CN106380122B - A kind of photochromic bionical quartz and preparation method thereof - Google Patents

Abstract

The invention discloses photochromic bionical quartz of one kind and preparation method thereof, the preparation method comprises the following steps：Step A, prepares modified resin；Step B, by weight percentage, 80 ~ 90% quartz, 8 ~ 12% modified resins, 0.01 ~ 1% curing agent, 0.01 ~ 1% coupling agent, 1 ~ 5% photochromic compound, 1 ~ 3% aluminium hydrate powder and 0.1 ~ 2% colorant is stirred, compound is obtained；Step C, carries out first time cloth in template by compound, shakes molded, be stripped, and cutting arranges to obtain semi-finished product by predetermined pattern；Second of cloth is carried out again, is shaken molded, and then drying forming carries out post-processing to obtain finished product.Compare, bionical quartz dispensing science produced by the present invention, it is reasonable to prepare, performance is stable, high mechanical strength, be unlikely to deform and non-aging with existing bionical quartz；And by reasonably arrange in pairs or groups photochromic compound and antibacterial powder so that bionical quartz has excellent antibacterial and photochromic properties, has further widened the application of bionical quartz.

Description

A kind of photochromic bionical quartz and preparation method thereof

Technical field

The present invention relates to quartz technical field, more particularly to a kind of photochromic bionical quartz and its preparation Method.

Background technology

Bacterium, mould has very big harm to the mankind and animals and plants as pathogen, and the health of influence people even jeopardizes life Life, brings great economic loss.Therefore the research of anti-biotic material and its product increasingly causes the concern of people, antibacterial product Demand will constitute huge market.

Bionical quartz, which has, shrinks low, and manufacturing cost is low, it is easy to process and color and luster is abundant, product properties is protruded, hardness High the advantages of, it has been made various industrial and civilian floor and ornament materials, and has been widely used in industrial production and people In daily life, the decorative material material of floor tile, metope etc. is used as.

But, the bionical quartz on uniformity preferably stable antibacterial functions is also rarely reported at present.And it is existing There is the product that bionical quartz is usually simple function, function such as antibacterial, antistatic etc., i.e., a kind of product do not possess multinomial work( Can, this strongly limits its application, it need further raising.

The content of the invention

In order to solve above-mentioned the deficiencies in the prior art, the invention provides the photochromic bionical quartz of one kind and its preparation Method.

The technical problems to be solved by the invention are achieved by the following technical programs：

A kind of photochromic bionical quartz and preparation method thereof, the preparation method comprises the following steps：

Step A, prepares modified resin：By weight percentage, it is 85 ~ 90% resins, 5 ~ 10% antibacterial powders and 1 ~ 5% is scattered Agent is heated after being well mixed with homogenizer and melted, and is 1 using draw ratio：40 double screw extruder extruding pelletizations, it melts Melting the scattered extrusion temperature of mixing is：100 DEG C~280 DEG C；The resin is epoxy resin, phenolic resin, acrylic resin, poly- One or more in urethane resin；

Step B, by weight percentage, by 80 ~ 90% quartz, 8 ~ 12% modified resins, 0.01 ~ 1% curing agent, 0.01 ~ 1% Coupling agent, 1 ~ 5% photochromic compound, 1 ~ 3% aluminium hydrate powder and 0.1 ~ 2% colorant stir, and obtain compound；

Step C, carries out first time cloth in template by compound, shakes molded, be stripped, and cutting is arranged by predetermined pattern Arrange to obtain semi-finished product；Second of cloth is carried out again, is shaken molded, and then drying forming carries out post-processing to obtain finished product.

In the present invention, aluminium hydrate powder is used so that quartz has a good fire retardant performance, and can be to prevent Only smoke, generation toxic gas, use safety.

In the present invention, the curing agent is selected from peroxidating（2 ethyl hexanoic acid）The tert-butyl ester, methyl ethyl ketone peroxide, peroxidating One or more in t-butyl perbenzoate and fat polyamine.The silane coupler is gamma-methyl allyl acyloxypropyl three Methoxy silane, γ-(oxygen of 2,3- epoxies third) propyl trimethoxy silicane, N- β (aminoethyl)-γ-aminopropyltriethoxy dimethoxy Base silane, N- (β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, N- β (aminoethyl)-γ-aminopropyltrimethoxysilane, Anilinomethyl triethoxysilane, gamma-aminopropyl-triethoxy-silane, VTES, vinyl trimethoxy One or more in silane and γ-chloropropyl triethoxysilane.The colorant is colored pigment.

In the present invention, the photochromic compound preparation method is as follows：Under nitrogen environment, by concentration be 0.05 ~ 0.5mol/L protonic acid solution and concentration is 0.05 ~ 0.5mol/L DBSA with volume ratio 3:1 ~ 3 mixing, together When add aniline added after photochromic powder, 60 ~ 120min of magnetic agitation, photochromic powder is 1 with aniline mass ratio:5~10； Persistently after 60 ~ 90min of stirring, ammonium persulfate is added dropwise dropwise, aniline is 1 with ammonium persulfate mol ratio:1；It is anti-at 20 DEG C~30 DEG C Answer 12 ~ 36h；Acetone, deionized water washing are dried in vacuo afterwards for several times, nano polyaniline/photochromic flour complexes of milling to obtain；Will 1 ~ 10g nano polyanilines/photochromic flour complexes ultrasonic agitation is scattered in the aqueous solution；Volume ratio 4 is added afterwards:1 water And ammoniacal liquor, it is stirring evenly and then adding into tetraethyl orthosilicate（Mass ratio with nano polyaniline/photochromic flour complexes is 5:1~ 3）, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60 ~ 90min；Progress centrifuges and uses acetone and deionization successively Water cleaning is precipitated；This is deposited at 90 DEG C and dries 3h, to obtain nano polyaniline/photochromic flour complexes/SiO₂； By nano polyaniline/photochromic flour complexes/SiO₂It is placed under argon gas atmosphere and carries out 800 ~ 1000 DEG C of 1 ~ 2h of heat treatment, removes Polyaniline, photochromic powder/porous SiO₂, i.e., photochromic compound.

