CN106800846A - A kind of nano-powder and photochromic coating therefrom for photochromic coating - Google Patents

A kind of nano-powder and photochromic coating therefrom for photochromic coating Download PDF

Info

Publication number
CN106800846A
CN106800846A CN201710069283.9A CN201710069283A CN106800846A CN 106800846 A CN106800846 A CN 106800846A CN 201710069283 A CN201710069283 A CN 201710069283A CN 106800846 A CN106800846 A CN 106800846A
Authority
CN
China
Prior art keywords
weight portions
polyetheramine
room temperature
pyrrole throat
hyperbranched poly
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710069283.9A
Other languages
Chinese (zh)
Other versions
CN106800846B (en
Inventor
钟学群
杨雪英
陈建山
刘民
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ANYAN NANOMETER NEW MATERIAL TECHNOLOGY (GUANGZHOU) CO., LTD.
Original Assignee
Guangzhou New Composite Material Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangzhou New Composite Material Co Ltd filed Critical Guangzhou New Composite Material Co Ltd
Priority to CN201710069283.9A priority Critical patent/CN106800846B/en
Publication of CN106800846A publication Critical patent/CN106800846A/en
Application granted granted Critical
Publication of CN106800846B publication Critical patent/CN106800846B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
    • C08G65/2627—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aromatic or arylaliphatic amine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Plant Pathology (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention discloses a kind of nano-powder for photochromic coating, by weight, including following components：The epoxy-capped polyetheramine cladding nano silicon of 10 weight portions, the epoxy-capped polyetheramine cladding boccaro and the modification sulphonation polyetheramine hyperbranched poly pyrrole throat copolymer of 5 10 weight portions of 15 weight portions；The modification sulphonation polyetheramine hyperbranched poly pyrrole throat copolymer is obtained by polyquaternium and graphene oxide with sulfonated polyether amine hyperbranched poly pyrrole throat copolymer reaction.The invention also discloses the photochromic coating using the nano-powder.

