CN106800846B - 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

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CN106800846B
CN106800846B CN201710069283.9A CN201710069283A CN106800846B CN 106800846 B CN106800846 B CN 106800846B CN 201710069283 A CN201710069283 A CN 201710069283A CN 106800846 B CN106800846 B CN 106800846B
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weight
parts
polyetheramine
room temperature
pyrrole throat
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CN106800846A (en
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钟学群
杨雪英
陈建山
刘民
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ANYAN NANOMETER NEW MATERIAL TECHNOLOGY (GUANGZHOU) CO., LTD.
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Guangzhou New Composite Material Co Ltd
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    • 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
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    • 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
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    • C08L2312/00—Crosslinking

Abstract

The invention discloses a kind of nano-powders for photochromic coating, by weight, including following components: epoxy-capped polyetheramine cladding nano silica, the epoxy-capped polyetheramine cladding boccaro of 1-5 parts by weight and the modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer of 5-10 parts by weight of 10 parts by weight；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 coatings for 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 technique
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, craftwork, clock and watch, instrument board, weaving Product, fire-fighting equipment, military affairs, facility etc. of camping all have been widely used.Existing photochromic coating is lacked there is following Point:
(1) weatherability, water resistance of product cannot generally reach requirement；
(2) in the case of fire, the film forming matter of these fireproof coatings cannot bear sharply raised temperature and quickly by It burns, and fire-proof cannot be played the role of；
(3) performances such as anti-corrosion, acid and alkali-resistance, antibacterial are poor.
Therefore, the present invention wishes by the way that nano-powder is added, obtain that weatherability is strong, fire resistance is good and has anti-corrosion, resist The photochromic coating of bacterium and acidproof alkali ability.
Summary of the invention
To solve the above-mentioned 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 of 10 parts by weight coats the epoxy-capped polyetheramine packet of nano silica, 1-5 parts by weight Cover modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer of boccaro and 5-10 parts by weight；
The modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer passes through polyquaternium and graphene oxide and sulfonation Polyetheramine-hyperbranched poly pyrrole throat copolymer reaction obtains.
In one embodiment, the epoxy-capped polyetheramine cladding nano silica prepared by following methods and At:
In 3L dry three-necked bottle, sequentially add 100 grams epoxy resin E51,0.24mol benzylamine and 500 gram two Methyl sulfoxide leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heats up 80 DEG C and react 4h, be down to room temperature, be then added 500 grams of dimethyl sulfoxides and 300 grams of nano silicas, heat up 80 DEG C and react 1h, be down to room temperature, and pour into 3000mL rapidly In deionized water, a large amount of solid precipitatings are obtained；After washing the product repeatedly with deionized water, simultaneously collected polymer, Yu Zhen are filtered In empty baking oven, 60 DEG C drying 20 hours, obtain epoxy-capped polyetheramine cladding nano silica.
In one embodiment, the nano silica the preparation method comprises the following steps:
(1) SILICA FUME is dissolved in sodium hydroxide solution, centrifugation or filtering remove undissolved solid residue, and 50 DEG C add Heat is lower to react 10h；
(2) after using supernatant respectively cation exchange resin and anion exchange resin to remove impurity, by ion exchange After resin is separated with reaction solution；
(3) solution that step (2) processing obtains is dried to get nano silica is arrived；
The concentration of the sodium hydroxide solution is 30%~60%；
The w/v of the SILICA FUME and sodium hydroxide solution are as follows: 40%~80%g/mL.
In one embodiment, the epoxy-capped polyetheramine cladding boccaro is prepared by following methods:
In 3L dry three-necked bottle, sequentially add 100 grams epoxy resin E51,0.24mol benzylamine and 500 gram two Methyl sulfoxide leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heats up 80 DEG C and react 4h, be down to room temperature, be then added 700 grams of dimethyl sulfoxides and 400 grams of boccaros, heat up 80 DEG C and react 1h, be down to room temperature, and pour into 3000mL deionized water rapidly In, obtain a large amount of solid precipitatings；After washing the product repeatedly with deionized water, simultaneously collected polymer is filtered, in vacuum drying oven, 60 DEG C drying 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 It forms:
(1) polyquaternium is prepared
In 1000ml dry three-necked bottle, 1,12- dibromo-dodecane 0.1mol, Isosorbide-5-Nitrae-lupetazin is added 0.092mol and solvent dimethyl sulfoxide 80ml, after reacting 5 hours at 50 DEG C, add N- methylimidazole 0.0025mol with And N-methylmorpholine 0.0025mol, after reacting 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium；
(2) amino-terminated polyetheramine is prepared
In 1000mL dry three-necked bottle, sequentially add 95 grams epoxy resin E51,0.26mol benzylamine and 700 grams Dimethyl sulfoxide leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heats up 95 DEG C and react 6h, after reaction, be down to Room temperature, and pour into rapidly in 2000mL deionized water, obtain a large amount of solid precipitatings；After washing the product repeatedly with deionized water, Filter and collected polymer, in vacuum drying oven, 50 DEG C drying 24 hours, obtain amino-terminated polyetheramine；
(3) hyperbranched poly pyrrole throat is prepared
In 100mL dry three-necked bottle, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) benzene are sequentially added Three acid anhydrides and 25ml metacresol, are stirred under nitrogen protection, and after three acid anhydrides are completely dissolved, 0.006 mole of 3,3 '-diamino are added Benzidine after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction, It is down to room temperature, and is poured into rapidly in 2000mL methanol, a large amount of solid precipitatings are obtained；After washing the product repeatedly with methanol, filter And collected polymer, in vacuum drying oven, 50 DEG C drying 24 hours to get the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
(4) polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared
In 100mL dry three-necked bottle, 1 gram of the amino-terminated polyetheramine, 0.6 gram of the naphthalene anhydride are sequentially added Terminated hyperbranched poly- pyrrole throat, the dimethyl sulfoxide of 10mL and the metacresol of 10mL add after stirring 60min under nitrogen protection Heat reacts 4h to 80 DEG C, then at 185 DEG C, reacts 10h；After reaction, it is down to room temperature, and pours into 2000mL methanol rapidly In, obtain a large amount of solid precipitatings；After washing the product repeatedly with methanol, simultaneously collected polymer, in vacuum drying oven, 50 DEG C are filtered Dry 24 hours to get polyetheramine-hyperbranched poly pyrrole throat copolymer；
(5) sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer is prepared
In 100mL dry three-necked bottle, sequentially add 1 gram the polyetheramine-hyperbranched poly pyrrole throat copolymer and The concentrated sulfuric acid of the mass fraction 98% of 10mL after stirring 180min at 40 DEG C, pours into ice water under nitrogen protection, anti-with ice water After the product is washed in after backwashing, simultaneously collected polymer is filtered, in vacuum drying oven, 60 DEG C surpass for drying 24 hours up to sulfonated polyether amine- The poly- pyrrole throat copolymer of branching；
(6) modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared
In 1000ml three-necked bottle, 0.1 gram of 0.2 gram of polyquaternium, graphene oxide, the step that step (1) obtains is added (5) the sulfonated polyether amine obtained -0.5 gram of hyperbranched poly pyrrole throat copolymer, 0.2 gram of hexamethylene diamine, 0.05 gram of sodium hydroxide, deionization Water 2mL and n,N-Dimethylformamide 50ml, at room temperature after mixing evenly；After reacting 10 hours at 60 DEG C, it is down to room temperature, And pour into rapidly in 2000mL methanol, obtain a large amount of solid precipitatings；After washing the product repeatedly with methanol, filters and collect polymerization Object, in vacuum drying oven, 60 DEG C drying 24 hours, obtain modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer.