In the present invention, the antibacterial powder can be made by the following method：

（1）0.3 ~ 1gC60 powder is weighed, the concentrated sulfuric acid that 80 ~ 100ml mass fractions are 98% is measured, by C60 powder and dense Sulfuric acid is mixed in beaker, and beaker is placed in ice-water bath, while being stirred with 500 ~ 600rpm speed, obtains mixed liquor；Weigh 1 ~ 3g potassium permanganate powders, are slowly added in above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, bath temperature 30 ~ 40 is kept DEG C, react 3 ~ 5h；100 ~ 150ml pure water is rapidly joined, is filtered, then with the bag filter dialysis 3 ~ 5 that molecular cut off is 1000 My god, obtain graphene quantum dot（GQDs）Suspension；100 ~ 150rpm speed stirs GQDs suspension, while laser irradiation 30 ~ 60min, laser irradiation power is 0.5 ~ 2W；It is standby；

（2）Ultrasonic agitation 50 ~ 60mlGQDs suspension, dropwise addition concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solutions；By Concentration is added dropwise to for 0.1 ~ 0.5mol/L ammonium dihydrogen phosphates（Ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio be 2 ~ 3:1）, 10 ~ 20min of ultrasonic agitation；Be added dropwise 0.5 ~ 1mol/L sodium hydroxide solutions, regulation pH value to 11, then stand, from The heart, with deionized water and ethanol alternately washing three times, vacuum drying obtains GQDs/Ag₂O；

（3）Take 1 ~ 3gGQDs/Ag₂O ultrasonic agitations are scattered in 80 ~ 120ml aqueous solution；Be added dropwise concentration for 0.005 ~ Concentration is added dropwise after the 0.05mol/L cerous nitrate aqueous solution, 30 ~ 60min for 0.005 ~ 0.05mol/L zinc nitrate aqueous solutions, GQDs/Ag₂The O aqueous solution, the cerous nitrate aqueous solution and zinc nitrate aqueous solution volume ratio are 1:0.1~0.2:0.2~0.4；Continue ultrasound Stirring, regulation mixed solution pH value to 7.0；Side ultrasonic agitation, side adds the hydrazine hydrate that 4 ~ 8mL mass fractions are 50%, 30 ~ 0.5 ~ 1h of reduction reaction at 40 DEG C；Afterwards, the hydrazine hydrate that 40 ~ 50mL mass fractions are 50%, the reduction reaction at 85 DEG C are added After 30 ~ 48h；Filtering, is washed with deionized for several times, and vacuum drying obtains GQDs/Ag₂O/Ag-Zn-Ce；

（4）By 0.1 ~ 0.5gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitations are scattered in the aqueous solution；Volume ratio 3 is added afterwards ~5:1 water and ammoniacal liquor, is stirring evenly and then adding into tetraethyl orthosilicate（With GQDs/Ag₂O/Ag-Zn-Ce mass ratio is 3:1~3）, It is 9 ~ 10 to adjust pH value, and reaction temperature is 20 ~ 25 DEG C, reacts 30 ~ 60min；Progress centrifuges and uses acetone and deionized water successively Cleaning is precipitated；This is deposited at 80 ~ 90 DEG C and dries 2 ~ 4h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/ Ag₂O/Ag-Zn-Ce/SiO₂It is placed under argon gas atmosphere and carries out 500 ~ 800 DEG C of 1 ~ 2h of heat treatment, is cooled to after room temperature, is immersed in hydrogen 10 ~ 15min of ultrasound is carried out with 100 ~ 150W of ultrasonic power in fluoric acid, the local silica in surface is removed, centrifuges and dry, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；

（5）Take three-dimensional sponge shape graphene ultrasonic agitation to be scattered in the aqueous solution, GQDs/Ag is added dropwise₂O/Ag-Zn- Ce/SiO₂In the aqueous solution, three-dimensional sponge shape graphene and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Weight ratio be 1:1~5；10~ 100W 60 ~ 120min of ultrasound, are stood, and deionized water is washed for several times, and centrifugation is placed in confined space, and progress is vacuumized → heated Pressurized circulation 3 ~ 8 times（Pumpdown time is 20 ~ 30min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, it is forced into 0.3 ~ 0.6Mpa, 20 ~ 30min of pressurize）, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, That is antibacterial powder.

In the present invention, the antibacterial powder can also be made by the following method：

（1）0.3 ~ 1gC60 powder is weighed, the concentrated sulfuric acid that 80 ~ 100ml mass fractions are 98% is measured, by C60 powder and dense Sulfuric acid is mixed in beaker, and beaker is placed in ice-water bath, while being stirred with 500 ~ 600rpm speed, obtains mixed liquor；Weigh 1 ~ 3g potassium permanganate powders, are slowly added in above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, bath temperature 30 ~ 40 is kept DEG C, react 3 ~ 5h；100 ~ 150ml pure water is rapidly joined, is filtered, then with the bag filter dialysis 3 ~ 5 that molecular cut off is 1000 My god, obtain graphene quantum dot（GQDs）Suspension；100 ~ 150rpm speed stirs GQDs suspension, while laser irradiation 30 ~ 60min, laser irradiation power is 0.5 ~ 2W；It is standby；

（2）Ultrasonic agitation 50 ~ 60mlGQDs suspension, dropwise addition concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solutions；By Concentration is added dropwise to for 0.1 ~ 0.5mol/L ammonium dihydrogen phosphates（Ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio be 2 ~ 3:1）, 10 ~ 20min of ultrasonic agitation；Be added dropwise 0.5 ~ 1mol/L sodium hydroxide solutions, regulation pH value to 11, then stand, from The heart, with deionized water and ethanol alternately washing three times, vacuum drying obtains GQDs/Ag₂O；

（3）Take 1 ~ 3gGQDs/Ag₂O ultrasonic agitations are scattered in the aqueous solution；Concentration is added dropwise for 0.05 ~ 0.5g/ The 100mlZnO quantum dot aqueous solution, ultrasonic power mixing speed respectively halves；After 60 ~ 90min, stand, filtering is washed with deionized water Wash for several times, vacuum drying obtains GQDs/Ag₂O/ZnO；

（4）Take three-dimensional sponge shape graphene ultrasonic agitation to be scattered in the aqueous solution, GQDs/Ag is added dropwise₂O/ZnO is water-soluble In liquid, three-dimensional sponge shape graphene and GQDs/Ag₂O/ZnO weight ratio is 1:1~5；10 ~ 100W ultrasounds 60 ~ 120min, it is quiet Put, deionized water is washed for several times, centrifugation is placed in confined space, and progress vacuumizes → heated pressurized circulation 3 ~ 8 times（Vacuumize Time is 20 ~ 30min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, it is forced into 0.3 ~ 0.6Mpa, 20 ~ 30min of pressurize）, obtain GQDs/Ag₂O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder.

Wherein, the three-dimensional sponge shape graphene preparation method is as follows：By 3g graphite powders, 1g NaNO3 are in ice-water bath It is well mixed with the concentrated sulfuric acids of 250ml 98%, is slowly added to 6g KMnO4.Then heat at 35 DEG C, after stirring 40min, add 95ml deionized waters, are warming up to 98 DEG C of reaction 20min；The dilution of 270ml water is added, and it is many with the H2O2 of 5ml 30% neutralizations Remaining KMnO4, the color of mixed solution is brown color, is filtered while hot, with deionized water cyclic washing to neutrality, ultrasonic disperse is obtained GO；The graphene oxide solution for taking 200ml mass fractions to be 5mg/ml pours into diameter 25cm, high 2cm discoid reaction utensil In, adding ascorbic acid (VC) 0.5g stirrings is sufficiently mixed it；Then confined reaction ware is placed in 80 DEG C of hydro-thermal reaction 15h, Graphene oxide Spontaneous Contraction in reaction utensil is cross-linked into three-dimensional sponge structure, freeze-drying, obtains the three-dimensional sponge shape of flexibility Graphene.