Description

A kind of nano-powder for photochromic coating and therefrom photochromic Coating
Technical field
The invention belongs to nano-powder technical field, more particularly it relates to a kind of for photochromic coating Nano-powder and photochromic coating therefrom.
Background technology
Photochromic coating is a kind of new type functional coating, and good indicating effect and landscaping effect can be presented, and is being answered Anxious label, gap marker, power switch, enamel place name plates, way mark, toy, handicraft, clock and watch, instrument board, weaving The aspects such as product, fire-fighting equipment, military affairs, facility of camping all have been widely used.Existing photochromic coating has following lacking Point：
(1) weatherability of product, water resistance can not typically reach requirement；
(2) when there is fire, the film forming matter of these fireproof coatings can not bear drastically elevated temperature and be burned out quickly, And fire-proof can not be played a part of；
(3) poor performance such as anti-corrosion, acid and alkali-resistance, antibacterial.
Therefore, the present invention wished by adding nano-powder, obtain that weatherability is strong, fire resistance is good and with anti-corrosion, resist Bacterium and the photochromic coating of acidproof alkali ability.
The content of the invention
In order to solve the above problems, one aspect of the present invention provides a kind of nano powder for photochromic coating Body, by weight, including following components：
The epoxy-capped polyetheramine cladding nano silicon of 10 weight portions, the epoxy-capped polyetheramine cladding of 1-5 weight portions are purple The modification sulphonation polyetheramine of sand and 5-10 weight portions-hyperbranched poly pyrrole throat copolymer；
The modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer passes through polyquaternium and graphene oxide and sulfonated polyether Amine-hyperbranched poly pyrrole throat copolymer reaction is obtained.
In one embodiment, the epoxy-capped polyetheramine cladding nano silicon is by following methods preparation Into：
In the dry three-necked bottles of 3L, the benzylamine and 500 grams of dimethyl of 100 grams epoxy resin E51,0.24mol are sequentially added Sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 80 DEG C of reaction 4h, is down to room temperature, is subsequently adding 500 grams Dimethyl sulfoxide (DMSO) and 300 grams of nano silicons, heat up 80 DEG C reaction 1h, be down to room temperature, and pour into rapidly 3000mL go from In sub- water, a large amount of solids of sedimentation are obtained；With after the deionized water cyclic washing product, suction filtration and collected polymer dry in vacuum In case, 60 DEG C of dryings 20 hours obtain epoxy-capped polyetheramine cladding nano silicon.
In one embodiment, the preparation method of the nano silicon is：
(1) SILICA FUME is dissolved in sodium hydroxide solution, centrifugation or filtering remove undissolved solid residue, under 50 DEG C of heating Reaction 10h；
(2) after supernatant being gone into the removal of impurity with cationic ion-exchange resin and anion exchange resin respectively, by ion exchange resin After being separated with reaction solution；
(3) solution that step (2) treatment is obtained is dried, that is, obtains nano silicon；
The concentration of the sodium hydroxide solution is 30%~60%；
The SILICA FUME is with the w/v of sodium hydroxide solution：40%~80%g/mL.
In one embodiment, the epoxy-capped polyetheramine cladding boccaro is prepared from by following methods：
In the dry three-necked bottles of 3L, the benzylamine and 500 grams of dimethyl of 100 grams epoxy resin E51,0.24mol are sequentially added Sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 80 DEG C of reaction 4h, is down to room temperature, is subsequently adding 700 grams Dimethyl sulfoxide (DMSO) and 400 grams of boccaros, heat up 80 DEG C of reaction 1h, is down to room temperature, and pours into rapidly in 3000mL deionized waters, obtains To a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C Dry 20 hours, obtain epoxy-capped polyetheramine cladding boccaro.
In one embodiment, the modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared by following methods Form：
（1）Prepare polyquaternium
In the dry three-necked bottles of 1000ml, add 1,12- dibromo-dodecanes 0.1mol, Isosorbide-5-Nitrae-lupetazin 0.092mol with And solvent dimethyl sulfoxide (DMSO) 80ml, after being reacted 5 hours at 50 DEG C, add N- methylimidazole 0.0025mol and N- methyl Quinoline 0.0025mol, after being reacted 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium；
（2）Prepare amino-terminated polyetheramine
In the dry three-necked bottles of 1000mL, the benzylamine and 700 grams of diformazans of 95 grams epoxy resin E51,0.26mol are sequentially added Base sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature, And pour into rapidly in 2000mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration is simultaneously Collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain amino-terminated polyetheramine；
（3）Prepare hyperbranched poly pyrrole throat
In the dry three-necked bottles of 100mL, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) acid anhydrides of benzene three are sequentially added With 25ml metacresols, stir under nitrogen protection, after three acid anhydrides are completely dissolved, add the 3 of 0.006 mole, 3 '-benzidine Amine, after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction terminates, it is down to Room temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously received Collection polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
（4）Prepare polyetheramine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of described amino-terminated polyetheramine, 0.6 gram of naphthalene anhydride end-blocking is sequentially added The metacresol of hyperbranched poly pyrrole throat, the dimethyl sulfoxide (DMSO) of 10mL and 10mL, after stirring 60min under nitrogen protection, is heated to 80 DEG C, 4h is reacted, then at 185 DEG C, react 10h；After reaction terminates, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol, obtained To a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours, obtain final product polyetheramine-hyperbranched poly pyrrole throat copolymer；
（5）Prepare sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of the polyetheramine-hyperbranched poly pyrrole throat copolymer and 10mL is sequentially added Mass fraction 98% the concentrated sulfuric acid, under nitrogen protection, at 40 DEG C stir 180min after, pour into frozen water, washed repeatedly with frozen water After washing the product, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C of dryings obtain final product sulfonated polyether amine-hyperbranched for 24 hours Poly- pyrrole throat copolymer；
（6）Prepare modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer
In 1000ml three-necked bottles, step is added（1）0.2 gram of the polyquaternium for obtaining, 0.1 gram of graphene oxide, step（5） The sulfonated polyether amine for obtaining -0.5 gram of hyperbranched poly pyrrole throat copolymer, 0.2 gram of hexamethylene diamine, 0.05 gram of NaOH, deionized water 2mL and DMF 50ml, after stirring at room temperature；After being reacted 10 hours at 60 DEG C, room temperature is down to, and Pour into 2000mL methyl alcohol rapidly, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration simultaneously collects polymerization Thing, in vacuum drying oven, 60 DEG C of dryings 24 hours obtain modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer.
In one embodiment, the nano-powder for photochromic coating is also organic including 1-5 weight portions Sodium base modified montmorillonoid, and the preparation method of organic sodium base modified montmorillonoid is：
15g calcium-base montmorillonites, plus 800ml distilled water are taken, 20min is stirred, Na is added2CO3 5g, stirs, and staticly settles and removes It is miscellaneous, 5min is centrifuged under the conditions of 2000r/min, separate and obtain sodium-based montmorillonite.
Another aspect of the present invention provides a kind of photochromic coating, by weight, including following components：
The acrylic emulsion of 100 weight portions, the tungstic acid of 30-60 weight portions, the titanium dioxide of 20-40 weight portions, 5-10 weights Measure the copper chloride of part, the described nano-powder for photochromic coating of 20-60 weight portions, the KH-560 of 1-5 weight portions, The ethanol of KH-550,1-5 weight portion of 1-5 weight portions and the deionized water of 5-10 weight portions；
Preferably, described photochromic coating, by weight, including following components：
The acrylic emulsion of 100 weight portions, the tungstic acid of 50 weight portions, the titanium dioxide of 30 weight portions, the chlorination of 8 weight portions Copper, the described nano-powder for photochromic coating of 45 weight portions, the KH-560 of 2 weight portions, the KH- of 3 weight portions 550th, the deionized water of the ethanol of 3 weight portions and 9 weight portions.
Compared with prior art, beneficial effects of the present invention are：
1st, epoxy-capped polyetheramine contains great amount of hydroxy group, can greatly improve the cohesive force of coating and base material, improves the resistance to of coating Aging ability, additionally, it can also react with amino, improves crosslink density and solidification rate, a large amount of rigidity phenyl ring on this outside chain Introducing, can improve the distance of strand, improve flame retardant effect.By coating filler, filler is substantially increased with system Compatibility, so as to provide Advantageous Effects of the invention.