In one embodiment, the nano-powder for photochromic coating further includes the organic of 1-5 parts by weight Sodium base modified montmorillonoid, and organic sodium base modified montmorillonoid the preparation method comprises the following steps:
15g calcium-base montmorillonite is taken, 800ml distilled water is added, stirs 20min, Na is added2CO3 5g is stirred evenly, and it is heavy to stand It forms sediment and cleans, be centrifuged 5min 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 parts by weight, the tungstic acid of 30-60 parts by weight, 20-40 parts by weight titanium dioxide, 5- The copper chlorides of 10 parts by weight, the described nano-powder for photochromic coating of 20-60 parts by weight, 1-5 parts by weight KH- 560, the deionized water of the ethyl alcohol of KH-550,1-5 parts by weight of 1-5 parts by weight and 5-10 parts by weight；
Preferably, the photochromic coating, by weight, including following components:
The acrylic emulsion of 100 parts by weight, the tungstic acid of 50 parts by weight, the titanium dioxide of 30 parts by weight, 8 parts by weight Copper chloride, 45 parts by weight it is described for the nano-powder of photochromic coating, the KH-560 of 2 parts by weight, 3 parts by weight The deionized water of KH-550, the ethyl alcohol of 3 parts by weight and 9 parts by weight.
Compared with prior art, the invention has the benefit that
1, epoxy-capped polyetheramine contains great amount of hydroxy group, can greatly improve the cohesive force of coating and substrate, improves coating Ageing-resistant ability improve crosslink density and solidification rate, a large amount of rigidity on this outside chain in addition, it can also be reacted with amino The distance of strand can be improved in the introducing of phenyl ring, improves flame retardant effect.By coating filler, filler and body are substantially increased The compatibility of system, to provide advantageous effects of the invention.
2, modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer addition can both provide excellent weatherability, higher Intensity, good flame retardant property and excellent anti-microbial property, and can play plasticization again prevents system excessively crisp, also Processing step can be greatly reduced and substantially increase the degree of cross linking of system, 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, and are not necessarily to It is further purified.Coupling agent KH-550, KH-560, boccaro (500 mesh of average grain diameter), calcium-base montmorillonite (500 mesh of average grain diameter), Tungstic acid (2000 mesh of average grain diameter) and titanium dioxide (200 nanometers of average grain diameter) are limited purchased from Chinese medicines group chemical reagent Company.Graphene oxide is rich purchased from Suzhou carbon.Acrylic emulsion is purchased from Guangdong Xin Yi Chemical Co., Ltd., trade mark NACRYLIC 2800。
Nano silica (average grain diameter 100nm) self-control, the preparation method comprises the following steps:
(1) SILICA FUME is dissolved in sodium hydroxide solution, centrifugation or filtering remove undissolved solid residue, and 50 DEG C add Heat is lower to react 10h；
(2) after using supernatant respectively cation exchange resin and anion exchange resin to remove impurity, by ion exchange After resin is separated with reaction solution；
(3) solution that step (2) processing obtains is dried to get nano silica is arrived；
The concentration of the sodium hydroxide solution is 50%；
The w/v of the SILICA FUME and sodium hydroxide solution are as follows: 75%g/mL.
Other raw materials are purchased from Aladdin reagent Co., Ltd.
Embodiment 1
By the epoxy-capped polyetheramine packet of the epoxy-capped polyetheramine cladding nano silica of 10 parts by weight, 3 parts by weight It covers in boccaro and modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer addition blender of 6 parts by weight and is sufficiently mixed 15 points The nano-powder for photochromic coating is obtained after clock, the stirring rate of the blender is 600 revs/min；
Wherein, the epoxy-capped polyetheramine cladding nano silica is prepared by following methods:
In 3L dry three-necked bottle, sequentially add 100 grams epoxy resin E51,0.24mol benzylamine and 500 gram two Methyl sulfoxide leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heats up 80 DEG C and react 4h, be down to room temperature, be then added 500 grams of dimethyl sulfoxides and 300 grams of nano silicas, heat up 80 DEG C and react 1h, be down to room temperature, and pour into 3000mL rapidly In deionized water, a large amount of solid precipitatings are obtained；After washing the product repeatedly with deionized water, simultaneously collected polymer, Yu Zhen are filtered In empty baking oven, 60 DEG C drying 20 hours, obtain epoxy-capped polyetheramine cladding nano silica；
The epoxy-capped polyetheramine cladding boccaro is prepared by following methods:
In 3L dry three-necked bottle, sequentially add 100 grams epoxy resin E51,0.24mol benzylamine and 500 gram two Methyl sulfoxide leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heats up 80 DEG C and react 4h, be down to room temperature, be then added 700 grams of dimethyl sulfoxides and 400 grams of boccaros, heat up 80 DEG C and react 1h, be down to room temperature, and pour into 3000mL deionized water rapidly In, obtain a large amount of solid precipitatings；After washing the product repeatedly with deionized water, simultaneously collected polymer is filtered, in vacuum drying oven, 60 DEG C drying 20 hours, obtain epoxy-capped polyetheramine cladding boccaro；
The modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared by following methods:
(1) polyquaternium is prepared
In 1000ml dry three-necked bottle, 1,12- dibromo-dodecane 0.1mol, Isosorbide-5-Nitrae-lupetazin is added 0.092mol and solvent dimethyl sulfoxide 80ml, after reacting 5 hours at 50 DEG C, add N- methylimidazole 0.0025mol with And N-methylmorpholine 0.0025mol, after reacting 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium；
(2) amino-terminated polyetheramine is prepared