The present invention has the advantages that：

Compared with existing bionical quartz, bionical quartz dispensing science produced by the present invention, it is reasonable to prepare, and performance is steady It is fixed, high mechanical strength, it is unlikely to deform and non-aging；And by reasonably arrange in pairs or groups photochromic compound and antibacterial powder, make Obtaining bionical quartz has excellent antibacterial and photochromic properties, has further widened the application of bionical quartz；

This method is loaded and fixed antiseptic on three-dimensional grapheme, is not only prevented it from reuniting, is significantly improved metal nano The stability of the antiseptics such as particle, can more preferably be dispersed in bionical quartz, and with more efficient antibacterial activity and Silver ion will not overflow oxidation stain；The anti-microbial property of a variety of antiseptics is compounded with simultaneously, compared to single silver nano antibacterial Agent has more preferable antibacterial effect, and antibacterial is lasting；Photochromic compound has photochromic effect, product is more enriched It is colorful, it is to use the Ceramic Tiles of conventional colorants production incomparable using the Ceramic Tiles of its production, can be with irradiation light Strong and weak difference and a variety of colors changed, are a splendid legacy, full of magnificent carriage, so that ceramic product seems beautiful magical, pure and fresh Elegance, intersperses city night life, and sentiment and artistic effect are increased to building and interior decoration.

Embodiment

Technical scheme is further illustrated below by specific preferred embodiment.

Embodiment 1

A kind of photochromic bionical quartz and preparation method thereof, the preparation method comprises the following steps：

Step A, prepares modified resin：By weight percentage, by 85% resin, 10% antibacterial powder and 5% dispersant at a high speed Melting is heated after mixer is well mixed, is 1 using draw ratio：40 double screw extruder extruding pelletizations, its melting mixing point Scattered extrusion temperature is：100 DEG C~280 DEG C；The resin is epoxy resin, phenolic resin, acrylic resin, polyurethane resin are pressed Weight compares 3:2:2:1 mixing；

Step B, by weight percentage, weighs 80% quartz（Quartz sand presses 3 with silica flour：1 mixing）, 11% be modified tree Fat, 0.5% methyl ethyl ketone peroxide, 0.5% VTES, 5% photochromic compound, 2% aluminium hydrate powder and 1% Colorant；Quartz sand, aluminium hydrate powder, photochromic compound are placed in the first mixer the premix that stirs to obtain, stirred Mix speed 1000r/min, mixing time 20min；Silica flour, modified resin, curing agent, coupling agent and colorant are placed in into second to stir Mix in machine and stir, mixing speed 1000r/min, mixing time 20min；Premix is added in the second mixer and stirred Uniformly, mixing speed 250r/min, mixing time 30min, obtains compound；

Step C, C01, by compound carry out first time cloth in template, i.e., compound is paved in mould by material distributing machine On plate；

C02, carry out by press shaking molded for the first time, obtain idiosome；Wherein, vibration frequency is 45Hz, time of vibration 200s；

C03, gained idiosome is stripped and cut by cutter device, semi-finished product are obtained by predetermined pattern arrangement；

C04, by gained semi-finished product carry out second of cloth；

C07, shaken for the second time by press molded, vibration frequency is 50Hz, time of vibration 240s；

C08, shake for the second time it is molded after, carry out drying forming, drying temperature be 92 DEG C, drying time 1.5h；

C09, the semi-finished product to drying forming are post-processed, such as fixed thick processing, polishing, obtain finished product.

Wherein, the preparation method of the photochromic compound is as follows：Under nitrogen environment, by the matter that concentration is 0.4mol/L Sub- acid solution and concentration for 0.3mol/L DBSA with volume ratio 3:2 mixing, while adding photochromic powder （Nd₂O₃、Pr₂O₃、La₂O₃And Yb₂O₃By weight 1:2:2:1 is obtained by mixing）, aniline, light-induced variable are added after magnetic agitation 90min Toner is 1 with aniline mass ratio:8；Persistently after stirring 90min, ammonium persulfate is added dropwise dropwise, aniline is with ammonium persulfate mol ratio 1:1；20h is reacted at 20 DEG C~30 DEG C；Acetone, deionized water washing are dried in vacuo afterwards for several times, the nano polyaniline/photic of milling to obtain Change colour flour complexes；6g nano polyanilines/photochromic flour complexes ultrasonic agitation is scattered in the aqueous solution；Body is added afterwards Product compares 4:1 water and ammoniacal liquor, is stirring evenly and then adding into tetraethyl orthosilicate（With the matter of nano polyaniline/photochromic flour complexes Amount is than being 5:2）, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Progress centrifuge and successively with acetone and Deionized water cleaning is precipitated；This is deposited at 90 DEG C and dries 3h, is combined with obtaining nano polyaniline/photochromic powder Thing/SiO₂；By nano polyaniline/photochromic flour complexes/SiO₂It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, removes Polyaniline, obtains photochromic powder/porous SiO₂, i.e., photochromic compound.

Wherein, the preparation method of the antibacterial powder is as follows：

（1）0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fractions are 98% is measured, by C60 powder and the concentrated sulfuric acid Mixed in beaker, beaker is placed in ice-water bath, while being stirred with 600rpm speed, obtain mixed liquor；Weigh 1g potassium permanganate Powder, is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, 4h is reacted；It hurry up Speed adds 120ml pure water, and then filtering is dialysed 4 days for 1000 bag filter with molecular cut off, obtain graphene quantum dot （GQDs）Suspension；100rpm speed stirs GQDs suspension, while laser irradiates 40min, laser irradiation power is 1W；It is standby With；

（2）Ultrasonic agitation 60mlGQDs suspension, dropwise addition concentration is 0.001mol/L silver nitrate aqueous solutions；It is added dropwise dense Spend for 0.1mol/L ammonium dihydrogen phosphates（Ammonium dihydrogen phosphate is 2 with silver nitrate aqueous solution volume ratio:1）, ultrasonic agitation 20min；1mol/L sodium hydroxide solutions are added dropwise, regulation pH value to 11 then stands, centrifuged, with deionized water and ethanol Alternately washing three times, vacuum drying obtains GQDs/Ag₂O；

（3）Take 1gGQDs/Ag₂O ultrasonic agitations are scattered in the 100ml aqueous solution；Concentration is added dropwise for 0.05mol/L nitre Concentration is added dropwise after the sour cerium aqueous solution, 30min for 0.005mol/L zinc nitrate aqueous solutions, GQDs/Ag₂The O aqueous solution, cerous nitrate The aqueous solution is 1 with zinc nitrate aqueous solution volume ratio:0.1:0.4；Continue ultrasonic agitation, regulation mixed solution pH value to 7.0；Bian Chao Sound is stirred, and side adds the hydrazine hydrate that 6mL mass fractions are 50%, the reduction reaction 0.5h at 30 DEG C；Afterwards, 45mL matter is added The hydrazine hydrate that fraction is 50% is measured, at 85 DEG C after reduction reaction 36h；Filtering, is washed with deionized for several times, and vacuum drying is obtained GQDs/Ag₂O/Ag-Zn-Ce；

（4）By 0.5gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitations are scattered in the aqueous solution；Volume ratio 4 is added afterwards:1 Water and ammoniacal liquor, are stirring evenly and then adding into tetraethyl orthosilicate（With GQDs/Ag₂O/Ag-Zn-Ce mass ratio is 3:2）, adjust pH value For 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 30min；Progress, which is centrifuged and cleaned successively with acetone and deionized water, is sunk Form sediment；This is deposited at 90 DEG C and dries 3h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/ SiO₂It is placed under argon gas atmosphere and carries out 600 DEG C of heat treatment 1h, is cooled to after room temperature, is immersed in hydrofluoric acid with ultrasonic power 100W Ultrasound 10min is carried out, the local silica in surface is removed, centrifuges and dry, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；

（5）Take three-dimensional sponge shape graphene ultrasonic agitation to be scattered in the aqueous solution, GQDs/Ag is added dropwise₂O/Ag-Zn- Ce/SiO₂In the aqueous solution, three-dimensional sponge shape graphene and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Weight ratio be 1:5；50W ultrasounds 100min, is stood, and deionized water is washed for several times, and centrifugation is placed in confined space, and progress vacuumizes → heated pressurized circulation 3 times （Pumpdown time is 25min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, i.e. antibacterial powder.