2nd, the addition of modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer can both provide excellent weatherability, higher Intensity, good fire resistance and excellent anti-microbial property, and can play plasticization again prevents system excessively crisp, also Processing step can be greatly reduced and the degree of cross linking of system is substantially increased, so as to provide Advantageous Effects of the invention.
Specific embodiment
Raw material:
All tetramines, diacid are purchased from CTI, SigmaAldrich, AlfaAesar or SCRC, and directly use, without entering one Step purifying.Coupling agent KH-550, KH-560, boccaro（The mesh of average grain diameter 500）, calcium-base montmorillonite（The mesh of average grain diameter 500）, three oxygen Change tungsten（The mesh of average grain diameter 2000）And titanium dioxide（200 nanometers of average grain diameter）Purchased from the limited public affairs of Chinese medicines group chemical reagent Department.Graphene oxide is rich purchased from Suzhou carbon.Acrylic emulsion is purchased from Guangdong Xin Yi Chemical Co., Ltd.s, and the trade mark is NACRYLIC 2800。
Nano silicon（Average grain diameter 100nm）Make by oneself, preparation method is：
(1) SILICA FUME is dissolved in sodium hydroxide solution, centrifugation or filtering remove undissolved solid residue, under 50 DEG C of heating Reaction 10h；
(2) after supernatant being gone into the removal of impurity with cationic ion-exchange resin and anion exchange resin respectively, by ion exchange resin After being separated with reaction solution；
(3) solution that step (2) treatment is obtained is dried, that is, obtains nano silicon；
The concentration of the sodium hydroxide solution is 50%；
The SILICA FUME is with the w/v of sodium hydroxide solution：75%g/mL.
Other raw materials are purchased from Aladdin reagent Co., Ltd.
Embodiment 1
The epoxy-capped polyetheramine of the epoxy-capped polyetheramine cladding nano silicon of 10 weight portions, 3 weight portions is coated purple The modification sulphonation polyetheramine of sand and 6 weight portions-hyperbranched poly pyrrole throat copolymer is added after being sufficiently mixed 15 minutes in mixer The nano-powder for photochromic coating is obtained, the stir speed (S.S.) of the mixer is 600 revs/min；
Wherein, the epoxy-capped polyetheramine cladding nano silicon is prepared from by following methods：
In the dry three-necked bottles of 3L, the benzylamine and 500 grams of dimethyl of 100 grams epoxy resin E51,0.24mol are sequentially added Sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 80 DEG C of reaction 4h, is down to room temperature, is subsequently adding 500 grams Dimethyl sulfoxide (DMSO) and 300 grams of nano silicons, heat up 80 DEG C reaction 1h, be down to room temperature, and pour into rapidly 3000mL go from In sub- water, a large amount of solids of sedimentation are obtained；With after the deionized water cyclic washing product, suction filtration and collected polymer dry in vacuum In case, 60 DEG C of dryings 20 hours obtain epoxy-capped polyetheramine cladding nano silicon；
The epoxy-capped polyetheramine cladding boccaro is prepared from by following methods：
In the dry three-necked bottles of 3L, the benzylamine and 500 grams of dimethyl of 100 grams epoxy resin E51,0.24mol are sequentially added Sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 80 DEG C of reaction 4h, is down to room temperature, is subsequently adding 700 grams Dimethyl sulfoxide (DMSO) and 400 grams of boccaros, heat up 80 DEG C of reaction 1h, is down to room temperature, and pours into rapidly in 3000mL deionized waters, obtains To a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C Dry 20 hours, obtain epoxy-capped polyetheramine cladding boccaro；
The modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared from by following methods：
（1）Prepare polyquaternium
In the dry three-necked bottles of 1000ml, add 1,12- dibromo-dodecanes 0.1mol, Isosorbide-5-Nitrae-lupetazin 0.092mol with And solvent dimethyl sulfoxide (DMSO) 80ml, after being reacted 5 hours at 50 DEG C, add N- methylimidazole 0.0025mol and N- methyl Quinoline 0.0025mol, after being reacted 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium；
（2）Prepare amino-terminated polyetheramine
In the dry three-necked bottles of 1000mL, the benzylamine and 700 grams of diformazans of 95 grams epoxy resin E51,0.26mol are sequentially added Base sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature, And pour into rapidly in 2000mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration is simultaneously Collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain amino-terminated polyetheramine；
（3）Prepare hyperbranched poly pyrrole throat
In the dry three-necked bottles of 100mL, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) acid anhydrides of benzene three are sequentially added With 25ml metacresols, stir under nitrogen protection, after three acid anhydrides are completely dissolved, add the 3 of 0.006 mole, 3 '-benzidine Amine, after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction terminates, it is down to Room temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously received Collection polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
（4）Prepare polyetheramine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of described amino-terminated polyetheramine, 0.6 gram of naphthalene anhydride end-blocking is sequentially added The metacresol of hyperbranched poly pyrrole throat, the dimethyl sulfoxide (DMSO) of 10mL and 10mL, after stirring 60min under nitrogen protection, is heated to 80 DEG C, 4h is reacted, then at 185 DEG C, react 10h；After reaction terminates, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol, obtained To a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours, obtain final product polyetheramine-hyperbranched poly pyrrole throat copolymer；
（5）Prepare sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of the polyetheramine-hyperbranched poly pyrrole throat copolymer and 10mL is sequentially added Mass fraction 98% the concentrated sulfuric acid, under nitrogen protection, at 40 DEG C stir 180min after, pour into frozen water, washed repeatedly with frozen water After washing the product, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C of dryings obtain final product sulfonated polyether amine-hyperbranched for 24 hours Poly- pyrrole throat copolymer；
（6）Prepare modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer
In 1000ml three-necked bottles, step is added（1）0.2 gram of the polyquaternium for obtaining, 0.1 gram of graphene oxide, step（5） The sulfonated polyether amine for obtaining -0.5 gram of hyperbranched poly pyrrole throat copolymer, 0.2 gram of hexamethylene diamine, 0.05 gram of NaOH, deionized water 2mL and DMF 50ml, after stirring at room temperature；After being reacted 10 hours at 60 DEG C, room temperature is down to, and Pour into 2000mL methyl alcohol rapidly, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration simultaneously collects polymerization Thing, in vacuum drying oven, 60 DEG C of dryings 24 hours obtain modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer；
By the acrylic emulsion of 100 weight portions, the tungstic acid of 50 weight portions, the titanium dioxide of 30 weight portions, 8 weight portions chlorine Change copper, above-mentioned nano-powder, the KH-560 of 2 weight portions, the KH- of 3 weight portions for photochromic coating of 45 weight portions 550th, during the deionized water of the ethanol of 3 weight portions and 9 weight portions adds agravic blender, fly cutter is opened, to avoid the occurrence of Bonding, prevents stirring uneven, and mixing time is 30 minutes, discharging.
Embodiment 2
By the epoxy-capped polyetheramine cladding nano silicon of 10 weight portions and the epoxy-capped polyetheramine cladding of 3 weight portions Boccaro adds the nano-powder for obtaining for photochromic coating after being sufficiently mixed 15 minutes in mixer, and the mixer is stirred Speed is mixed for 600 revs/min；
Wherein, the epoxy-capped polyetheramine cladding nano silicon is prepared from by following methods：
In the dry three-necked bottles of 3L, the benzylamine and 500 grams of dimethyl of 100 grams epoxy resin E51,0.24mol are sequentially added Sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 80 DEG C of reaction 4h, is down to room temperature, is subsequently adding 500 grams Dimethyl sulfoxide (DMSO) and 300 grams of nano silicons, heat up 80 DEG C reaction 1h, be down to room temperature, and pour into rapidly 3000mL go from In sub- water, a large amount of solids of sedimentation are obtained；With after the deionized water cyclic washing product, suction filtration and collected polymer dry in vacuum In case, 60 DEG C of dryings 20 hours obtain epoxy-capped polyetheramine cladding nano silicon；
The epoxy-capped polyetheramine cladding boccaro is prepared from by following methods：
In the dry three-necked bottles of 3L, the benzylamine and 500 grams of dimethyl of 100 grams epoxy resin E51,0.24mol are sequentially added Sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 80 DEG C of reaction 4h, is down to room temperature, is subsequently adding 700 grams Dimethyl sulfoxide (DMSO) and 400 grams of boccaros, heat up 80 DEG C of reaction 1h, is down to room temperature, and pours into rapidly in 3000mL deionized waters, obtains To a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C Dry 20 hours, obtain epoxy-capped polyetheramine cladding nano silicon；