In 1000mL dry three-necked bottle, sequentially add 95 grams epoxy resin E51,0.26mol benzylamine and 700 grams Dimethyl sulfoxide leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heats up 95 DEG C and react 6h, after reaction, be down to Room temperature, and pour into rapidly in 2000mL deionized water, obtain a large amount of solid precipitatings；After washing the product repeatedly with deionized water, Filter and collected polymer, in vacuum drying oven, 50 DEG C drying 24 hours, obtain amino-terminated polyetheramine；
(3) hyperbranched poly pyrrole throat is prepared
In 100mL dry three-necked bottle, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) benzene are sequentially added Three acid anhydrides and 25ml metacresol, are stirred under nitrogen protection, and after three acid anhydrides are completely dissolved, 0.006 mole of 3,3 '-diamino are added Benzidine after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction, It is down to room temperature, and is poured into rapidly in 2000mL methanol, a large amount of solid precipitatings are obtained；After washing the product repeatedly with methanol, filter And collected polymer, in vacuum drying oven, 50 DEG C drying 24 hours to get the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
(4) polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared
In 100mL dry three-necked bottle, 1 gram of the amino-terminated polyetheramine, 0.6 gram of the naphthalene anhydride are sequentially added Terminated hyperbranched poly- pyrrole throat, the dimethyl sulfoxide of 10mL and the metacresol of 10mL add after stirring 60min under nitrogen protection Heat reacts 4h to 80 DEG C, then at 185 DEG C, reacts 10h；After reaction, it is down to room temperature, and pours into 2000mL methanol rapidly In, obtain a large amount of solid precipitatings；After washing the product repeatedly with methanol, simultaneously collected polymer, in vacuum drying oven, 50 DEG C are filtered Dry 24 hours to get polyetheramine-hyperbranched poly pyrrole throat copolymer；
(5) sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer is prepared
In 100mL dry three-necked bottle, sequentially add 1 gram the polyetheramine-hyperbranched poly pyrrole throat copolymer and The concentrated sulfuric acid of the mass fraction 98% of 10mL after stirring 180min at 40 DEG C, pours into ice water under nitrogen protection, anti-with ice water After the product is washed in after backwashing, simultaneously collected polymer is filtered, in vacuum drying oven, 60 DEG C surpass for drying 24 hours up to sulfonated polyether amine- The poly- pyrrole throat copolymer of branching；
(6) modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared
In 1000ml three-necked bottle, 0.1 gram of 0.2 gram of polyquaternium, graphene oxide, the step that step (1) obtains is added (5) the sulfonated polyether amine obtained -0.5 gram of hyperbranched poly pyrrole throat copolymer, 0.2 gram of hexamethylene diamine, 0.05 gram of sodium hydroxide, deionization Water 2mL and n,N-Dimethylformamide 50ml, at room temperature after mixing evenly；After reacting 10 hours at 60 DEG C, it is down to room temperature, And pour into rapidly in 2000mL methanol, obtain a large amount of solid precipitatings；After washing the product repeatedly with methanol, filters and collect polymerization Object, in vacuum drying oven, 60 DEG C drying 24 hours, obtain modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer；
By the acrylic emulsion of 100 parts by weight, the tungstic acid of 50 parts by weight, the titanium dioxide of 30 parts by weight, 8 parts by weight Copper chloride, 45 parts by weight it is above-mentioned for the nano-powder of photochromic coating, the KH-560 of 2 parts by weight, 3 parts by weight The deionized water of KH-550, the ethyl alcohol of 3 parts by weight and 9 parts by weight are added in agravic blender, open fly cutter, to avoid going out It now bonds, prevents stirring uneven, mixing time is 30 minutes, discharging.
Embodiment 2
The epoxy-capped polyetheramine of 10 parts by weight is coated to the epoxy-capped polyetheramine of nano silica and 3 parts by weight The nano-powder for photochromic coating, the blender are obtained after being sufficiently mixed 15 minutes in cladding boccaro addition blender Stirring rate be 600 revs/min；
Wherein, the epoxy-capped polyetheramine cladding nano silica is prepared by following methods:
In 3L dry three-necked bottle, sequentially add 100 grams epoxy resin E51,0.24mol benzylamine and 500 gram two Methyl sulfoxide leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heats up 80 DEG C and react 4h, be down to room temperature, be then added 500 grams of dimethyl sulfoxides and 300 grams of nano silicas, heat up 80 DEG C and react 1h, be down to room temperature, and pour into 3000mL rapidly In deionized water, a large amount of solid precipitatings are obtained；After washing the product repeatedly with deionized water, simultaneously collected polymer, Yu Zhen are filtered In empty baking oven, 60 DEG C drying 20 hours, obtain epoxy-capped polyetheramine cladding nano silica；
The epoxy-capped polyetheramine cladding boccaro is prepared by following methods:
In 3L dry three-necked bottle, sequentially add 100 grams epoxy resin E51,0.24mol benzylamine and 500 gram two Methyl sulfoxide leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heats up 80 DEG C and react 4h, be down to room temperature, be then added 700 grams of dimethyl sulfoxides and 400 grams of boccaros, heat up 80 DEG C and react 1h, be down to room temperature, and pour into 3000mL deionized water rapidly In, obtain a large amount of solid precipitatings；After washing the product repeatedly with deionized water, simultaneously collected polymer is filtered, in vacuum drying oven, 60 DEG C drying 20 hours, obtain epoxy-capped polyetheramine cladding nano silica；
By the acrylic emulsion of 100 parts by weight, the tungstic acid of 50 parts by weight, the titanium dioxide of 30 parts by weight, 8 parts by weight Copper chloride, 45 parts by weight it is above-mentioned for the nano-powder of photochromic coating, the KH-560 of 2 parts by weight, 3 parts by weight The deionized water of KH-550, the ethyl alcohol of 3 parts by weight and 9 parts by weight are added in agravic blender, open fly cutter, to avoid going out It now bonds, prevents stirring uneven, mixing time is 30 minutes, discharging.