Embodiment 2

A kind of photochromic bionical quartz and preparation method thereof, the preparation method comprises the following steps：

Step A, prepares modified resin：By weight percentage, by 88% resin, 8% antibacterial powder and 4% dispersant at a high speed Melting is heated after mixer is well mixed, is 1 using draw ratio：40 double screw extruder extruding pelletizations, its melting mixing point Scattered extrusion temperature is：100 DEG C~280 DEG C；The resin is epoxy resin, phenolic resin, acrylic resin, polyurethane resin are pressed Weight compares 3:2:2:1 mixing；

Step B, by weight percentage, weighs 80% quartz（Quartz sand presses 3 with silica flour：1 mixing）, 12% be modified tree Fat, 0.5% methyl ethyl ketone peroxide, 0.5% VTES, 3% photochromic compound, 3% aluminium hydrate powder and 1% Colorant；Quartz sand, aluminium hydrate powder, photochromic compound are placed in the first mixer the premix that stirs to obtain, stirred Mix speed 1000r/min, mixing time 20min；Silica flour, modified resin, curing agent, coupling agent and colorant are placed in into second to stir Mix in machine and stir, mixing speed 1000r/min, mixing time 20min；Premix is added in the second mixer and stirred Uniformly, mixing speed 250r/min, mixing time 30min, obtains compound；

Step C, C01, by compound carry out first time cloth in template, i.e., compound is paved in mould by material distributing machine On plate；

C02, carry out by press shaking molded for the first time, obtain idiosome；Wherein, vibration frequency is 45Hz, time of vibration 200s；

C03, gained idiosome is stripped and cut by cutter device, semi-finished product are obtained by predetermined pattern arrangement；

C04, by gained semi-finished product carry out second of cloth；

C07, shaken for the second time by press molded, vibration frequency is 50Hz, time of vibration 240s；

C08, shake for the second time it is molded after, carry out drying forming, drying temperature be 92 DEG C, drying time 1.5h；

C09, the semi-finished product to drying forming are post-processed, such as fixed thick processing, polishing, obtain finished product.

Wherein, the preparation method of the photochromic compound is as follows：Under nitrogen environment, by the matter that concentration is 0.4mol/L Sub- acid solution and concentration for 0.3mol/L DBSA with volume ratio 3:2 mixing, while adding photochromic powder （Nd₂O₃、Pr₂O₃、La₂O₃And Yb₂O₃By weight 1:2:2:1 is obtained by mixing）, aniline, light-induced variable are added after magnetic agitation 90min Toner is 1 with aniline mass ratio:8；Persistently after stirring 90min, ammonium persulfate is added dropwise dropwise, aniline is with ammonium persulfate mol ratio 1:1；20h is reacted at 20 DEG C~30 DEG C；Acetone, deionized water washing are dried in vacuo afterwards for several times, the nano polyaniline/photic of milling to obtain Change colour flour complexes；6g nano polyanilines/photochromic flour complexes ultrasonic agitation is scattered in the aqueous solution；Body is added afterwards Product compares 4:1 water and ammoniacal liquor, is stirring evenly and then adding into tetraethyl orthosilicate（With the matter of nano polyaniline/photochromic flour complexes Amount is than being 5:2）, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Progress centrifuge and successively with acetone and Deionized water cleaning is precipitated；This is deposited at 90 DEG C and dries 3h, is combined with obtaining nano polyaniline/photochromic powder Thing/SiO₂；By nano polyaniline/photochromic flour complexes/SiO₂It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, removes Polyaniline, obtains photochromic powder/porous SiO₂, i.e., photochromic compound.

Wherein, the preparation method of the antibacterial powder is as follows：

（1）0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fractions are 98% is measured, by C60 powder and the concentrated sulfuric acid Mixed in beaker, beaker is placed in ice-water bath, while being stirred with 600rpm speed, obtain mixed liquor；Weigh 1g potassium permanganate Powder, is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, 4h is reacted；It hurry up Speed adds 120ml pure water, and then filtering is dialysed 4 days for 1000 bag filter with molecular cut off, obtain graphene quantum dot （GQDs）Suspension；100rpm speed stirs GQDs suspension, while laser irradiates 40min, laser irradiation power is 1W；It is standby With；

（2）Ultrasonic agitation 60mlGQDs suspension, dropwise addition concentration is 0.005mol/L silver nitrate aqueous solutions；It is added dropwise dense Spend for 0.2mol/L ammonium dihydrogen phosphates（Ammonium dihydrogen phosphate is 2 with silver nitrate aqueous solution volume ratio:1）, ultrasonic agitation 20min；1mol/L sodium hydroxide solutions are added dropwise, regulation pH value to 11 then stands, centrifuged, with deionized water and ethanol Alternately washing three times, vacuum drying obtains GQDs/Ag₂O；

（3）Take 2gGQDs/Ag₂O ultrasonic agitations are scattered in the 100ml aqueous solution；Concentration is added dropwise for 0.03mol/L nitre Concentration is added dropwise after the sour cerium aqueous solution, 30min for 0.03mol/L zinc nitrate aqueous solutions, GQDs/Ag₂The O aqueous solution, cerous nitrate The aqueous solution is 1 with zinc nitrate aqueous solution volume ratio:0.2:0.3；Continue ultrasonic agitation, regulation mixed solution pH value to 7.0；Bian Chao Sound is stirred, and side adds the hydrazine hydrate that 6mL mass fractions are 50%, the reduction reaction 0.5h at 30 DEG C；Afterwards, 45mL matter is added The hydrazine hydrate that fraction is 50% is measured, at 85 DEG C after reduction reaction 36h；Filtering, is washed with deionized for several times, and vacuum drying is obtained GQDs/Ag₂O/Ag-Zn-Ce；

（4）By 0.3gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitations are scattered in the aqueous solution；Volume ratio 4 is added afterwards:1 Water and ammoniacal liquor, are stirring evenly and then adding into tetraethyl orthosilicate（With GQDs/Ag₂O/Ag-Zn-Ce mass ratio is 3:2）, adjust pH value For 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 45min；Progress, which is centrifuged and cleaned successively with acetone and deionized water, is sunk Form sediment；This is deposited at 90 DEG C and dries 3h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/ SiO₂It is placed under argon gas atmosphere and carries out 600 DEG C of heat treatment 1h, is cooled to after room temperature, is immersed in hydrofluoric acid with ultrasonic power 100W Ultrasound 12min is carried out, the local silica in surface is removed, centrifuges and dry, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；

（5）Take three-dimensional sponge shape graphene ultrasonic agitation to be scattered in the aqueous solution, GQDs/Ag is added dropwise₂O/Ag-Zn- Ce/SiO₂In the aqueous solution, three-dimensional sponge shape graphene and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Weight ratio be 1:3；50W ultrasounds 100min, is stood, and deionized water is washed for several times, and centrifugation is placed in confined space, and progress vacuumizes → heated pressurized circulation 5 times （Pumpdown time is 25min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, i.e. antibacterial powder.