By the acrylic emulsion of 100 weight portions, the tungstic acid of 50 weight portions, the titanium dioxide of 30 weight portions, 8 weight portions chlorine Change copper, above-mentioned nano-powder, the KH-560 of 2 weight portions, the KH- of 3 weight portions for photochromic coating of 45 weight portions 550th, during the deionized water of the ethanol of 3 weight portions and 9 weight portions adds agravic blender, fly cutter is opened, to avoid the occurrence of Bonding, prevents stirring uneven, and mixing time is 30 minutes, discharging.
Embodiment 3
By the modification sulphonation polyetheramine of the epoxy-capped polyetheramine of 10 weight portions cladding nano silicon and 6 weight portions-super Branched poly- pyrrole throat copolymer adds the nano-powder obtained after being sufficiently mixed 15 minutes in mixer for photochromic coating, institute The stir speed (S.S.) for stating mixer is 600 revs/min；
Wherein, the epoxy-capped polyetheramine cladding nano silicon is prepared from by following methods：
In the dry three-necked bottles of 3L, the benzylamine and 500 grams of dimethyl of 100 grams epoxy resin E51,0.24mol are sequentially added Sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 80 DEG C of reaction 4h, is down to room temperature, is subsequently adding 500 grams Dimethyl sulfoxide (DMSO) and 300 grams of nano silicons, heat up 80 DEG C reaction 1h, be down to room temperature, and pour into rapidly 3000mL go from In sub- water, a large amount of solids of sedimentation are obtained；With after the deionized water cyclic washing product, suction filtration and collected polymer dry in vacuum In case, 60 DEG C of dryings 20 hours obtain epoxy-capped polyetheramine cladding nano silicon；
The modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared from by following methods：
（1）Prepare polyquaternium
In the dry three-necked bottles of 1000ml, add 1,12- dibromo-dodecanes 0.1mol, Isosorbide-5-Nitrae-lupetazin 0.092mol with And solvent dimethyl sulfoxide (DMSO) 80ml, after being reacted 5 hours at 50 DEG C, add N- methylimidazole 0.0025mol and N- methyl Quinoline 0.0025mol, after being reacted 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium；
（2）Prepare amino-terminated polyetheramine
In the dry three-necked bottles of 1000mL, the benzylamine and 700 grams of diformazans of 95 grams epoxy resin E51,0.26mol are sequentially added Base sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature, And pour into rapidly in 2000mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration is simultaneously Collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain amino-terminated polyetheramine；
（3）Prepare hyperbranched poly pyrrole throat
In the dry three-necked bottles of 100mL, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) acid anhydrides of benzene three are sequentially added With 25ml metacresols, stir under nitrogen protection, after three acid anhydrides are completely dissolved, add the 3 of 0.006 mole, 3 '-benzidine Amine, after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction terminates, it is down to Room temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously received Collection polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
（4）Prepare polyetheramine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of described amino-terminated polyetheramine, 0.6 gram of naphthalene anhydride end-blocking is sequentially added The metacresol of hyperbranched poly pyrrole throat, the dimethyl sulfoxide (DMSO) of 10mL and 10mL, after stirring 60min under nitrogen protection, is heated to 80 DEG C, 4h is reacted, then at 185 DEG C, react 10h；After reaction terminates, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol, obtained To a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours, obtain final product polyetheramine-hyperbranched poly pyrrole throat copolymer；
（5）Prepare sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of the polyetheramine-hyperbranched poly pyrrole throat copolymer and 10mL is sequentially added Mass fraction 98% the concentrated sulfuric acid, under nitrogen protection, at 40 DEG C stir 180min after, pour into frozen water, washed repeatedly with frozen water After washing the product, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C of dryings obtain final product sulfonated polyether amine-hyperbranched for 24 hours Poly- pyrrole throat copolymer；
（6）Prepare modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer
In 1000ml three-necked bottles, step is added（1）0.2 gram of the polyquaternium for obtaining, 0.1 gram of graphene oxide, step（5） The sulfonated polyether amine for obtaining -0.5 gram of hyperbranched poly pyrrole throat copolymer, 0.2 gram of hexamethylene diamine, 0.05 gram of NaOH, deionized water 2mL and DMF 50ml, after stirring at room temperature；After being reacted 10 hours at 60 DEG C, room temperature is down to, and Pour into 2000mL methyl alcohol rapidly, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration simultaneously collects polymerization Thing, in vacuum drying oven, 60 DEG C of dryings 24 hours obtain modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer.
By the acrylic emulsion of 100 weight portions, the tungstic acid of 50 weight portions, the titanium dioxide of 30 weight portions, 8 weight portions Copper chloride, the above-mentioned nano-powder for photochromic coating of 45 weight portions, the KH-560 of 2 weight portions, 3 weight portions The deionized water of KH-550, the ethanol of 3 weight portions and 9 weight portions is added in agravic blender, fly cutter is opened, to avoid out Now bond, prevent stirring uneven, mixing time is 30 minutes, discharging.
Embodiment 4
The epoxy-capped polyetheramine of the epoxy-capped polyetheramine cladding nano silicon of 10 weight portions, 3 weight portions is coated purple The modified polyether amine of sand and 6 weight portions-hyperbranched poly pyrrole throat copolymer is added after being sufficiently mixed 15 minutes in mixer and obtained For the nano-powder of photochromic coating, the stir speed (S.S.) of the mixer is 600 revs/min；
Wherein, the epoxy-capped polyetheramine cladding nano silicon is prepared from by following methods：
In the dry three-necked bottles of 3L, the benzylamine and 500 grams of dimethyl of 100 grams epoxy resin E51,0.24mol are sequentially added Sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 80 DEG C of reaction 4h, is down to room temperature, is subsequently adding 500 grams Dimethyl sulfoxide (DMSO) and 300 grams of nano silicons, heat up 80 DEG C reaction 1h, be down to room temperature, and pour into rapidly 3000mL go from In sub- water, a large amount of solids of sedimentation are obtained；With after the deionized water cyclic washing product, suction filtration and collected polymer dry in vacuum In case, 60 DEG C of dryings 20 hours obtain epoxy-capped polyetheramine cladding nano silicon；
The epoxy-capped polyetheramine cladding boccaro is prepared from by following methods：
In the dry three-necked bottles of 3L, the benzylamine and 500 grams of dimethyl of 100 grams epoxy resin E51,0.24mol are sequentially added Sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 80 DEG C of reaction 4h, is down to room temperature, is subsequently adding 700 grams Dimethyl sulfoxide (DMSO) and 400 grams of boccaros, heat up 80 DEG C of reaction 1h, is down to room temperature, and pours into rapidly in 3000mL deionized waters, obtains To a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C Dry 20 hours, obtain epoxy-capped polyetheramine cladding nano silicon；
The modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared from by following methods：
（1）Prepare polyquaternium
In the dry three-necked bottles of 1000ml, add 1,12- dibromo-dodecanes 0.1mol, Isosorbide-5-Nitrae-lupetazin 0.092mol with And solvent dimethyl sulfoxide (DMSO) 80ml, after being reacted 5 hours at 50 DEG C, add N- methylimidazole 0.0025mol and N- methyl Quinoline 0.0025mol, after being reacted 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium；
（2）Prepare amino-terminated polyetheramine
In the dry three-necked bottles of 1000mL, the benzylamine and 700 grams of diformazans of 95 grams epoxy resin E51,0.26mol are sequentially added Base sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature, And pour into rapidly in 2000mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration is simultaneously Collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain amino-terminated polyetheramine；
（3）Prepare hyperbranched poly pyrrole throat
In the dry three-necked bottles of 100mL, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) acid anhydrides of benzene three are sequentially added With 25ml metacresols, stir under nitrogen protection, after three acid anhydrides are completely dissolved, add the 3 of 0.006 mole, 3 '-benzidine Amine, after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction terminates, it is down to Room temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously received Collection polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
（4）Prepare polyetheramine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of described amino-terminated polyetheramine, 0.6 gram of naphthalene anhydride end-blocking is sequentially added The metacresol of hyperbranched poly pyrrole throat, the dimethyl sulfoxide (DMSO) of 10mL and 10mL, after stirring 60min under nitrogen protection, is heated to 80 DEG C, 4h is reacted, then at 185 DEG C, react 10h；After reaction terminates, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol, obtained To a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours, obtain final product polyetheramine-hyperbranched poly pyrrole throat copolymer；
