CN107603296A - A kind of stalk is modified wall powdery paints - Google Patents
A kind of stalk is modified wall powdery paints Download PDFInfo
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Abstract
The invention discloses a kind of stalk to be modified wall powdery paints, and it is included：Portland cement, cellulose ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, quaternary ammonium salt-modified sulfonated phosphazene sulfonated polyimide compound, beta cyclodextrin, corn stalk powder, KH 550, KH 560, starch.Powdery paints of the invention is nonpoisonous and tasteless, green, security is good, cost is cheap, good weatherability, construction is simple, anti-microbial property are good and case hardness is high.
Description
Technical field
The invention belongs to technical field of coatings, more particularly it relates to which a kind of stalk is modified wall powdery paints.
Background technology
Powdery paints is a kind of new without solvent, 100% solid powdery coating, and it is entirely different with general coating
Form, with existing for the state of attritive powder, due to without using solvent, so referred to as powdery paints.
With the continuous enhancing of social progress, development in science and technology and people's environmental consciousness, people fit up to house decoraton
It is required that also more and more higher, not only need beautiful attractive in appearance, more require environment protection health.However, powdery paints on the market, holds after making moist
Fugitive color, yellowing, it is mouldy, come off, and the problem of easy to aging and inflammable potential safety hazard be present.In addition, big fire accident in recent years
Frequently occur, these all bring huge economic loss, therefore research safety, nontoxic, fire prevention, decoration effect to the country and people
The building and ornament materials that fruit is abundant, good weatherability, cost are cheap turn into study hotspot, and greatly developing such building and ornament materials is
The demand in epoch and the needs of reality.Stalk yield is high and cost is low, is very suitable for modified powder coating, competing to improve market
Strive power.
The content of the invention
The technical problem to be solved in the present invention is to provide it is a kind of it is nonpoisonous and tasteless, green, security is good, cost is cheap,
Good weatherability, construction is simple, anti-microbial property are good, case hardness is high and environmentally friendly wall powdery paints.
In order to solve the above problems, one aspect of the present invention provides a kind of stalk and is modified wall powdery paints, with weight
Part meter, its preparing raw material include following components：
100 parts of portland cement
Cellulose ether 1-10 parts
Polyoxyethylene polyoxy propyl alcohol amidogen ether 1-10 parts
Quaternary ammonium salt-modified sulfonated phosphazene-sulfonated polyimide compound 5-10 parts
Beta-schardinger dextrin 10-20 parts
Corn stalk powder 10-20 parts
KH-550 1-10 parts
KH-560 1-10 parts
Starch 1-5 parts；
Preferably, its preparing raw material includes following components：
100 parts of portland cement
Cellulose ether 3-8 parts
Polyoxyethylene polyoxy propyl alcohol amidogen ether 2-9 parts
Quaternary ammonium salt-modified sulfonated phosphazene-sulfonated polyimide compound 6-9 parts
Beta-schardinger dextrin 15-18 parts
Corn stalk powder 12-17 parts
KH-550 3-8 parts
KH-560 3-7 parts
Starch 2-4 parts；
It is highly preferred that its preparing raw material includes following components：
100 parts of portland cement
5 parts of cellulose ether
6 parts of polyoxyethylene polyoxy propyl alcohol amidogen ether
Quaternary ammonium salt-modified sulfonated phosphazene -7 parts of sulfonated polyimide compound
16 parts of beta-schardinger dextrin
15 parts of corn stalk powder
6 parts of KH-550
5 parts of KH-560
3 parts of starch.