Embodiment 3

A kind of photochromic bionical quartz and preparation method thereof, the preparation method comprises the following steps：

Step A, prepares modified resin：By weight percentage, by 90% resin, 5% antibacterial powder and 5% dispersant at a high speed Melting is heated after mixer is well mixed, is 1 using draw ratio：40 double screw extruder extruding pelletizations, its melting mixing point Scattered extrusion temperature is：100 DEG C~280 DEG C；The resin is epoxy resin, phenolic resin, acrylic resin, polyurethane resin are pressed Weight compares 3:2:2:1 mixing；

Step B, by weight percentage, weighs 84% quartz（Quartz sand presses 3 with silica flour：1 mixing）, 12% be modified tree Fat, 0.5% methyl ethyl ketone peroxide, 0.5% VTES, 1% photochromic compound, 1% aluminium hydrate powder and 1% Colorant；Quartz sand, aluminium hydrate powder, photochromic compound are placed in the first mixer the premix that stirs to obtain, stirred Mix speed 1000r/min, mixing time 20min；Silica flour, modified resin, curing agent, coupling agent and colorant are placed in into second to stir Mix in machine and stir, mixing speed 1000r/min, mixing time 20min；Premix is added in the second mixer and stirred Uniformly, mixing speed 250r/min, mixing time 30min, obtains compound；

Step C, C01, by compound carry out first time cloth in template, i.e., compound is paved in mould by material distributing machine On plate；

C02, carry out by press shaking molded for the first time, obtain idiosome；Wherein, vibration frequency is 45Hz, time of vibration 200s；

C03, gained idiosome is stripped and cut by cutter device, semi-finished product are obtained by predetermined pattern arrangement；

C04, by gained semi-finished product carry out second of cloth；

C07, shaken for the second time by press molded, vibration frequency is 50Hz, time of vibration 240s；

C08, shake for the second time it is molded after, carry out drying forming, drying temperature be 92 DEG C, drying time 1.5h；

C09, the semi-finished product to drying forming are post-processed, such as fixed thick processing, polishing, obtain finished product.

Wherein, the preparation method of the photochromic compound is as follows：Under nitrogen environment, by the matter that concentration is 0.4mol/L Sub- acid solution and concentration for 0.3mol/L DBSA with volume ratio 3:2 mixing, while adding photochromic powder （Nd₂O₃、Pr₂O₃、La₂O₃And Yb₂O₃By weight 1:2:2:1 is obtained by mixing）, aniline, light-induced variable are added after magnetic agitation 90min Toner is 1 with aniline mass ratio:8；Persistently after stirring 90min, ammonium persulfate is added dropwise dropwise, aniline is with ammonium persulfate mol ratio 1:1；20h is reacted at 20 DEG C~30 DEG C；Acetone, deionized water washing are dried in vacuo afterwards for several times, the nano polyaniline/photic of milling to obtain Change colour flour complexes；6g nano polyanilines/photochromic flour complexes ultrasonic agitation is scattered in the aqueous solution；Body is added afterwards Product compares 4:1 water and ammoniacal liquor, is stirring evenly and then adding into tetraethyl orthosilicate（With the matter of nano polyaniline/photochromic flour complexes Amount is than being 5:2）, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Progress centrifuge and successively with acetone and Deionized water cleaning is precipitated；This is deposited at 90 DEG C and dries 3h, is combined with obtaining nano polyaniline/photochromic powder Thing/SiO₂；By nano polyaniline/photochromic flour complexes/SiO₂It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, removes Polyaniline, obtains photochromic powder/porous SiO₂, i.e., photochromic compound.

Wherein, the preparation method of the antibacterial powder is as follows：

（1）0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fractions are 98% is measured, by C60 powder and the concentrated sulfuric acid Mixed in beaker, beaker is placed in ice-water bath, while being stirred with 600rpm speed, obtain mixed liquor；Weigh 1g potassium permanganate Powder, is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, 4h is reacted；It hurry up Speed adds 120ml pure water, and then filtering is dialysed 4 days for 1000 bag filter with molecular cut off, obtain graphene quantum dot （GQDs）Suspension；100rpm speed stirs GQDs suspension, while laser irradiates 40min, laser irradiation power is 1W；It is standby With；

（2）Ultrasonic agitation 60mlGQDs suspension, dropwise addition concentration is 0.01mol/L silver nitrate aqueous solutions；It is added dropwise dense Spend for 0.5mol/L ammonium dihydrogen phosphates（Ammonium dihydrogen phosphate is 2 with silver nitrate aqueous solution volume ratio:1）, ultrasonic agitation 20min；1mol/L sodium hydroxide solutions are added dropwise, regulation pH value to 11 then stands, centrifuged, with deionized water and ethanol Alternately washing three times, vacuum drying obtains GQDs/Ag₂O；

（3）Take 3gGQDs/Ag₂O ultrasonic agitations are scattered in the 100ml aqueous solution；Concentration is added dropwise for 0.005mol/L Concentration is added dropwise after the cerous nitrate aqueous solution, 30min for 0.05mol/L zinc nitrate aqueous solutions, GQDs/Ag₂The O aqueous solution, nitric acid The cerium aqueous solution is 1 with zinc nitrate aqueous solution volume ratio:0.2:0.4；Continue ultrasonic agitation, regulation mixed solution pH value to 7.0；Side Ultrasonic agitation, side adds the hydrazine hydrate that 6mL mass fractions are 50%, the reduction reaction 0.5h at 30 DEG C；Afterwards, 45mL is added Mass fraction is 50% hydrazine hydrate, at 85 DEG C after reduction reaction 36h；Filtering, is washed with deionized for several times, vacuum drying, Obtain GQDs/Ag₂O/Ag-Zn-Ce；

（4）By 0.1gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitations are scattered in the aqueous solution；Volume ratio 4 is added afterwards:1 Water and ammoniacal liquor, are stirring evenly and then adding into tetraethyl orthosilicate（With GQDs/Ag₂O/Ag-Zn-Ce mass ratio is 3:2）, adjust pH value For 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 60min；Progress, which is centrifuged and cleaned successively with acetone and deionized water, is sunk Form sediment；This is deposited at 90 DEG C and dries 3h, to obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/ SiO₂It is placed under argon gas atmosphere and carries out 600 DEG C of heat treatment 1h, is cooled to after room temperature, is immersed in hydrofluoric acid with ultrasonic power 100W Ultrasound 15min is carried out, the local silica in surface is removed, centrifuges and dry, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；

（5）Take three-dimensional sponge shape graphene ultrasonic agitation to be scattered in the aqueous solution, GQDs/Ag is added dropwise₂O/Ag-Zn- Ce/SiO₂In the aqueous solution, three-dimensional sponge shape graphene and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Weight ratio be 1:1；50W ultrasounds 100min, is stood, and deionized water is washed for several times, and centrifugation is placed in confined space, and progress vacuumizes → heated pressurized circulation 8 times （Pumpdown time is 25min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, i.e. antibacterial powder.