（5）Prepare modified polyether amine-hyperbranched poly pyrrole throat copolymer
In 1000ml three-necked bottles, step is added（1）0.2 gram of the polyquaternium for obtaining, 0.1 gram of graphene oxide, step（5） The polyetheramine for obtaining -0.5 gram of hyperbranched poly pyrrole throat copolymer, 0.2 gram of hexamethylene diamine, 0.05 gram of NaOH, deionized water 2mL with And DMF 50ml, after stirring at room temperature；After being reacted 10 hours at 60 DEG C, room temperature is down to, and rapidly Pour into 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in In vacuum drying oven, 60 DEG C of dryings 24 hours obtain modified polyether amine-hyperbranched poly pyrrole throat copolymer.
By the acrylic emulsion of 100 weight portions, the tungstic acid of 50 weight portions, the titanium dioxide of 30 weight portions, 8 weight portions Copper chloride, the above-mentioned nano-powder for photochromic coating of 45 weight portions, the KH-560 of 2 weight portions, 3 weight portions The deionized water of KH-550, the ethanol of 3 weight portions and 9 weight portions is added in agravic blender, fly cutter is opened, to avoid out Now bond, prevent stirring uneven, mixing time is 30 minutes, discharging.
Embodiment 5
By the epoxy-capped polyetheramine cladding boccaro of the nano silicon of 10 weight portions, 3 weight portions and being modified for 6 weight portions Sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer is added after being sufficiently mixed 15 minutes in mixer and obtained for photochromic coating Nano-powder, the stir speed (S.S.) of the mixer is 600 revs/min；
The epoxy-capped polyetheramine cladding boccaro is prepared from by following methods：
In the dry three-necked bottles of 3L, the benzylamine and 500 grams of dimethyl of 100 grams epoxy resin E51,0.24mol are sequentially added Sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 80 DEG C of reaction 4h, is down to room temperature, is subsequently adding 700 grams Dimethyl sulfoxide (DMSO) and 400 grams of boccaros, heat up 80 DEG C of reaction 1h, is down to room temperature, and pours into rapidly in 3000mL deionized waters, obtains To a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C Dry 20 hours, obtain epoxy-capped polyetheramine cladding nano silicon；
The modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared from by following methods：
（1）Prepare polyquaternium
In the dry three-necked bottles of 1000ml, add 1,12- dibromo-dodecanes 0.1mol, Isosorbide-5-Nitrae-lupetazin 0.092mol with And solvent dimethyl sulfoxide (DMSO) 80ml, after being reacted 5 hours at 50 DEG C, add N- methylimidazole 0.0025mol and N- methyl Quinoline 0.0025mol, after being reacted 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium；
（2）Prepare amino-terminated polyetheramine
In the dry three-necked bottles of 1000mL, the benzylamine and 700 grams of diformazans of 95 grams epoxy resin E51,0.26mol are sequentially added Base sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature, And pour into rapidly in 2000mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration is simultaneously Collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain amino-terminated polyetheramine；
（3）Prepare hyperbranched poly pyrrole throat
In the dry three-necked bottles of 100mL, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) acid anhydrides of benzene three are sequentially added With 25ml metacresols, stir under nitrogen protection, after three acid anhydrides are completely dissolved, add the 3 of 0.006 mole, 3 '-benzidine Amine, after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction terminates, it is down to Room temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously received Collection polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
（4）Prepare polyetheramine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of described amino-terminated polyetheramine, 0.6 gram of naphthalene anhydride end-blocking is sequentially added The metacresol of hyperbranched poly pyrrole throat, the dimethyl sulfoxide (DMSO) of 10mL and 10mL, after stirring 60min under nitrogen protection, is heated to 80 DEG C, 4h is reacted, then at 185 DEG C, react 10h；After reaction terminates, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol, obtained To a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours, obtain final product polyetheramine-hyperbranched poly pyrrole throat copolymer；
（5）Prepare sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of the polyetheramine-hyperbranched poly pyrrole throat copolymer and 10mL is sequentially added Mass fraction 98% the concentrated sulfuric acid, under nitrogen protection, at 40 DEG C stir 180min after, pour into frozen water, washed repeatedly with frozen water After washing the product, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C of dryings obtain final product sulfonated polyether amine-hyperbranched for 24 hours Poly- pyrrole throat copolymer；
（6）Prepare modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer
In 1000ml three-necked bottles, step is added（1）0.2 gram of the polyquaternium for obtaining, 0.1 gram of graphene oxide, step（5） The sulfonated polyether amine for obtaining -0.5 gram of hyperbranched poly pyrrole throat copolymer, 0.2 gram of hexamethylene diamine, 0.05 gram of NaOH, deionized water 2mL and DMF 50ml, after stirring at room temperature；After being reacted 10 hours at 60 DEG C, room temperature is down to, and Pour into 2000mL methyl alcohol rapidly, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration simultaneously collects polymerization Thing, in vacuum drying oven, 60 DEG C of dryings 24 hours obtain modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer.
By the acrylic emulsion of 100 weight portions, the tungstic acid of 50 weight portions, the titanium dioxide of 30 weight portions, 8 weight portions Copper chloride, the above-mentioned nano-powder for photochromic coating of 45 weight portions, the KH-560 of 2 weight portions, 3 weight portions The deionized water of KH-550, the ethanol of 3 weight portions and 9 weight portions is added in agravic blender, fly cutter is opened, to avoid out Now bond, prevent stirring uneven, mixing time is 30 minutes, discharging.
Embodiment 6
By the modified of the epoxy-capped polyetheramine cladding nano silicon of 10 weight portions, the boccaro of 3 weight portions and 6 weight portions Sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer is added after being sufficiently mixed 15 minutes in mixer and obtained for photochromic coating Nano-powder, the stir speed (S.S.) of the mixer is 600 revs/min；
Wherein, the epoxy-capped polyetheramine cladding nano silicon is prepared from by following methods：
In the dry three-necked bottles of 3L, the benzylamine and 500 grams of dimethyl of 100 grams epoxy resin E51,0.24mol are sequentially added Sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 80 DEG C of reaction 4h, is down to room temperature, is subsequently adding 500 grams Dimethyl sulfoxide (DMSO) and 300 grams of nano silicons, heat up 80 DEG C reaction 1h, be down to room temperature, and pour into rapidly 3000mL go from In sub- water, a large amount of solids of sedimentation are obtained；With after the deionized water cyclic washing product, suction filtration and collected polymer dry in vacuum In case, 60 DEG C of dryings 20 hours obtain epoxy-capped polyetheramine cladding nano silicon；
The modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared from by following methods：
（1）Prepare polyquaternium
In the dry three-necked bottles of 1000ml, add 1,12- dibromo-dodecanes 0.1mol, Isosorbide-5-Nitrae-lupetazin 0.092mol with And solvent dimethyl sulfoxide (DMSO) 80ml, after being reacted 5 hours at 50 DEG C, add N- methylimidazole 0.0025mol and N- methyl Quinoline 0.0025mol, after being reacted 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium；
（2）Prepare amino-terminated polyetheramine
In the dry three-necked bottles of 1000mL, the benzylamine and 700 grams of diformazans of 95 grams epoxy resin E51,0.26mol are sequentially added Base sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature, And pour into rapidly in 2000mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration is simultaneously Collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain amino-terminated polyetheramine；
（3）Prepare hyperbranched poly pyrrole throat
In the dry three-necked bottles of 100mL, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) acid anhydrides of benzene three are sequentially added With 25ml metacresols, stir under nitrogen protection, after three acid anhydrides are completely dissolved, add the 3 of 0.006 mole, 3 '-benzidine Amine, after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction terminates, it is down to Room temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously received Collection polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
（4）Prepare polyetheramine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of described amino-terminated polyetheramine, 0.6 gram of naphthalene anhydride end-blocking is sequentially added The metacresol of hyperbranched poly pyrrole throat, the dimethyl sulfoxide (DMSO) of 10mL and 10mL, after stirring 60min under nitrogen protection, is heated to 80 DEG C, 4h is reacted, then at 185 DEG C, react 10h；After reaction terminates, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol, obtained To a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours, obtain final product polyetheramine-hyperbranched poly pyrrole throat copolymer；