Preferably, the preparation method of the quaternary ammonium salt-modified sulfonated phosphazene-sulfonated polyimide compound is：
（1）In 300 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.94 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.5 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 10 hours in 190 milliliters of acetonitriles, reaction knot
Shu Hou, solvent is centrifuged off, distinguishes washed product 5 times with deionized water and acetone, finally vacuum drying 25 is small at 50 DEG C
When obtain white polyphosphazene powder；
（2）In 100 milliliters of dry three-necked bottles, 1.6mmol 2,2 '-bis- (4- sulfonic benzos epoxides) biphenyl two is sequentially added
Amine, 12.5 milliliters of m-creso1 and 0.8 milliliter of triethylamines, lead to nitrogen protection and magnetic agitation；Treat 2,2 '-bis- (4- sulfonic benzos
Epoxide) after benzidine is completely dissolved, sequentially add the tetracarboxylic anhydrides of 1.55mmol 3,4,9,10-, 3.0mmol benzoic acid
And 0.6 milliliter of isoquinolin；After being stirred at room temperature 1 hour, heat up 80 DEG C and react 4 hours, 180 DEG C are reacted 20 hours；Reaction knot
Shu Hou, room temperature is down to, then adds 1 gram of above-mentioned gained white polyphosphazene powder and 0.3 gram of KH-560, lead to nitrogen protection and magnetic
After power stirs 1 hour, heat up 80 DEG C after reacting 4 hours, be down to room temperature, add the concentrated hydrochloric acid of 0.5 milliliter of mass fraction 37%,
Simultaneously magnetic agitation after 1 hour, heats up 100 DEG C after reacting 5 hours, is down to room temperature, and pour into 150mL methanol rapidly for logical nitrogen protection
In, obtain a large amount of solid precipitations；After washing the product repeatedly with methanol, simultaneously collected polymer, in vacuum drying oven, 60 DEG C are filtered
Dry 20 hours, obtain polyphosphazene-sulfonated polyimide compound；
（3）1 gram of above-mentioned polyphosphazene-sulfonated polyimide compound is added in 100 milliliters of three-neck flasks, adds 10 milliliters of matter
The concentrated sulfuric acid of fraction 98% is measured, is placed in 50 DEG C of water-baths, is reacted 15 hours under mechanical stirring, after reaction terminates, product is delayed
It is slow to pour into cold water, and be stirred continuously, unreacted sulfuric acid is centrifuged off, product is then washed with deionized 5 times, is finally existed
It is dried in vacuo at 50 DEG C 48 hours and obtains sulfonated phosphazene-sulfonated polyimide compound；
（4）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（3）Gained sulfonated phosphazene-sulfonated polyimide is compound
10 grams of thing, 1 gram of graphene oxide, 200 milliliters of dimethyl sulfoxide (DMSO), 0.5 gram of triethylamine, 2 grams of 1,6- dibromo-hexanes, silane coupler
3 grams of KH-550 and 3 grams of silane coupler KH-560, system temperature rise to 50 DEG C, after reacting 6 hours, add mass fraction
0.5 milliliter of 37% concentrated hydrochloric acid, continue after being reacted 1 hour at 50 DEG C, discharge in water, obtain fluffy solid, use deionized water
Wash the fluffy solid respectively with ethanol 3 times, be finally dried in vacuo 24 hours at 50 DEG C and obtain the poly- phosphorus of quaternary ammonium salt-modified sulfonation
Nitrile-sulfonated polyimide compound.
Preferably, described stalk is modified wall powdery paints, and in parts by weight, its preparing raw material also includes the poly- phosphorus of sulfonation
Nitrile modified nano-titanium dioxide 1-5 parts.
Preferably, the preparation method of the sulfonated phosphazene modified nano-titanium dioxide is：
In 250 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.92 gram 4,4 '-dihydroxydiphenylsulisomer is dissolved in
In 200 milliliters of acetonitriles, 1.3 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 4 hours, after reaction terminates, from
The heart removes solvent, distinguishes washed product 5 times with deionized water and acetone, is finally dried in vacuo 18 hours at 50 DEG C and obtains white
Polyphosphazene powder；
0.6 gram of above-mentioned white polyphosphazene powder is added in 100 milliliters of three-neck flasks, adds 10 milliliters of mass fractions 98%
The concentrated sulfuric acid, it is placed in 50 DEG C of water-baths, reacts 15 hours under mechanical stirring, after reaction terminates, product is slowly poured into cold water
In, and be stirred continuously, unreacted sulfuric acid is centrifuged off, product is then washed with deionized 5 times, finally the vacuum at 50 DEG C
Dry 48 hours and obtain sulfonated phosphazene powder；
0.7 gram of above-mentioned sulfonated phosphazene powder, 0.07 gram of epoxy resin E51, average grain diameter are added in 50 milliliters of three-neck flasks
For 0.5 gram of 150 nanometers of 3 grams of nano titanium oxide, 0.2 gram of silane resin acceptor kh-550 and silane coupler KH-560 with
And 10 milliliters of dimethyl sulfoxide (DMSO)s, heat up 120 DEG C after reacting 2 hours, be down to room temperature and slowly pour into product in cold water, and constantly
Stirring, is then washed with deionized product 5 times, and it is to obtain sulfonated phosphazene to change that 48 hours are finally dried in vacuo at 50 DEG C
Property nano titanium oxide.
Preferably, described stalk is modified wall powdery paints, and in parts by weight, its preparing raw material also includes N, N'- bis-
Imidazole radicals oxalamide 1-10 parts.
Another aspect of the present invention provides the preparation method that a kind of stalk is modified wall powdery paints, including：By described material
After being sufficiently mixed 50 minutes in composition addition mixer, discharging obtains.
In one embodiment, the stir speed (S.S.) of the mixer is 500 ~ 1000 revs/min；Preferably, the stirring
The stir speed (S.S.) of machine is 800 revs/min.
Compared with prior art, beneficial effects of the present invention are：
1st, weatherability, intensity, resistance can be improved by the addition of quaternary ammonium salt-modified sulfonated phosphazene-sulfonated polyimide compound
Fire performance and excellent anti-microbial property.