Embodiment 4

Based on the preparation method of embodiment 1, it the difference is that only：The antibacterial powder is made by the following method：

（1）0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fractions are 98% is measured, by C60 powder and the concentrated sulfuric acid Mixed in beaker, beaker is placed in ice-water bath, while being stirred with 600rpm speed, obtain mixed liquor；Weigh 1g potassium permanganate Powder, is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, 4h is reacted；It hurry up Speed adds 120ml pure water, and then filtering is dialysed 4 days for 1000 bag filter with molecular cut off, obtain graphene quantum dot （GQDs）Suspension；100rpm speed stirs GQDs suspension, while laser irradiates 40min, laser irradiation power is 1W；It is standby With；

（2）Ultrasonic agitation 60mlGQDs suspension, dropwise addition concentration is 0.001mol/L silver nitrate aqueous solutions；It is added dropwise dense Spend for 0.1mol/L ammonium dihydrogen phosphates（Ammonium dihydrogen phosphate is 2 with silver nitrate aqueous solution volume ratio:1）, ultrasonic agitation 20min；1mol/L sodium hydroxide solutions are added dropwise, regulation pH value to 11 then stands, centrifuged, with deionized water and ethanol Alternately washing three times, vacuum drying obtains GQDs/Ag₂O；

（3）Take 1gGQDs/Ag₂O ultrasonic agitations are scattered in the aqueous solution；Concentration is added dropwise for 0.5g/100mlZnO amounts The son point aqueous solution, ultrasonic power mixing speed respectively halves；After 60min, stand, filtering is washed with deionized for several times, and vacuum is done It is dry, obtain GQDs/Ag₂O/ZnO；

（4）Take three-dimensional sponge shape graphene ultrasonic agitation to be scattered in the aqueous solution, GQDs/Ag is added dropwise₂O/ZnO is water-soluble In liquid, three-dimensional sponge shape graphene and GQDs/Ag₂O/ZnO weight ratio is 1:5；50W ultrasound 100min, stand, deionized water For several times, centrifugation is placed in confined space, and progress vacuumizes → heated pressurized circulation 3 times for washing（Pumpdown time is 25min；Plus Heat, which is pressurised into, is passed through high temperature and high pressure gas, and gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, obtain GQDs/Ag₂O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder.

Embodiment 5

Based on the preparation method of embodiment 2, it the difference is that only：The antibacterial powder is made by the following method：

（1）0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fractions are 98% is measured, by C60 powder and the concentrated sulfuric acid Mixed in beaker, beaker is placed in ice-water bath, while being stirred with 600rpm speed, obtain mixed liquor；Weigh 1g potassium permanganate Powder, is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, 4h is reacted；It hurry up Speed adds 120ml pure water, and then filtering is dialysed 4 days for 1000 bag filter with molecular cut off, obtain graphene quantum dot （GQDs）Suspension；100rpm speed stirs GQDs suspension, while laser irradiates 40min, laser irradiation power is 1W；It is standby With；

（2）Ultrasonic agitation 60mlGQDs suspension, dropwise addition concentration is 0.005mol/L silver nitrate aqueous solutions；It is added dropwise dense Spend for 0.2mol/L ammonium dihydrogen phosphates（Ammonium dihydrogen phosphate is 2 with silver nitrate aqueous solution volume ratio:1）, ultrasonic agitation 20min；1mol/L sodium hydroxide solutions are added dropwise, regulation pH value to 11 then stands, centrifuged, with deionized water and ethanol Alternately washing three times, vacuum drying obtains GQDs/Ag₂O；

（3）Take 2gGQDs/Ag₂O ultrasonic agitations are scattered in the aqueous solution；Concentration is added dropwise for 0.2g/100mlZnO amounts The son point aqueous solution, ultrasonic power mixing speed respectively halves；After 80min, stand, filtering is washed with deionized for several times, and vacuum is done It is dry, obtain GQDs/Ag₂O/ZnO；

（4）Take three-dimensional sponge shape graphene ultrasonic agitation to be scattered in the aqueous solution, GQDs/Ag is added dropwise₂O/ZnO is water-soluble In liquid, three-dimensional sponge shape graphene and GQDs/Ag₂O/ZnO weight ratio is 1:3；50W ultrasound 100min, stand, deionized water For several times, centrifugation is placed in confined space, and progress vacuumizes → heated pressurized circulation 5 times for washing（Pumpdown time is 25min；Plus Heat, which is pressurised into, is passed through high temperature and high pressure gas, and gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, obtain GQDs/Ag₂O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder.

Embodiment 6

Based on the preparation method of embodiment 3, it the difference is that only：The antibacterial powder is made by the following method：

（1）0.6gC60 powder is weighed, the concentrated sulfuric acid that 100ml mass fractions are 98% is measured, by C60 powder and the concentrated sulfuric acid Mixed in beaker, beaker is placed in ice-water bath, while being stirred with 600rpm speed, obtain mixed liquor；Weigh 1g potassium permanganate Powder, is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, 4h is reacted；It hurry up Speed adds 120ml pure water, and then filtering is dialysed 4 days for 1000 bag filter with molecular cut off, obtain graphene quantum dot （GQDs）Suspension；100rpm speed stirs GQDs suspension, while laser irradiates 40min, laser irradiation power is 1W；It is standby With；

（2）Ultrasonic agitation 60mlGQDs suspension, dropwise addition concentration is 0.01mol/L silver nitrate aqueous solutions；It is added dropwise dense Spend for 0.5mol/L ammonium dihydrogen phosphates（Ammonium dihydrogen phosphate is 2 with silver nitrate aqueous solution volume ratio:1）, ultrasonic agitation 20min；1mol/L sodium hydroxide solutions are added dropwise, regulation pH value to 11 then stands, centrifuged, with deionized water and ethanol Alternately washing three times, vacuum drying obtains GQDs/Ag₂O；

（3）Take 3gGQDs/Ag₂O ultrasonic agitations are scattered in the aqueous solution；Concentration is added dropwise for 0.05g/100mlZnO amounts The son point aqueous solution, ultrasonic power mixing speed respectively halves；After 90min, stand, filtering is washed with deionized for several times, and vacuum is done It is dry, obtain GQDs/Ag₂O/ZnO；

（4）Take three-dimensional sponge shape graphene ultrasonic agitation to be scattered in the aqueous solution, GQDs/Ag is added dropwise₂O/ZnO is water-soluble In liquid, three-dimensional sponge shape graphene and GQDs/Ag₂O/ZnO weight ratio is 1:1；50W ultrasound 100min, stand, deionized water For several times, centrifugation is placed in confined space, and progress vacuumizes → heated pressurized circulation 8 times for washing（Pumpdown time is 25min；Plus Heat, which is pressurised into, is passed through high temperature and high pressure gas, and gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, obtain GQDs/Ag₂O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder.