（5）Prepare sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of the polyetheramine-hyperbranched poly pyrrole throat copolymer and 10mL is sequentially added Mass fraction 98% the concentrated sulfuric acid, under nitrogen protection, at 40 DEG C stir 180min after, pour into frozen water, washed repeatedly with frozen water After washing the product, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C of dryings obtain final product sulfonated polyether amine-hyperbranched for 24 hours Poly- pyrrole throat copolymer；
（6）Prepare modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer
In 1000ml three-necked bottles, step is added（1）0.2 gram of the polyquaternium for obtaining, 0.1 gram of graphene oxide, step（5） The sulfonated polyether amine for obtaining -0.5 gram of hyperbranched poly pyrrole throat copolymer, 0.2 gram of hexamethylene diamine, 0.05 gram of NaOH, deionized water 2mL and DMF 50ml, after stirring at room temperature；After being reacted 10 hours at 60 DEG C, room temperature is down to, and Pour into 2000mL methyl alcohol rapidly, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration simultaneously collects polymerization Thing, in vacuum drying oven, 60 DEG C of dryings 24 hours obtain modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer.
By the acrylic emulsion of 100 weight portions, the tungstic acid of 50 weight portions, the titanium dioxide of 30 weight portions, 8 weight portions Copper chloride, the above-mentioned nano-powder for photochromic coating of 45 weight portions, the KH-560 of 2 weight portions, 3 weight portions The deionized water of KH-550, the ethanol of 3 weight portions and 9 weight portions is added in agravic blender, fly cutter is opened, to avoid out Now bond, prevent stirring uneven, mixing time is 30 minutes, discharging.
Embodiment 7
The epoxy-capped polyetheramine of the epoxy-capped polyetheramine cladding nano silicon of 10 weight portions, 3 weight portions is coated purple Modification sulphonation polyetheramine-hyperbranched poly pyrrole throat the copolymer and organic sodium base modified montmorillonoid of 3 weight portions of sand, 6 weight portions Add the nano-powder obtained after being sufficiently mixed 15 minutes in mixer for photochromic coating, the stirring speed of the mixer Rate is 600 revs/min；
Wherein, the epoxy-capped polyetheramine cladding nano silicon is prepared from by following methods：
In the dry three-necked bottles of 3L, the benzylamine and 500 grams of dimethyl of 100 grams epoxy resin E51,0.24mol are sequentially added Sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 80 DEG C of reaction 4h, is down to room temperature, is subsequently adding 500 grams Dimethyl sulfoxide (DMSO) and 300 grams of nano silicons, heat up 80 DEG C reaction 1h, be down to room temperature, and pour into rapidly 3000mL go from In sub- water, a large amount of solids of sedimentation are obtained；With after the deionized water cyclic washing product, suction filtration and collected polymer dry in vacuum In case, 60 DEG C of dryings 20 hours obtain epoxy-capped polyetheramine cladding nano silicon；
The epoxy-capped polyetheramine cladding boccaro is prepared from by following methods：
In the dry three-necked bottles of 3L, the benzylamine and 500 grams of dimethyl of 100 grams epoxy resin E51,0.24mol are sequentially added Sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 80 DEG C of reaction 4h, is down to room temperature, is subsequently adding 700 grams Dimethyl sulfoxide (DMSO) and 400 grams of boccaros, heat up 80 DEG C of reaction 1h, is down to room temperature, and pours into rapidly in 3000mL deionized waters, obtains To a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C Dry 20 hours, obtain epoxy-capped polyetheramine cladding boccaro；
The modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared from by following methods：
（1）Prepare polyquaternium
In the dry three-necked bottles of 1000ml, add 1,12- dibromo-dodecanes 0.1mol, Isosorbide-5-Nitrae-lupetazin 0.092mol with And solvent dimethyl sulfoxide (DMSO) 80ml, after being reacted 5 hours at 50 DEG C, add N- methylimidazole 0.0025mol and N- methyl Quinoline 0.0025mol, after being reacted 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium；
（2）Prepare amino-terminated polyetheramine
In the dry three-necked bottles of 1000mL, the benzylamine and 700 grams of diformazans of 95 grams epoxy resin E51,0.26mol are sequentially added Base sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature, And pour into rapidly in 2000mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration is simultaneously Collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain amino-terminated polyetheramine；
（3）Prepare hyperbranched poly pyrrole throat
In the dry three-necked bottles of 100mL, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) acid anhydrides of benzene three are sequentially added With 25ml metacresols, stir under nitrogen protection, after three acid anhydrides are completely dissolved, add the 3 of 0.006 mole, 3 '-benzidine Amine, after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction terminates, it is down to Room temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously received Collection polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
（4）Prepare polyetheramine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of described amino-terminated polyetheramine, 0.6 gram of naphthalene anhydride end-blocking is sequentially added The metacresol of hyperbranched poly pyrrole throat, the dimethyl sulfoxide (DMSO) of 10mL and 10mL, after stirring 60min under nitrogen protection, is heated to 80 DEG C, 4h is reacted, then at 185 DEG C, react 10h；After reaction terminates, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol, obtained To a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours, obtain final product polyetheramine-hyperbranched poly pyrrole throat copolymer；
（5）Prepare sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of the polyetheramine-hyperbranched poly pyrrole throat copolymer and 10mL is sequentially added Mass fraction 98% the concentrated sulfuric acid, under nitrogen protection, at 40 DEG C stir 180min after, pour into frozen water, washed repeatedly with frozen water After washing the product, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C of dryings obtain final product sulfonated polyether amine-hyperbranched for 24 hours Poly- pyrrole throat copolymer；
（6）Prepare modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer
In 1000ml three-necked bottles, step is added（1）0.2 gram of the polyquaternium for obtaining, 0.1 gram of graphene oxide, step（5） The sulfonated polyether amine for obtaining -0.5 gram of hyperbranched poly pyrrole throat copolymer, 0.2 gram of hexamethylene diamine, 0.05 gram of NaOH, deionized water 2mL and DMF 50ml, after stirring at room temperature；After being reacted 10 hours at 60 DEG C, room temperature is down to, and Pour into 2000mL methyl alcohol rapidly, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration simultaneously collects polymerization Thing, in vacuum drying oven, 60 DEG C of dryings 24 hours obtain modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer.
By the acrylic emulsion of 100 weight portions, the tungstic acid of 50 weight portions, the titanium dioxide of 30 weight portions, 8 weight portions Copper chloride, the above-mentioned nano-powder for photochromic coating of 45 weight portions, the KH-560 of 2 weight portions, 3 weight portions The deionized water of KH-550, the ethanol of 3 weight portions and 9 weight portions is added in agravic blender, fly cutter is opened, to avoid out Now bond, prevent stirring uneven, mixing time is 30 minutes, discharging；
The preparation method of organic sodium base modified montmorillonoid is：
15g calcium-base montmorillonites, plus 800ml distilled water are taken, 20min is stirred, Na is added2CO35g, stirs, and staticly settles and removes It is miscellaneous, 5min is centrifuged under the conditions of 2000r/min, separate and obtain sodium-based montmorillonite.
Test condition
Photochromic coating obtained by embodiment 1-7 is coated on road, and test performance.
According to GA98-2005 standard testings, specially：
1st, surface drying time answers≤24h
2nd, adhesion strength >=0.1Mpa
3rd, water resistance：After 720h, coating does not ftracture, aliquation, come off
4th, acid resistance：After 360h, coating does not ftracture, aliquation, come off
5th, alkali resistance：After 360h, coating does not ftracture, aliquation, come off
6th, freeze-thawing resistant circulation experiment（It is secondary）：After 15 times, coating does not ftracture, aliquation, come off
7th, fire resistance：Coating layer thickness is 20mm, and fire endurance is not less than 2h
Test result is shown in Table 1.
Table 1
Test event Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7
Drying time, surface drying/h 1.2 6.9 5.5 4.3 3.5 3.7 1.0
Adhesion strength/Mpa 0.72 0.33 0.42 0.45 0.59 0.55 0.88
Water resistance/h 2567 1780 2003 2157 2226 2300 2719
Acid resistance/h 1651 908 1129 1221 1357 1409 1890
Alkali resistance/h 1123 765 888 903 955 1001 1235
Freeze-thawing resistant circulation/number of times 69 40 46 50 55 58 76
Fire endurance/h 6.1 4.7 5.0 5.0 5.2 5.5 7.8
Antibiotic rate 99% 96% 98% 0 98% 98% 99%
Data above can be seen that and not use epoxy-capped polyetheramine cladding nano silicon, modification sulphonation polyetheramine-super The coating of branched poly- pyrrole throat copolymer and epoxy-capped polyetheramine cladding boccaro is compared, and coating of the invention has substantially more preferably Performance, be thus provided that Advantageous Effects of the invention.