Embodiment 3
The epoxy-capped polyetheramine of 10 parts by weight is coated to the modification sulphonation polyethers of nano silica and 6 parts by weight The nano powder for photochromic coating is obtained after being sufficiently mixed 15 minutes in amine-hyperbranched poly pyrrole throat copolymer addition blender Body, the stirring rate of the blender are 600 revs/min；
Wherein, the epoxy-capped polyetheramine cladding nano silica is prepared by following methods:
In 3L dry three-necked bottle, sequentially add 100 grams epoxy resin E51,0.24mol benzylamine and 500 gram two Methyl sulfoxide leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heats up 80 DEG C and react 4h, be down to room temperature, be then added 500 grams of dimethyl sulfoxides and 300 grams of nano silicas, heat up 80 DEG C and react 1h, be down to room temperature, and pour into 3000mL rapidly In deionized water, a large amount of solid precipitatings are obtained；After washing the product repeatedly with deionized water, simultaneously collected polymer, Yu Zhen are filtered In empty baking oven, 60 DEG C drying 20 hours, obtain epoxy-capped polyetheramine cladding nano silica；
The modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared by following methods:
(1) polyquaternium is prepared
In 1000ml dry three-necked bottle, 1,12- dibromo-dodecane 0.1mol, Isosorbide-5-Nitrae-lupetazin is added 0.092mol and solvent dimethyl sulfoxide 80ml, after reacting 5 hours at 50 DEG C, add N- methylimidazole 0.0025mol with And N-methylmorpholine 0.0025mol, after reacting 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium；
(2) amino-terminated polyetheramine is prepared
In 1000mL dry three-necked bottle, sequentially add 95 grams epoxy resin E51,0.26mol benzylamine and 700 grams Dimethyl sulfoxide leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heats up 95 DEG C and react 6h, after reaction, be down to Room temperature, and pour into rapidly in 2000mL deionized water, obtain a large amount of solid precipitatings；After washing the product repeatedly with deionized water, Filter and collected polymer, in vacuum drying oven, 50 DEG C drying 24 hours, obtain amino-terminated polyetheramine；
(3) hyperbranched poly pyrrole throat is prepared
In 100mL dry three-necked bottle, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) benzene are sequentially added Three acid anhydrides and 25ml metacresol, are stirred under nitrogen protection, and after three acid anhydrides are completely dissolved, 0.006 mole of 3,3 '-diamino are added Benzidine after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction, It is down to room temperature, and is poured into rapidly in 2000mL methanol, a large amount of solid precipitatings are obtained；After washing the product repeatedly with methanol, filter And collected polymer, in vacuum drying oven, 50 DEG C drying 24 hours to get the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
(4) polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared
In 100mL dry three-necked bottle, 1 gram of the amino-terminated polyetheramine, 0.6 gram of the naphthalene anhydride are sequentially added Terminated hyperbranched poly- pyrrole throat, the dimethyl sulfoxide of 10mL and the metacresol of 10mL add after stirring 60min under nitrogen protection Heat reacts 4h to 80 DEG C, then at 185 DEG C, reacts 10h；After reaction, it is down to room temperature, and pours into 2000mL methanol rapidly In, obtain a large amount of solid precipitatings；After washing the product repeatedly with methanol, simultaneously collected polymer, in vacuum drying oven, 50 DEG C are filtered Dry 24 hours to get polyetheramine-hyperbranched poly pyrrole throat copolymer；
(5) sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer is prepared
In 100mL dry three-necked bottle, sequentially add 1 gram the polyetheramine-hyperbranched poly pyrrole throat copolymer and The concentrated sulfuric acid of the mass fraction 98% of 10mL after stirring 180min at 40 DEG C, pours into ice water under nitrogen protection, anti-with ice water After the product is washed in after backwashing, simultaneously collected polymer is filtered, in vacuum drying oven, 60 DEG C surpass for drying 24 hours up to sulfonated polyether amine- The poly- pyrrole throat copolymer of branching；
(6) modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared
In 1000ml three-necked bottle, 0.1 gram of 0.2 gram of polyquaternium, graphene oxide, the step that step (1) obtains is added (5) the sulfonated polyether amine obtained -0.5 gram of hyperbranched poly pyrrole throat copolymer, 0.2 gram of hexamethylene diamine, 0.05 gram of sodium hydroxide, deionization Water 2mL and n,N-Dimethylformamide 50ml, at room temperature after mixing evenly；After reacting 10 hours at 60 DEG C, it is down to room temperature, And pour into rapidly in 2000mL methanol, obtain a large amount of solid precipitatings；After washing the product repeatedly with methanol, filters and collect polymerization Object, in vacuum drying oven, 60 DEG C drying 24 hours, obtain modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer.
By the acrylic emulsion of 100 parts by weight, the tungstic acid of 50 parts by weight, the titanium dioxide of 30 parts by weight, 8 parts by weight Copper chloride, 45 parts by weight it is above-mentioned for the nano-powder of photochromic coating, the KH-560 of 2 parts by weight, 3 parts by weight The deionized water of KH-550, the ethyl alcohol of 3 parts by weight and 9 parts by weight are added in agravic blender, open fly cutter, to avoid going out It now bonds, prevents stirring uneven, mixing time is 30 minutes, discharging.
Embodiment 4
By the epoxy-capped polyetheramine packet of the epoxy-capped polyetheramine cladding nano silica of 10 parts by weight, 3 parts by weight It covers after being sufficiently mixed 15 minutes in boccaro and modified polyether amine-hyperbranched poly pyrrole throat copolymer addition blender of 6 parts by weight The nano-powder for photochromic coating is obtained, the stirring rate of the blender is 600 revs/min；
Wherein, the epoxy-capped polyetheramine cladding nano silica is prepared by following methods:
In 3L dry three-necked bottle, sequentially add 100 grams epoxy resin E51,0.24mol benzylamine and 500 gram two Methyl sulfoxide leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heats up 80 DEG C and react 4h, be down to room temperature, be then added 500 grams of dimethyl sulfoxides and 300 grams of nano silicas, heat up 80 DEG C and react 1h, be down to room temperature, and pour into 3000mL rapidly In deionized water, a large amount of solid precipitatings are obtained；After washing the product repeatedly with deionized water, simultaneously collected polymer, Yu Zhen are filtered In empty baking oven, 60 DEG C drying 20 hours, obtain epoxy-capped polyetheramine cladding nano silica；
The epoxy-capped polyetheramine cladding boccaro is prepared by following methods:
In 3L dry three-necked bottle, sequentially add 100 grams epoxy resin E51,0.24mol benzylamine and 500 gram two Methyl sulfoxide leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heats up 80 DEG C and react 4h, be down to room temperature, be then added 700 grams of dimethyl sulfoxides and 400 grams of boccaros, heat up 80 DEG C and react 1h, be down to room temperature, and pour into 3000mL deionized water rapidly In, obtain a large amount of solid precipitatings；After washing the product repeatedly with deionized water, simultaneously collected polymer is filtered, in vacuum drying oven, 60 DEG C drying 20 hours, obtain epoxy-capped polyetheramine cladding nano silica；
The modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared by following methods:
(1) polyquaternium is prepared
In 1000ml dry three-necked bottle, 1,12- dibromo-dodecane 0.1mol, Isosorbide-5-Nitrae-lupetazin is added 0.092mol and solvent dimethyl sulfoxide 80ml, after reacting 5 hours at 50 DEG C, add N- methylimidazole 0.0025mol with And N-methylmorpholine 0.0025mol, after reacting 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium；
(2) amino-terminated polyetheramine is prepared