Comparative example 1

Based on the preparation method of embodiment 1, difference is：The antibacterial powder is metal antibacterial agent；The light-induced variable Color compound is by Nd₂O₃、Pr₂O₃、La₂O₃And Yb₂O₃By weight 1:2:2:1 is obtained by mixing.

Comparative example 2

Based on the preparation method of embodiment 4, difference is：The antibacterial powder is zinc oxide antiseptic；Without light Mutagens color compound.

Performance test is carried out to embodiment 1 ~ 6, comparative example 1 ~ 2, test result is as follows：

Wear testing：From the abrasive material that Mohs' hardness is 3~4, rubbed on bionical quartz for 1000 times and imitate paving Using the effect after 2 years, its sterilization rate is tested.

Heat stability testing：Bionical quartz is placed in electric furnace, 200 DEG C are raised to from room temperature, 20min is incubated, it is rapid to throw Enter in 25 DEG C of water, take out and dry after 10min, test its sterilization rate.

Sterilize Evaluation for Uniformity：100 regions are chosen on same bionical quartz and carry out sterilizing test, to the number measured According to Uniformity Analysis is carried out, pass through the uniformity=100* (1- standard deviations/average value).When the uniformity is more than 97%, then it is labeled as ▲；When the uniformity is more than 90% and less than 97%, then labeled as ☆；When the uniformity is less than 90%, then Biao Ji Wei ╳.

Radiate performance：Detection indicate that, quartz prepared by the present invention meets GB6566-2001《Construction material is radiated Property radionuclides limitation》Middle A classes finishing material requirement.

Embodiment described above only expresses embodiments of the present invention, and it describes more specific and detailed, but can not Therefore the limitation to the scope of the claims of the present invention is interpreted as, as long as the skill obtained using the form of equivalent substitution or equivalent transformation Art scheme, all should fall within the scope and spirit of the invention.

Claims (4)

1. a kind of preparation method of photochromic bionical quartz, it comprises the following steps：

Step A, prepares modified resin：By weight percentage, 85 ~ 90% resins, 5 ~ 10% antibacterial powders and 1 ~ 5% dispersant are used Melting is heated after homogenizer is well mixed, using double screw extruder extruding pelletization, its melting mixing disperses extrusion temperature For：100 DEG C~280 DEG C；The antibacterial powder is GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder；

Step B, by weight percentage, by 80 ~ 90% quartz, 8 ~ 12% modified resins, 0.01 ~ 1% curing agent, 0.01 ~ 1% coupling Agent, 1 ~ 5% photochromic compound, 1 ~ 3% aluminium hydrate powder and 0.1 ~ 2% colorant stir, and obtain compound；

Step C, carries out first time cloth in template by compound, shakes molded, be stripped, and cutting is arranged by predetermined pattern Semi-finished product；Second of cloth is carried out again, is shaken molded, and then drying forming carries out post-processing to obtain finished product；Wherein,

The photochromic compound preparation method is as follows：It is under nitrogen environment, concentration is molten for 0.05 ~ 0.5mol/L Bronsted acid Liquid and concentration for 0.05 ~ 0.5mol/L DBSA with volume ratio 3:1 ~ 3 mixing, while photochromic powder is added, Aniline is added after 60 ~ 120min of magnetic agitation, photochromic powder is 1 with aniline mass ratio:5~10；Persistently stir 60 ~ 90min Afterwards, ammonium persulfate is added dropwise dropwise, aniline is 1 with ammonium persulfate mol ratio:1；12 ~ 36h is reacted at 20 DEG C~30 DEG C；Acetone, go Ion water washing is dried in vacuo afterwards for several times, nano polyaniline/photochromic flour complexes of milling to obtain；By 1 ~ 10g nano polyanilines/ Photochromic flour complexes ultrasonic agitation is scattered in the aqueous solution；Volume ratio 4 is added afterwards:1 water and ammoniacal liquor, after stirring Tetraethyl orthosilicate is added, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60 ~ 90min；Centrifuged and used successively Acetone and deionized water cleaning are precipitated；This is deposited at 90 DEG C and dries 3h, to obtain nano polyaniline/photochromic powder Compound/SiO₂；By nano polyaniline/photochromic flour complexes/SiO₂It is placed under argon gas atmosphere and carries out at 800 ~ 1000 DEG C of heat 1 ~ 2h is managed, polyaniline, photochromic powder/porous SiO is removed₂, i.e., photochromic compound；

The preparation method of the antibacterial powder is as follows：

（1）0.3 ~ 1gC60 powder is weighed, the concentrated sulfuric acid that 80 ~ 100ml mass fractions are 98% is measured, by C60 powder and the concentrated sulfuric acid Mixed in beaker, beaker is placed in ice-water bath, while being stirred with 500 ~ 600rpm speed, obtain mixed liquor；Weigh 1 ~ 3g high Potassium manganate powder, is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, instead Answer 3 ~ 5h；100 ~ 150ml pure water is rapidly joined, is filtered, is then dialysed 3 ~ 5 days, obtained for 1000 bag filter with molecular cut off GQDs suspension；100 ~ 150rpm speed stirs GQDs suspension, while laser irradiates 30 ~ 60min, laser irradiation power is 0.5~2W；It is standby；

（2）Ultrasonic agitation 50 ~ 60mlGQDs suspension, dropwise addition concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solutions；Dropwise plus Enter concentration for 0.1 ~ 0.5mol/L ammonium dihydrogen phosphates, 10 ~ 20min of ultrasonic agitation；0.5 ~ 1mol/L hydroxides are added dropwise Sodium solution, regulation pH value to 11 is then stood, centrifuged, and with deionized water and ethanol alternately washing three times, vacuum drying is obtained GQDs/Ag₂O；

（3）Take 1 ~ 3gGQDs/Ag₂O ultrasonic agitations are scattered in 80 ~ 120ml aqueous solution；Be added dropwise concentration for 0.005 ~ Concentration is added dropwise after the 0.05mol/L cerous nitrate aqueous solution, 30 ~ 60min for 0.005 ~ 0.05mol/L zinc nitrate aqueous solutions；After Continuous ultrasonic agitation, regulation mixed solution pH value to 7.0；Side ultrasonic agitation, side adds the hydrazine hydrate that 4 ~ 8mL mass fractions are 50%, 0.5 ~ 1h of reduction reaction at 30 ~ 40 DEG C；Afterwards, the hydrazine hydrate that 40 ~ 50mL mass fractions are 50% is added, at 85 DEG C also After 30 ~ 48h of original reaction；Filtering, is washed with deionized for several times, and vacuum drying obtains GQDs/Ag₂O/Ag-Zn-Ce；

（4）By 0.1 ~ 0.5gGQDs/Ag₂O/Ag-Zn-Ce ultrasonic agitations are scattered in the aqueous solution；Volume ratio 3 ~ 5 is added afterwards:1 Water and ammoniacal liquor, be stirring evenly and then adding into tetraethyl orthosilicate, regulation pH value is 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reaction 30 ~ 60min；Progress is centrifuged and cleaned successively with acetone and deionized water and precipitated；This is deposited at 80 ~ 90 DEG C and dries 2 ~ 4h, To obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；By GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Be placed under argon gas atmosphere carry out 500 ~ 800 DEG C heat treatment 1 ~ 2h, be cooled to after room temperature, be immersed in hydrofluoric acid with 100 ~ 150W of ultrasonic power carry out ultrasound 10 ~ 15min, removes the local silica in surface, centrifuges and dry, obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂；

（5）Take three-dimensional sponge shape graphene ultrasonic agitation to be scattered in the aqueous solution, GQDs/Ag is added dropwise₂O/Ag-Zn-Ce/ SiO₂In the aqueous solution；10 ~ 100W, 60 ~ 120min of ultrasound, are stood, and deionized water is washed for several times, and centrifugation is placed in confined space, Progress vacuumizes → heated pressurized circulation 3 ~ 8 times, obtains GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder, i.e. antibacterial powder.