Claims (6)

1. a kind of nano-powder for photochromic coating, it is characterised in that by weight, including following components：
The epoxy-capped polyetheramine cladding nano silicon of 10 weight portions, the epoxy-capped polyetheramine cladding of 1-5 weight portions are purple The modification sulphonation polyetheramine of sand and 5-10 weight portions-hyperbranched poly pyrrole throat copolymer；
The modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer passes through polyquaternium and graphene oxide and sulfonated polyether Amine-hyperbranched poly pyrrole throat copolymer reaction is obtained.
2. the nano-powder for photochromic coating according to claim 1, it is characterised in that described epoxy-capped poly- Ether amines cladding nano silicon is prepared from by following methods：
In the dry three-necked bottles of 3L, the benzylamine and 500 grams of dimethyl of 100 grams epoxy resin E51,0.24mol are sequentially added Sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 80 DEG C of reaction 4h, is down to room temperature, is subsequently adding 500 grams Dimethyl sulfoxide (DMSO) and 300 grams of nano silicons, heat up 80 DEG C reaction 1h, be down to room temperature, and pour into rapidly 3000mL go from In sub- water, a large amount of solids of sedimentation are obtained；With after the deionized water cyclic washing product, suction filtration and collected polymer dry in vacuum In case, 60 DEG C of dryings 20 hours obtain epoxy-capped polyetheramine cladding nano silicon.
3. the nano-powder for photochromic coating according to claim 1, it is characterised in that described epoxy-capped poly- Ether amines cladding boccaro is prepared from by following methods：
In the dry three-necked bottles of 3L, the benzylamine and 500 grams of dimethyl of 100 grams epoxy resin E51,0.24mol are sequentially added Sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 80 DEG C of reaction 4h, is down to room temperature, is subsequently adding 700 grams Dimethyl sulfoxide (DMSO) and 400 grams of boccaros, heat up 80 DEG C of reaction 1h, is down to room temperature, and pours into rapidly in 3000mL deionized waters, obtains To a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C Dry 20 hours, obtain epoxy-capped polyetheramine cladding boccaro.
4. the nano-powder for photochromic coating according to claim 1, it is characterised in that the modification sulphonation gathers Ether amines-hyperbranched poly pyrrole throat copolymer is prepared from by following methods：
（1）Prepare polyquaternium
In the dry three-necked bottles of 1000ml, add 1,12- dibromo-dodecanes 0.1mol, Isosorbide-5-Nitrae-lupetazin 0.092mol with And solvent dimethyl sulfoxide (DMSO) 80ml, after being reacted 5 hours at 50 DEG C, add N- methylimidazole 0.0025mol and N- methyl Quinoline 0.0025mol, after being reacted 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium；
（2）Prepare amino-terminated polyetheramine
In the dry three-necked bottles of 1000mL, the benzylamine and 700 grams of diformazans of 95 grams epoxy resin E51,0.26mol are sequentially added Base sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature, And pour into rapidly in 2000mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration is simultaneously Collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain amino-terminated polyetheramine；
（3）Prepare hyperbranched poly pyrrole throat
In the dry three-necked bottles of 100mL, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) acid anhydrides of benzene three are sequentially added With 25ml metacresols, stir under nitrogen protection, after three acid anhydrides are completely dissolved, add the 3 of 0.006 mole, 3 '-benzidine Amine, after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction terminates, it is down to Room temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously received Collection polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
（4）Prepare polyetheramine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of described amino-terminated polyetheramine, 0.6 gram of naphthalene anhydride end-blocking is sequentially added The metacresol of hyperbranched poly pyrrole throat, the dimethyl sulfoxide (DMSO) of 10mL and 10mL, after stirring 60min under nitrogen protection, is heated to 80 DEG C, 4h is reacted, then at 185 DEG C, react 10h；After reaction terminates, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol, obtained To a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours, obtain final product polyetheramine-hyperbranched poly pyrrole throat copolymer；
（5）Prepare sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of the polyetheramine-hyperbranched poly pyrrole throat copolymer and 10mL is sequentially added Mass fraction 98% the concentrated sulfuric acid, under nitrogen protection, at 40 DEG C stir 180min after, pour into frozen water, washed repeatedly with frozen water After washing the product, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C of dryings obtain final product sulfonated polyether amine-hyperbranched for 24 hours Poly- pyrrole throat copolymer；
（6）Prepare modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer
In 1000ml three-necked bottles, step is added（1）0.2 gram of the polyquaternium for obtaining, 0.1 gram of graphene oxide, step（5） The sulfonated polyether amine for obtaining -0.5 gram of hyperbranched poly pyrrole throat copolymer, 0.2 gram of hexamethylene diamine, 0.05 gram of NaOH, deionized water 2mL and DMF 50ml, after stirring at room temperature；After being reacted 10 hours at 60 DEG C, room temperature is down to, and Pour into 2000mL methyl alcohol rapidly, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration simultaneously collects polymerization Thing, in vacuum drying oven, 60 DEG C of dryings 24 hours obtain modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer.
5. a kind of photochromic coating, it is characterised in that by weight, including following components：
The acrylic emulsion of 100 weight portions, the tungstic acid of 30-60 weight portions, the titanium dioxide of 20-40 weight portions, 5-10 weights Measure the nano-powder for photochromic coating described in the copper chloride of part, the claim any one of 1-4 of 20-60 weight portions, The ethanol of KH-550,1-5 weight portion of KH-560,1-5 weight portion of 1-5 weight portions and the deionized water of 5-10 weight portions.
6. photochromic coating according to claim 5, it is characterised in that by weight, including following components：
The acrylic emulsion of 100 weight portions, the tungstic acid of 50 weight portions, the titanium dioxide of 30 weight portions, the chlorination of 8 weight portions The nano-powder for photochromic coating, the KH- of 2 weight portions described in copper, the claim any one of 1-4 of 45 weight portions 560th, the deionized water of the KH-550 of 3 weight portions, the ethanol of 3 weight portions and 9 weight portions.
CN201710069283.9A 2017-02-08 2017-02-08 A kind of nano-powder and photochromic coating therefrom for photochromic coating Active CN106800846B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710069283.9A CN106800846B (en) 2017-02-08 2017-02-08 A kind of nano-powder and photochromic coating therefrom for photochromic coating