In 1000mL dry three-necked bottle, sequentially add 95 grams epoxy resin E51,0.26mol benzylamine and 700 grams Dimethyl sulfoxide leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heats up 95 DEG C and react 6h, after reaction, be down to Room temperature, and pour into rapidly in 2000mL deionized water, obtain a large amount of solid precipitatings；After washing the product repeatedly with deionized water, Filter and collected polymer, in vacuum drying oven, 50 DEG C drying 24 hours, obtain amino-terminated polyetheramine；
(3) hyperbranched poly pyrrole throat is prepared
In 100mL dry three-necked bottle, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) benzene are sequentially added Three acid anhydrides and 25ml metacresol, are stirred under nitrogen protection, and after three acid anhydrides are completely dissolved, 0.006 mole of 3,3 '-diamino are added Benzidine after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction, It is down to room temperature, and is poured into rapidly in 2000mL methanol, a large amount of solid precipitatings are obtained；After washing the product repeatedly with methanol, filter And collected polymer, in vacuum drying oven, 50 DEG C drying 24 hours to get the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
(4) polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared
In 100mL dry three-necked bottle, 1 gram of the amino-terminated polyetheramine, 0.6 gram of the naphthalene anhydride are sequentially added Terminated hyperbranched poly- pyrrole throat, the dimethyl sulfoxide of 10mL and the metacresol of 10mL add after stirring 60min under nitrogen protection Heat reacts 4h to 80 DEG C, then at 185 DEG C, reacts 10h；After reaction, it is down to room temperature, and pours into 2000mL methanol rapidly In, obtain a large amount of solid precipitatings；After washing the product repeatedly with methanol, simultaneously collected polymer, in vacuum drying oven, 50 DEG C are filtered Dry 24 hours to get polyetheramine-hyperbranched poly pyrrole throat copolymer；
(5) modified polyether amine-hyperbranched poly pyrrole throat copolymer is prepared
In 1000ml three-necked bottle, 0.1 gram of 0.2 gram of polyquaternium, graphene oxide, the step that step (1) obtains is added (5) polyetheramine obtained -0.5 gram of hyperbranched poly pyrrole throat copolymer, 0.2 gram of hexamethylene diamine, 0.05 gram of sodium hydroxide, deionized water 2mL and n,N-Dimethylformamide 50ml, at room temperature after mixing evenly；After reacting 10 hours at 60 DEG C, it is down to room temperature, and It pours into 2000mL methanol rapidly, obtains a large amount of solid precipitatings；After washing the product repeatedly with methanol, filters and collect polymerization Object, in vacuum drying oven, 60 DEG C drying 24 hours, obtain modified polyether amine-hyperbranched poly pyrrole throat copolymer.
By the acrylic emulsion of 100 parts by weight, the tungstic acid of 50 parts by weight, the titanium dioxide of 30 parts by weight, 8 parts by weight Copper chloride, 45 parts by weight it is above-mentioned for the nano-powder of photochromic coating, the KH-560 of 2 parts by weight, 3 parts by weight The deionized water of KH-550, the ethyl alcohol of 3 parts by weight and 9 parts by weight are added in agravic blender, open fly cutter, to avoid going out It now bonds, prevents stirring uneven, mixing time is 30 minutes, discharging.
Embodiment 5
The epoxy-capped polyetheramines of the nano silica of 10 parts by weight, 3 parts by weight is coated into boccaro and 6 parts by weight It obtains after being sufficiently mixed 15 minutes in modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer addition blender for photochromic The nano-powder of coating, the stirring rate of the blender are 600 revs/min；
The epoxy-capped polyetheramine cladding boccaro is prepared by following methods:
In 3L dry three-necked bottle, sequentially add 100 grams epoxy resin E51,0.24mol benzylamine and 500 gram two Methyl sulfoxide leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heats up 80 DEG C and react 4h, be down to room temperature, be then added 700 grams of dimethyl sulfoxides and 400 grams of boccaros, heat up 80 DEG C and react 1h, be down to room temperature, and pour into 3000mL deionized water rapidly In, obtain a large amount of solid precipitatings；After washing the product repeatedly with deionized water, simultaneously collected polymer is filtered, in vacuum drying oven, 60 DEG C drying 20 hours, obtain epoxy-capped polyetheramine cladding nano silica；
The modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared by following methods:
(1) polyquaternium is prepared
In 1000ml dry three-necked bottle, 1,12- dibromo-dodecane 0.1mol, Isosorbide-5-Nitrae-lupetazin is added 0.092mol and solvent dimethyl sulfoxide 80ml, after reacting 5 hours at 50 DEG C, add N- methylimidazole 0.0025mol with And N-methylmorpholine 0.0025mol, after reacting 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium；
(2) amino-terminated polyetheramine is prepared
In 1000mL dry three-necked bottle, sequentially add 95 grams epoxy resin E51,0.26mol benzylamine and 700 grams Dimethyl sulfoxide leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heats up 95 DEG C and react 6h, after reaction, be down to Room temperature, and pour into rapidly in 2000mL deionized water, obtain a large amount of solid precipitatings；After washing the product repeatedly with deionized water, Filter and collected polymer, in vacuum drying oven, 50 DEG C drying 24 hours, obtain amino-terminated polyetheramine；
(3) hyperbranched poly pyrrole throat is prepared
In 100mL dry three-necked bottle, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) benzene are sequentially added Three acid anhydrides and 25ml metacresol, are stirred under nitrogen protection, and after three acid anhydrides are completely dissolved, 0.006 mole of 3,3 '-diamino are added Benzidine after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction, It is down to room temperature, and is poured into rapidly in 2000mL methanol, a large amount of solid precipitatings are obtained；After washing the product repeatedly with methanol, filter And collected polymer, in vacuum drying oven, 50 DEG C drying 24 hours to get the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
(4) polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared
In 100mL dry three-necked bottle, 1 gram of the amino-terminated polyetheramine, 0.6 gram of the naphthalene anhydride are sequentially added Terminated hyperbranched poly- pyrrole throat, the dimethyl sulfoxide of 10mL and the metacresol of 10mL add after stirring 60min under nitrogen protection Heat reacts 4h to 80 DEG C, then at 185 DEG C, reacts 10h；After reaction, it is down to room temperature, and pours into 2000mL methanol rapidly In, obtain a large amount of solid precipitatings；After washing the product repeatedly with methanol, simultaneously collected polymer, in vacuum drying oven, 50 DEG C are filtered Dry 24 hours to get polyetheramine-hyperbranched poly pyrrole throat copolymer；
(5) sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer is prepared
In 100mL dry three-necked bottle, sequentially add 1 gram the polyetheramine-hyperbranched poly pyrrole throat copolymer and The concentrated sulfuric acid of the mass fraction 98% of 10mL after stirring 180min at 40 DEG C, pours into ice water under nitrogen protection, anti-with ice water After the product is washed in after backwashing, simultaneously collected polymer is filtered, in vacuum drying oven, 60 DEG C surpass for drying 24 hours up to sulfonated polyether amine- The poly- pyrrole throat copolymer of branching；
(6) modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared
In 1000ml three-necked bottle, 0.1 gram of 0.2 gram of polyquaternium, graphene oxide, the step that step (1) obtains is added (5) the sulfonated polyether amine obtained -0.5 gram of hyperbranched poly pyrrole throat copolymer, 0.2 gram of hexamethylene diamine, 0.05 gram of sodium hydroxide, deionization Water 2mL and n,N-Dimethylformamide 50ml, at room temperature after mixing evenly；After reacting 10 hours at 60 DEG C, it is down to room temperature, And pour into rapidly in 2000mL methanol, obtain a large amount of solid precipitatings；After washing the product repeatedly with methanol, filters and collect polymerization Object, in vacuum drying oven, 60 DEG C drying 24 hours, obtain modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer.