2. a kind of preparation method of photochromic bionical quartz, it comprises the following steps：

Step A, prepares modified resin：By weight percentage, 85 ~ 90% resins, 5 ~ 10% antibacterial powders and 1 ~ 5% dispersant are used Melting is heated after homogenizer is well mixed, using double screw extruder extruding pelletization, its melting mixing disperses extrusion temperature For：100 DEG C~280 DEG C；The antibacterial powder is GQDs/Ag₂O/ZnO/ Graphene antibiosis powder；

Step B, by weight percentage, by 80 ~ 90% quartz, 8 ~ 12% modified resins, 0.01 ~ 1% curing agent, 0.01 ~ 1% coupling Agent, 1 ~ 5% photochromic compound, 1 ~ 3% aluminium hydrate powder and 0.1 ~ 2% colorant stir, and obtain compound；

Step C, carries out first time cloth in template by compound, shakes molded, be stripped, and cutting is arranged by predetermined pattern Semi-finished product；Second of cloth is carried out again, is shaken molded, and then drying forming carries out post-processing to obtain finished product；Wherein,

The photochromic compound preparation method is as follows：It is under nitrogen environment, concentration is molten for 0.05 ~ 0.5mol/L Bronsted acid Liquid and concentration for 0.05 ~ 0.5mol/L DBSA with volume ratio 3:1 ~ 3 mixing, while photochromic powder is added, Aniline is added after 60 ~ 120min of magnetic agitation, photochromic powder is 1 with aniline mass ratio:5~10；Persistently stir 60 ~ 90min Afterwards, ammonium persulfate is added dropwise dropwise, aniline is 1 with ammonium persulfate mol ratio:1；12 ~ 36h is reacted at 20 DEG C~30 DEG C；Acetone, go Ion water washing is dried in vacuo afterwards for several times, nano polyaniline/photochromic flour complexes of milling to obtain；By 1 ~ 10g nano polyanilines/ Photochromic flour complexes ultrasonic agitation is scattered in the aqueous solution；Volume ratio 4 is added afterwards:1 water and ammoniacal liquor, after stirring Tetraethyl orthosilicate is added, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60 ~ 90min；Centrifuged and used successively Acetone and deionized water cleaning are precipitated；This is deposited at 90 DEG C and dries 3h, to obtain nano polyaniline/photochromic powder Compound/SiO₂；By nano polyaniline/photochromic flour complexes/SiO₂It is placed under argon gas atmosphere and carries out at 800 ~ 1000 DEG C of heat 1 ~ 2h is managed, polyaniline, photochromic powder/porous SiO is removed₂, i.e., photochromic compound；

The preparation method of the antibacterial powder is as follows：

（1）0.3 ~ 1gC60 powder is weighed, the concentrated sulfuric acid that 80 ~ 100ml mass fractions are 98% is measured, by C60 powder and the concentrated sulfuric acid Mixed in beaker, beaker is placed in ice-water bath, while being stirred with 500 ~ 600rpm speed, obtain mixed liquor；Weigh 1 ~ 3g high Potassium manganate powder, is slowly added in above-mentioned mixed liquor；Ice-water bath is removed, water-bath is changed into, 30 ~ 40 DEG C of bath temperature is kept, instead Answer 3 ~ 5h；100 ~ 150ml pure water is rapidly joined, is filtered, is then dialysed 3 ~ 5 days, obtained for 1000 bag filter with molecular cut off GQDs suspension；100 ~ 150rpm speed stirs GQDs suspension, while laser irradiates 30 ~ 60min, laser irradiation power is 0.5~2W；It is standby；

（2）Ultrasonic agitation 50 ~ 60mlGQDs suspension, dropwise addition concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solutions；Dropwise plus Enter concentration for 0.1 ~ 0.5mol/L ammonium dihydrogen phosphates, 10 ~ 20min of ultrasonic agitation；0.5 ~ 1mol/L hydroxides are added dropwise Sodium solution, regulation pH value to 11 is then stood, centrifuged, and with deionized water and ethanol alternately washing three times, vacuum drying is obtained GQDs/Ag₂O；

（3）Take 1 ~ 3gGQDs/Ag₂O ultrasonic agitations are scattered in the aqueous solution；Concentration is added dropwise for 0.05 ~ 0.5g/100mlZnO The quantum dot aqueous solution, ultrasonic power mixing speed respectively halves；After 60 ~ 90min, stand, filtering is washed with deionized for several times, Vacuum drying, obtains GQDs/Ag₂O/ZnO；

（4）Take three-dimensional sponge shape graphene ultrasonic agitation to be scattered in the aqueous solution, GQDs/Ag is added dropwise₂In the O/ZnO aqueous solution； 10 ~ 100W, 60 ~ 120min of ultrasound, are stood, and deionized water is washed for several times, and centrifugation is placed in confined space, and progress is vacuumized → added Hot pressurized circulation 3 ~ 8 times, obtains GQDs/Ag₂O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder.

3. the preparation method of photochromic bionical quartz according to claim 1 or 2, it is characterised in that the three-dimensional Spongy graphene preparation method is as follows：By 3g graphite powders, 1g NaNO₃Mixed in ice-water bath with the concentrated sulfuric acids of 250ml 98% Uniformly, 6g KMnO are slowly added to₄；Then heat at 35 DEG C, after stirring 40min, add 95ml deionized waters, be warming up to 98 DEG C of reaction 20min；The dilution of 270ml water is added, and with the H of 5ml 30%₂O₂Neutralize unnecessary KMnO₄, the color of mixed solution For brown color, filter while hot, with deionized water cyclic washing to neutrality, ultrasonic disperse obtains GO；The 200ml mass fractions are taken to be 5mg/ml graphene oxide solution is poured into diameter 25cm, high 2cm discoid reaction utensil, adds ascorbic acid (VC) 0.5g Stirring is sufficiently mixed it；Then the graphene oxide that confined reaction ware is placed in 80 DEG C of hydro-thermal reaction 15h, reaction utensil is spontaneous Contraction is cross-linked into three-dimensional sponge structure, freeze-drying, obtains the three-dimensional sponge shape graphene of flexibility.

4. a kind of photochromic bionical quartz, it is characterised in that as the preparation method system as described in as any such as claims 1 to 3 .