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710069283.9A CN106800846B (en) 2017-02-08 2017-02-08 A kind of nano-powder and photochromic coating therefrom for photochromic coating

Publications (2)

Publication Number Publication Date
CN106800846A true CN106800846A (en) 2017-06-06
CN106800846B CN106800846B (en) 2019-04-30

Family

ID=58988556

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710069283.9A Active CN106800846B (en) 2017-02-08 2017-02-08 A kind of nano-powder and photochromic coating therefrom for photochromic coating

Country Status (1)

Country Link
CN (1) CN106800846B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110776669A (en) * 2019-09-24 2020-02-11 惠州市志海新威科技有限公司 Heat-conducting flame retardant and preparation method thereof
US11795107B2 (en) 2020-08-12 2023-10-24 Saudi Arabian Oil Company Encapsulation of silica nanoparticle for release
CN117229695A (en) * 2023-09-22 2023-12-15 辽宁顺风新材料科技有限公司 Modified high-solid-content coating and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1180721A (en) * 1996-10-17 1998-05-06 宜兴市金砂特种紫砂工艺陶有限公司 Purple sand paint and application thereof
CN103468074A (en) * 2013-09-03 2013-12-25 吴江市冰心文教用品有限公司 Photochromic paint
CN105670420A (en) * 2016-03-28 2016-06-15 云南佑琳生科技有限公司 Ultrathin steel structural fireproof anti-radiation coating
CN105754431A (en) * 2016-04-01 2016-07-13 云南佑琳生科技有限公司 Exterior wall coating material capable of finishing working through one-time painting
CN106318198A (en) * 2016-09-18 2017-01-11 北京佑琳生科技有限公司 Water-based nano-resin outdoor ultrathin fireproof coating for steel structure

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1180721A (en) * 1996-10-17 1998-05-06 宜兴市金砂特种紫砂工艺陶有限公司 Purple sand paint and application thereof
CN103468074A (en) * 2013-09-03 2013-12-25 吴江市冰心文教用品有限公司 Photochromic paint
CN105670420A (en) * 2016-03-28 2016-06-15 云南佑琳生科技有限公司 Ultrathin steel structural fireproof anti-radiation coating
CN105754431A (en) * 2016-04-01 2016-07-13 云南佑琳生科技有限公司 Exterior wall coating material capable of finishing working through one-time painting
CN106318198A (en) * 2016-09-18 2017-01-11 北京佑琳生科技有限公司 Water-based nano-resin outdoor ultrathin fireproof coating for steel structure

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110776669A (en) * 2019-09-24 2020-02-11 惠州市志海新威科技有限公司 Heat-conducting flame retardant and preparation method thereof
US11795107B2 (en) 2020-08-12 2023-10-24 Saudi Arabian Oil Company Encapsulation of silica nanoparticle for release
US12054424B2 (en) 2020-08-12 2024-08-06 Saudi Arabian Oil Company Encapsulation of silica nanoparticle for release
CN117229695A (en) * 2023-09-22 2023-12-15 辽宁顺风新材料科技有限公司 Modified high-solid-content coating and preparation method thereof

Also Published As

Publication number Publication date
CN106800846B (en) 2019-04-30

Similar Documents

Publication Publication Date Title
CN105670420B (en) A kind of ultra-thin steel structure fireproof and radiation-proof coating
CN106800846A (en) A kind of nano-powder and photochromic coating therefrom for photochromic coating
CN105623325B (en) A kind of thicker steel structure fireproofing radiation shielding coating
CN106318128A (en) Outdoor ultrathin fireproof coating
CN106007582B (en) A kind of slim dry powder fire-resistant coating for steel structure
CN105602480B (en) High cohesive force building marine glue of environment-friendly type high durable and preparation method thereof
CN106800812A (en) Compound flatting silica of a kind of improved silica and preparation method thereof
CN106630872B (en) A kind of fireproof coating exclusively for tunnel
CN102432979A (en) Preparation method of epoxy resin-attapulgite nanocomposite material
CN106866074A (en) A kind of high temperature resistant high-hardness water-proof wall covering and preparation method thereof
CN105694723B (en) A kind of three-in-one dry powder paint of interior wall
CN105505289B (en) High intensity polysulfide waterproof construction glue and preparation method thereof
CN101891936A (en) Preparation method of composite material based on epoxy resin and phosphazene nanotubes
CN105860355B (en) High ferro high fire-retardance high durable rubber floor covering and preparation method thereof
CN106700929B (en) A kind of environmentally protective high durable radiation protection exterior coating
CN106675402B (en) A kind of environment-friendly type is without aldehyde radiation protection interior wall luminous ornament coating
CN105440999B (en) Room curing and high temperature resistant anti-corrosion epoxy structural rubber and preparation method thereof
CN107057569A (en) A kind of nano inorganic silicate zinc-rich composite anticorrosion coating and preparation method thereof
CN105837088B (en) A kind of exterior wall inorganic silicon-aluminum dry powder paint
CN106854434A (en) A kind of energy-accumulating luminous paint
CN106675401A (en) Corona-resistant wire enamel and preparation method thereof
CN106833053A (en) A kind of wall covering and preparation method thereof
CN107298943A (en) A kind of sound-absorbing fireproof coating
CN106700928A (en) Special luminescent energy storage coating for tunnels
CN106700896A (en) Anti-haze coating

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20190624

Address after: 511340 East of 1st floor, No. 11 Yinsha Second Road, Xintang Town, Zengcheng District, Guangzhou City, Guangdong Province

Patentee after: ANYAN NANOMETER NEW MATERIAL TECHNOLOGY (GUANGZHOU) CO., LTD.

Address before: 511340 Meiji Industrial Zone, Nan'an Village, Xintang Town, Zengcheng District, Guangzhou City, Guangdong Province

Patentee before: Guangzhou new composite material Co., Ltd.

TR01 Transfer of patent right