By the acrylic emulsion of 100 parts by weight, the tungstic acid of 50 parts by weight, the titanium dioxide of 30 parts by weight, 8 parts by weight Copper chloride, 45 parts by weight it is above-mentioned for the nano-powder of photochromic coating, the KH-560 of 2 parts by weight, 3 parts by weight The deionized water of KH-550, the ethyl alcohol of 3 parts by weight and 9 parts by weight are added in agravic blender, open fly cutter, to avoid going out It now bonds, prevents stirring uneven, mixing time is 30 minutes, discharging.
Embodiment 6
By the epoxy-capped polyetheramine cladding nano silica of 10 parts by weight, the boccaro of 3 parts by weight and 6 parts by weight It obtains after being sufficiently mixed 15 minutes in modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer addition blender for photochromic The nano-powder of coating, the stirring rate of the blender are 600 revs/min；
Wherein, the epoxy-capped polyetheramine cladding nano silica is prepared by following methods:
In 3L dry three-necked bottle, sequentially add 100 grams epoxy resin E51,0.24mol benzylamine and 500 gram two Methyl sulfoxide leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heats up 80 DEG C and react 4h, be down to room temperature, be then added 500 grams of dimethyl sulfoxides and 300 grams of nano silicas, heat up 80 DEG C and react 1h, be down to room temperature, and pour into 3000mL rapidly In deionized water, a large amount of solid precipitatings are obtained；After washing the product repeatedly with deionized water, simultaneously collected polymer, Yu Zhen are filtered In empty baking oven, 60 DEG C drying 20 hours, obtain epoxy-capped polyetheramine cladding nano silica；
The modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared by following methods:
(1) polyquaternium is prepared
In 1000ml dry three-necked bottle, 1,12- dibromo-dodecane 0.1mol, Isosorbide-5-Nitrae-lupetazin is added 0.092mol and solvent dimethyl sulfoxide 80ml, after reacting 5 hours at 50 DEG C, add N- methylimidazole 0.0025mol with And N-methylmorpholine 0.0025mol, after reacting 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium；
(2) amino-terminated polyetheramine is prepared
In 1000mL dry three-necked bottle, sequentially add 95 grams epoxy resin E51,0.26mol benzylamine and 700 grams Dimethyl sulfoxide leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heats up 95 DEG C and react 6h, after reaction, be down to Room temperature, and pour into rapidly in 2000mL deionized water, obtain a large amount of solid precipitatings；After washing the product repeatedly with deionized water, Filter and collected polymer, in vacuum drying oven, 50 DEG C drying 24 hours, obtain amino-terminated polyetheramine；
(3) hyperbranched poly pyrrole throat is prepared
In 100mL dry three-necked bottle, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) benzene are sequentially added Three acid anhydrides and 25ml metacresol, are stirred under nitrogen protection, and after three acid anhydrides are completely dissolved, 0.006 mole of 3,3 '-diamino are added Benzidine after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction, It is down to room temperature, and is poured into rapidly in 2000mL methanol, a large amount of solid precipitatings are obtained；After washing the product repeatedly with methanol, filter And collected polymer, in vacuum drying oven, 50 DEG C drying 24 hours to get the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
(4) polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared
In 100mL dry three-necked bottle, 1 gram of the amino-terminated polyetheramine, 0.6 gram of the naphthalene anhydride are sequentially added Terminated hyperbranched poly- pyrrole throat, the dimethyl sulfoxide of 10mL and the metacresol of 10mL add after stirring 60min under nitrogen protection Heat reacts 4h to 80 DEG C, then at 185 DEG C, reacts 10h；After reaction, it is down to room temperature, and pours into 2000mL methanol rapidly In, obtain a large amount of solid precipitatings；After washing the product repeatedly with methanol, simultaneously collected polymer, in vacuum drying oven, 50 DEG C are filtered Dry 24 hours to get polyetheramine-hyperbranched poly pyrrole throat copolymer；
(5) sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer is prepared
In 100mL dry three-necked bottle, sequentially add 1 gram the polyetheramine-hyperbranched poly pyrrole throat copolymer and The concentrated sulfuric acid of the mass fraction 98% of 10mL after stirring 180min at 40 DEG C, pours into ice water under nitrogen protection, anti-with ice water After the product is washed in after backwashing, simultaneously collected polymer is filtered, in vacuum drying oven, 60 DEG C surpass for drying 24 hours up to sulfonated polyether amine- The poly- pyrrole throat copolymer of branching；
(6) modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared
In 1000ml three-necked bottle, 0.1 gram of 0.2 gram of polyquaternium, graphene oxide, the step that step (1) obtains is added (5) the sulfonated polyether amine obtained -0.5 gram of hyperbranched poly pyrrole throat copolymer, 0.2 gram of hexamethylene diamine, 0.05 gram of sodium hydroxide, deionization Water 2mL and n,N-Dimethylformamide 50ml, at room temperature after mixing evenly；After reacting 10 hours at 60 DEG C, it is down to room temperature, And pour into rapidly in 2000mL methanol, obtain a large amount of solid precipitatings；After washing the product repeatedly with methanol, filters and collect polymerization Object, in vacuum drying oven, 60 DEG C drying 24 hours, obtain modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer.
By the acrylic emulsion of 100 parts by weight, the tungstic acid of 50 parts by weight, the titanium dioxide of 30 parts by weight, 8 parts by weight Copper chloride, 45 parts by weight it is above-mentioned for the nano-powder of photochromic coating, the KH-560 of 2 parts by weight, 3 parts by weight The deionized water of KH-550, the ethyl alcohol of 3 parts by weight and 9 parts by weight are added in agravic blender, open fly cutter, to avoid going out It now bonds, prevents stirring uneven, mixing time is 30 minutes, discharging.
