, the fire prevention time is short, and illustrate that in the fire-resistant fluid of the composite fireproof glass of comparative example 1 and comparative example 2, water content is many, the existence of a large amount of microvesicle reduces the hardness of composite fireproof glass, reduces the fireproofing and heat resistant performance of composite fireproof glass; Antireflection layer has white point explanation antireflection layer to be subject to the corrosion of potash water glass, and extent of corrosion is difficult to control, and it has had a strong impact on apparent mass and the light transmission of composite fireproof glass.

By 7 pieces of composite fireproof glass prepared by the fire-resistant fluid of the composite fireproof glass adopting embodiment 1-7, without microvesicle, the fire prevention time is longer, and antireflection coatings is not corroded, and light transmission is good and apparent property is good, without microvesicle, the fire prevention time is longer, illustrate that in the fire-resistant fluid of composite fireproof glass of the present invention, water content is few, without microvesicle in fire prevention glue-line, composite fireproof glass has preferably fireproofing and heat resistant performance, and because of the fire-resistant fluid of composite fireproof glass of the present invention be the soap-free emulsion and the potassium hydroxide solution that have employed nucleocapsid structure, it just can the technique means of water generation reaction glass under the condition of the second-order transition temperature higher than sheath polymers, avoid antireflection layer directly to be corroded by water glass at depressed temperatures, or at room temperature, and once there is corrosion, control device can be taked immediately, prevent water glass from corroding antireflection layer further, emulsifying agent is not added in fire-resistant fluid again because of above-mentioned composite fireproof glass, and then also reduce the production cost of fire-resistant fluid of composite fireproof glass.

The specific embodiment of the present invention is only above; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses, change can be expected easily or replace, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of the claims.

Claims (10)

1. the preparation method of the fire-resistant fluid of composite fireproof glass, is characterized in that, comprises the following steps:

(1) by weight, 15-35 part polyvalent alcohol, 15-50 part function monomer, 2-14 part heat-resisting stabilizing agent, 0.05-0.3 part solidifying agent, 2-8 part carbon forming agent and 8-20 part deionized water are mixed, through stirring obtained first mixed emulsion;

By weight, described for 30-40 part the first mixed emulsion is mixed with 20-40 part hydrophilic nano silica dioxide granule, through stirring obtained nanometer silicon dioxide particle dispersion emulsion;

(2) by weight, 10-30 part vinylbenzene, 15-40 part methyl methacrylate and 20-50 part butyl acrylate are mixed, through stirring obtained second mix monomer emulsion;

By weight, described for 1-8 part the second mix monomer emulsion, 0.1-0.7 part linking agent and 5-15 part deionized water are joined in the described nanometer silicon dioxide particle dispersion emulsion of 50-80 part, and be heated to 60 DEG C-65 DEG C, 0.01-0.05 part redox type initiator is added again, through being obtained by reacting soapless seed emulsion polymerization in described nanometer silicon dioxide particle dispersion emulsion;

(3) by weight, 10-30 part vinylformic acid, 15-40 part vinylbenzene, 25-50 part methyl methacrylate and 5-20 part butyl acrylate are mixed, through stirring obtained 3rd mix monomer emulsion;

By weight, described for 5-25 part the 3rd mix monomer emulsion, 5-25 part deionized water, 0.01-0.22 part redox type initiator and 0.1-0.7 part linking agent are joined in the described soapless seed emulsion polymerization of 55-105 part, obtains soap-free core-shell emulsion 60 DEG C-65 DEG C reactions after 3-5 hour;

(4) by weight, the potassium hydroxide aqueous solution being 50% by described for 70-75 part soap-free core-shell emulsion and 5-8 part mass percentage concentration mixes, add 1-5 part again and become carbon auxiliary agent, 0.05-0.1 part ion fixing agent, 0.01-0.05 part defoamer, 0.1-0.2 part flow agent and 0.05-0.2 part solidifying agent, through stirring, leave standstill, refilter, gained filtrate is the fire-resistant fluid of composite fireproof glass.

2. the preparation method of the fire-resistant fluid of composite fireproof glass according to claim 1, is characterized in that, described polyvalent alcohol is one or more in glycerine, Xylitol and tetramethylolmethane; Described function monomer is one or more in vinylformic acid, methacrylic acid and polyacrylamide.

3. the preparation method of the fire-resistant fluid of composite fireproof glass according to claim 1, it is characterized in that, by weight, described first mixed emulsion is mixed obtained by 15-20 part glycerine, 2-4 part Xylitol, 2-4 part tetramethylolmethane, 10-15 part vinylformic acid, 10-15 part methacrylic acid, 5-10 part polyacrylamide, 3-5 part borax, 3-5 part boric acid, 3-6 part sucrose, 0.1-0.2 part Sodium Silicofluoride and 10-15 part deionized water.

4. the preparation method of the fire-resistant fluid of composite fireproof glass according to claim 1, it is characterized in that, by weight, described second mix monomer emulsion is mixed by 15-20 part vinylbenzene, 20-30 part methyl methacrylate and 30-40 part butyl acrylate to obtain.

5. the preparation method of the fire-resistant fluid of composite fireproof glass according to claim 1, it is characterized in that, by weight, described 3rd mix monomer emulsion is mixed by 15-20 part vinylformic acid, 20-30 part vinylbenzene, 30-40 part methyl methacrylate and 10-15 part butyl acrylate to obtain.

6. the preparation method of the fire-resistant fluid of composite fireproof glass according to claim 1, is characterized in that, described char-forming agent is one or more in sucrose, fructose, glucose and granulated sugar; Described one-tenth charcoal auxiliary agent is one or more in potassium primary phosphate, potassium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC and sodium hydrogen phosphate; Described ion fixing agent is one or more in zinc oxide, aluminum oxide and starch; Described defoamer is organic silicon modified by polyether and/or polyurethanes auxiliary agent; Described flow agent is polyethers auxiliary agent; Described heat-resisting stabilizing agent is borax and/or boric acid; Described solidifying agent is one or more in Sodium Silicofluoride, potassium silicofluoride and aluminum fluoride; Described linking agent is 1,2-Vinylstyrene; Described redox type initiator is formed with the mixed in molar ratio of 1:1 by ammonium persulphate and sodium bisulfite; The granularity of described hydrophilic nano silica dioxide granule is 60nm-150nm.

7. the fire-resistant fluid of composite fireproof glass, is characterized in that, the fire-resistant fluid of described composite fireproof glass is prepared from by the preparation method described in any one of claim 1-6.

8. composite fireproof glass, described composite fireproof glass comprises the first glass and the second glass, the Waterproof gum that described first glass and described second glass are solidified by fire-resistant fluid is combined layer by layer, it is characterized in that, described fire-resistant fluid is the fire-resistant fluid of composite fireproof glass according to claim 7, and the outside surface of described first glass has antireflection coatings.

9. composite fireproof glass according to claim 8, it is characterized in that, described second glass is combined by described fire prevention glue-line and the 3rd glass coating; The thickness of described first glass, described second glass and described 3rd glass is 4mm, and the thickness of described fire prevention glue-line is 1mm-2mm.

10. composite fireproof glass according to claim 8 or claim 9, it is characterized in that, described antireflection coatings is silicon dioxide layer film coating, titanium dioxide unitary film coating, earth silicon/titanic oxide duplicature coating, titania/silica duplicature coating or earth silicon/titanic oxide/silicon-dioxide MULTILAYER COMPOSITE film coating; The thickness of described silicon dioxide layer film coating or titanium dioxide unitary film coating is 0.0001mm-0.1mm.