Embodiment 7
By the epoxy-capped polyetheramine packet of the epoxy-capped polyetheramine cladding nano silica of 10 parts by weight, 3 parts by weight Cover the modified illiteracy of organic sodium base of boccaro, modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer of 6 parts by weight and 3 parts by weight The nano-powder for photochromic coating is obtained after being sufficiently mixed 15 minutes in de- soil addition blender, the blender stirs Mixing rate is 600 revs/min；
Wherein, the epoxy-capped polyetheramine cladding nano silica is prepared by following methods:
In 3L dry three-necked bottle, sequentially add 100 grams epoxy resin E51,0.24mol benzylamine and 500 gram two Methyl sulfoxide leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heats up 80 DEG C and react 4h, be down to room temperature, be then added 500 grams of dimethyl sulfoxides and 300 grams of nano silicas, heat up 80 DEG C and react 1h, be down to room temperature, and pour into 3000mL rapidly In deionized water, a large amount of solid precipitatings are obtained；After washing the product repeatedly with deionized water, simultaneously collected polymer, Yu Zhen are filtered In empty baking oven, 60 DEG C drying 20 hours, obtain epoxy-capped polyetheramine cladding nano silica；
The epoxy-capped polyetheramine cladding boccaro is prepared by following methods:
In 3L dry three-necked bottle, sequentially add 100 grams epoxy resin E51,0.24mol benzylamine and 500 gram two Methyl sulfoxide leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heats up 80 DEG C and react 4h, be down to room temperature, be then added 700 grams of dimethyl sulfoxides and 400 grams of boccaros, heat up 80 DEG C and react 1h, be down to room temperature, and pour into 3000mL deionized water rapidly In, obtain a large amount of solid precipitatings；After washing the product repeatedly with deionized water, simultaneously collected polymer is filtered, in vacuum drying oven, 60 DEG C drying 20 hours, obtain epoxy-capped polyetheramine cladding boccaro；
The modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared by following methods:
(1) polyquaternium is prepared
In 1000ml dry three-necked bottle, 1,12- dibromo-dodecane 0.1mol, Isosorbide-5-Nitrae-lupetazin is added 0.092mol and solvent dimethyl sulfoxide 80ml, after reacting 5 hours at 50 DEG C, add N- methylimidazole 0.0025mol with And N-methylmorpholine 0.0025mol, after reacting 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium；
(2) amino-terminated polyetheramine is prepared
In 1000mL dry three-necked bottle, sequentially add 95 grams epoxy resin E51,0.26mol benzylamine and 700 grams Dimethyl sulfoxide leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heats up 95 DEG C and react 6h, after reaction, be down to Room temperature, and pour into rapidly in 2000mL deionized water, obtain a large amount of solid precipitatings；After washing the product repeatedly with deionized water, Filter and collected polymer, in vacuum drying oven, 50 DEG C drying 24 hours, obtain amino-terminated polyetheramine；
(3) hyperbranched poly pyrrole throat is prepared
In 100mL dry three-necked bottle, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) benzene are sequentially added Three acid anhydrides and 25ml metacresol, are stirred under nitrogen protection, and after three acid anhydrides are completely dissolved, 0.006 mole of 3,3 '-diamino are added Benzidine after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction, It is down to room temperature, and is poured into rapidly in 2000mL methanol, a large amount of solid precipitatings are obtained；After washing the product repeatedly with methanol, filter And collected polymer, in vacuum drying oven, 50 DEG C drying 24 hours to get the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
(4) polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared
In 100mL dry three-necked bottle, 1 gram of the amino-terminated polyetheramine, 0.6 gram of the naphthalene anhydride are sequentially added Terminated hyperbranched poly- pyrrole throat, the dimethyl sulfoxide of 10mL and the metacresol of 10mL add after stirring 60min under nitrogen protection Heat reacts 4h to 80 DEG C, then at 185 DEG C, reacts 10h；After reaction, it is down to room temperature, and pours into 2000mL methanol rapidly In, obtain a large amount of solid precipitatings；After washing the product repeatedly with methanol, simultaneously collected polymer, in vacuum drying oven, 50 DEG C are filtered Dry 24 hours to get polyetheramine-hyperbranched poly pyrrole throat copolymer；
(5) sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer is prepared
In 100mL dry three-necked bottle, sequentially add 1 gram the polyetheramine-hyperbranched poly pyrrole throat copolymer and The concentrated sulfuric acid of the mass fraction 98% of 10mL after stirring 180min at 40 DEG C, pours into ice water under nitrogen protection, anti-with ice water After the product is washed in after backwashing, simultaneously collected polymer is filtered, in vacuum drying oven, 60 DEG C surpass for drying 24 hours up to sulfonated polyether amine- The poly- pyrrole throat copolymer of branching；
(6) modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared
In 1000ml three-necked bottle, 0.1 gram of 0.2 gram of polyquaternium, graphene oxide, the step that step (1) obtains is added (5) the sulfonated polyether amine obtained -0.5 gram of hyperbranched poly pyrrole throat copolymer, 0.2 gram of hexamethylene diamine, 0.05 gram of sodium hydroxide, deionization Water 2mL and n,N-Dimethylformamide 50ml, at room temperature after mixing evenly；After reacting 10 hours at 60 DEG C, it is down to room temperature, And pour into rapidly in 2000mL methanol, obtain a large amount of solid precipitatings；After washing the product repeatedly with methanol, filters and collect polymerization Object, in vacuum drying oven, 60 DEG C drying 24 hours, obtain modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer.
By the acrylic emulsion of 100 parts by weight, the tungstic acid of 50 parts by weight, the titanium dioxide of 30 parts by weight, 8 parts by weight Copper chloride, 45 parts by weight it is above-mentioned for the nano-powder of photochromic coating, the KH-560 of 2 parts by weight, 3 parts by weight The deionized water of KH-550, the ethyl alcohol of 3 parts by weight and 9 parts by weight are added in agravic blender, open fly cutter, to avoid going out It now bonds, prevents stirring uneven, mixing time is 30 minutes, discharging；
Organic sodium base modified montmorillonoid the preparation method comprises the following steps:
15g calcium-base montmorillonite is taken, 800ml distilled water is added, stirs 20min, Na is added2CO35g is stirred evenly, and it is heavy to stand It forms sediment and cleans, be centrifuged 5min under the conditions of 2000r/min, separate and obtain sodium-based montmorillonite.
Test condition
The resulting photochromic coating of embodiment 1-7 is coated on road, and test performance.
According to GA98-2005 standard testing, specifically:
1, surface drying time answer≤for 24 hours
2, adhesion strength >=0.1Mpa
3, water resistance: after 720h, coating does not crack, aliquation, falls off
4, acid resistance: after 360h, coating does not crack, aliquation, falls off
5, alkali resistance: after 360h, coating does not crack, aliquation, falls off
6, freeze-thawing resistant circulation experiment (secondary): after 15 times, coating does not crack, aliquation, falls off
7, fire resistance: coating layer thickness 20mm, fire endurance are not less than 2h
Test result is shown in Table 1.
Table 1
Test item 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 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%
Above data, which can be seen that, coats nano silica, modification sulphonation polyethers with without using epoxy-capped polyetheramine The coating of amine-hyperbranched poly pyrrole throat copolymer and epoxy-capped polyetheramine cladding boccaro is compared, and coating of the invention has bright Aobvious better performance, thus provides advantageous effects of the invention.

Claims (3)

1. a kind of nano-powder for photochromic coating, which is characterized in that by weight, including following components:
The epoxy-capped polyetheramine cladding nano silica of 10 parts by weight, the epoxy-capped polyetheramine of 1-5 parts by weight coat purple Sand and the modification sulphonation of 5-10 parts by weight polyetheramine-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 obtains；
The epoxy-capped polyetheramine cladding nano silica is prepared by following methods:
In 3L dry three-necked bottle, 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；It after 1h is stirred at room temperature, heats up 80 DEG C and reacts 4h, be down to room temperature, be then added 500 grams Dimethyl sulfoxide and 300 grams of nano silicas, heat up 80 DEG C and react 1h, be down to room temperature, and pour into rapidly 3000mL go from In sub- water, a large amount of solid precipitatings are obtained；After washing the product repeatedly with deionized water, simultaneously collected polymer is filtered, is dried in vacuum In case, 60 DEG C drying 20 hours, obtain epoxy-capped polyetheramine cladding nano silica；
The epoxy-capped polyetheramine cladding boccaro is prepared by following methods:
In 3L dry three-necked bottle, 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；It after 1h is stirred at room temperature, heats up 80 DEG C and reacts 4h, be down to room temperature, be then added 700 grams Dimethyl sulfoxide and 400 grams of boccaros, heat up 80 DEG C and react 1h, be down to room temperature, and pour into rapidly in 3000mL deionized water, obtain It is precipitated to a large amount of solids；After washing the product repeatedly with deionized water, simultaneously collected polymer, in vacuum drying oven, 60 DEG C are filtered It is 20 hours dry, obtain epoxy-capped polyetheramine cladding boccaro；
The modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared by following methods:
(1) polyquaternium is prepared
In 1000ml dry three-necked bottle, be added 1,12- dibromo-dodecane 0.1mol, Isosorbide-5-Nitrae-lupetazin 0.092mol with And solvent dimethyl sulfoxide 80ml adds N- methylimidazole 0.0025mol and N- methyl after reacting 5 hours at 50 DEG C Quinoline 0.0025mol, after reacting 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium；
(2) amino-terminated polyetheramine is prepared
In 1000mL dry three-necked bottle, 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, heats up 95 DEG C and reacts 6h, after reaction, be down to room temperature, And pour into rapidly in 2000mL deionized water, obtain a large amount of solid precipitatings；After washing the product repeatedly with deionized water, filter simultaneously Collected polymer, in vacuum drying oven, 50 DEG C drying 24 hours, obtain amino-terminated polyetheramine；
(3) hyperbranched poly pyrrole throat is prepared
In 100mL dry three-necked bottle, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) benzene, three acid anhydride are sequentially added It with 25ml metacresol, stirs under nitrogen protection, after three acid anhydrides are completely dissolved, 0.006 mole of 3,3 '-benzidines is added 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, it is down to Room temperature, and pour into rapidly in 2000mL methanol, obtain a large amount of solid precipitatings；After washing the product repeatedly with methanol, filters and receive Collect polymer, in vacuum drying oven, 50 DEG C drying 24 hours to get the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
(4) polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared
In 100mL dry three-necked bottle, 1 gram of the amino-terminated polyetheramine, 0.6 gram of naphthalene anhydride sealing end are sequentially added Hyperbranched poly pyrrole throat, the dimethyl sulfoxide of 10mL and the metacresol of 10mL are heated to after stirring 60min under nitrogen protection 80 DEG C, 4h is reacted, then at 185 DEG C, reacts 10h；After reaction, it is down to room temperature, and is poured into rapidly in 2000mL methanol, is obtained It is precipitated to a large amount of solids；After washing the product repeatedly with methanol, simultaneously collected polymer, in vacuum drying oven, 50 DEG C of dryings are filtered 24 hours to get polyetheramine-hyperbranched poly pyrrole throat copolymer；
(5) sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer is prepared
In 100mL dry three-necked bottle, 1 gram of the polyetheramine-hyperbranched poly pyrrole throat copolymer and 10mL are sequentially added Mass fraction 98% the concentrated sulfuric acid, under nitrogen protection, at 40 DEG C stir 180min after, pour into ice water, washed repeatedly with ice water It after washing the product, filters and collected polymer, in vacuum drying oven, sulfonated polyether amine-is hyperbranched to obtain the final product for 60 DEG C of drying 24 hours Poly- pyrrole throat copolymer；
(6) modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is prepared
In 1000ml three-necked bottle, 0.1 gram of 0.2 gram of polyquaternium, graphene oxide, the step (5) that step (1) obtains is added Obtained sulfonated polyether amine -0.5 gram of hyperbranched poly pyrrole throat copolymer, 0.2 gram of hexamethylene diamine, 0.05 gram of sodium hydroxide, deionized water 2mL and n,N-Dimethylformamide 50ml, at room temperature after mixing evenly；After reacting 10 hours at 60 DEG C, it is down to room temperature, and It pours into 2000mL methanol rapidly, obtains a large amount of solid precipitatings；After washing the product repeatedly with methanol, filters and collect polymerization Object, in vacuum drying oven, 60 DEG C drying 24 hours, obtain modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer.
2. a kind of photochromic coating, which is characterized in that by weight, including following components:
The acrylic emulsion of 100 parts by weight, the tungstic acid of 30-60 parts by weight, the titanium dioxide of 20-40 parts by weight, 5-10 weight Measure copper chloride, the nano-powder described in claim 1 for photochromic coating of 20-60 parts by weight, 1-5 parts by weight of part KH-560,1-5 parts by weight KH-550,1-5 parts by weight ethyl alcohol and 5-10 parts by weight deionized water.
3. photochromic coating according to claim 2, which is characterized in that by weight, including following components:
The chlorination of the acrylic emulsion of 100 parts by weight, the tungstic acid of 50 parts by weight, the titanium dioxide of 30 parts by weight, 8 parts by weight Copper, 45 parts by weight it is described in claim 1 for the nano-powder of photochromic coating, the KH-560 of 2 parts by weight, 3 weight The KH-550, the ethyl alcohol of 3 parts by weight and the deionized water of 9 parts by weight of part.
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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

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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 soil coating material and use 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
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