2nd, the addition of sulfonated phosphazene modified nano-titanium dioxide can further improve crosslink density, so as to improve system
Intensity, and weatherability and anti-flammability can be improved simultaneously.
3rd, the addition of N, N'- diimidazole base oxalamide further enhances water-resistant coating energy.
4th, the addition of stalk greatly reduces cost.
Embodiment
Raw material:
Portland cement（P.O42.5）Purchased from the new cement of Wuhan China.Cellulose ether is general purchased from Hercules day, model
BP440M.Nano titanium oxide（150 nanometers of average grain diameter）, corn stalk powder（800 mesh）, silane resin acceptor kh-550, silane
Coupling agent KH-560 is purchased from Aladdin reagent.Starch is beautiful purchased from Dongguan east, model DM-210.Graphene oxide is purchased from Heng Qiu sections
Skill.Other raw materials are purchased from Chinese medicines group.
Embodiment 1
By 100 grams of portland cement, 1 gram of cellulose ether, 1 gram of polyoxyethylene polyoxy propyl alcohol amidogen ether, the poly- phosphorus of quaternary ammonium salt-modified sulfonation
Nitrile -5 grams of sulfonated polyimide compound, 10 grams of beta-schardinger dextrin, 10 grams of corn stalk powder, 1 gram of KH-550,1 gram of KH-560 with
And after in 1 gram of addition mixer of starch being sufficiently mixed 50 minutes, discharging obtains, stir speed (S.S.) is 800 revs/min；
The preparation method of the quaternary ammonium salt-modified sulfonated phosphazene-sulfonated polyimide compound is：
（1）In 300 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.94 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.5 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 10 hours in 190 milliliters of acetonitriles, reaction knot
Shu Hou, solvent is centrifuged off, distinguishes washed product 5 times with deionized water and acetone, finally vacuum drying 25 is small at 50 DEG C
When obtain white polyphosphazene powder；
（2）In 100 milliliters of dry three-necked bottles, 1.6mmol 2,2 '-bis- (4- sulfonic benzos epoxides) biphenyl two is sequentially added
Amine, 12.5 milliliters of m-creso1 and 0.8 milliliter of triethylamines, lead to nitrogen protection and magnetic agitation；Treat 2,2 '-bis- (4- sulfonic benzos
Epoxide) after benzidine is completely dissolved, sequentially add the tetracarboxylic anhydrides of 1.55mmol 3,4,9,10-, 3.0mmol benzoic acid
And 0.6 milliliter of isoquinolin；After being stirred at room temperature 1 hour, heat up 80 DEG C and react 4 hours, 180 DEG C are reacted 20 hours；Reaction knot
Shu Hou, room temperature is down to, then adds 1 gram of above-mentioned gained white polyphosphazene powder and 0.3 gram of KH-560, lead to nitrogen protection and magnetic
After power stirs 1 hour, heat up 80 DEG C after reacting 4 hours, be down to room temperature, add the concentrated hydrochloric acid of 0.5 milliliter of mass fraction 37%,
Simultaneously magnetic agitation after 1 hour, heats up 100 DEG C after reacting 5 hours, is down to room temperature, and pour into 150mL methanol rapidly for logical nitrogen protection
In, obtain a large amount of solid precipitations；After washing the product repeatedly with methanol, simultaneously collected polymer, in vacuum drying oven, 60 DEG C are filtered
Dry 20 hours, obtain polyphosphazene-sulfonated polyimide compound；
（3）1 gram of above-mentioned polyphosphazene-sulfonated polyimide compound is added in 100 milliliters of three-neck flasks, adds 10 milliliters of matter
The concentrated sulfuric acid of fraction 98% is measured, is placed in 50 DEG C of water-baths, is reacted 15 hours under mechanical stirring, after reaction terminates, product is delayed
It is slow to pour into cold water, and be stirred continuously, unreacted sulfuric acid is centrifuged off, product is then washed with deionized 5 times, is finally existed
It is dried in vacuo at 50 DEG C 48 hours and obtains sulfonated phosphazene-sulfonated polyimide compound；
（4）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（3）Gained sulfonated phosphazene-sulfonated polyimide is compound
10 grams of thing, 1 gram of graphene oxide, 200 milliliters of dimethyl sulfoxide (DMSO), 0.5 gram of triethylamine, 2 grams of 1,6- dibromo-hexanes, silane coupler
3 grams of KH-550 and 3 grams of silane coupler KH-560, system temperature rise to 50 DEG C, after reacting 6 hours, add mass fraction
0.5 milliliter of 37% concentrated hydrochloric acid, continue after being reacted 1 hour at 50 DEG C, discharge in water, obtain fluffy solid, use deionized water
Wash the fluffy solid respectively with ethanol 3 times, be finally dried in vacuo 24 hours at 50 DEG C and obtain the poly- phosphorus of quaternary ammonium salt-modified sulfonation
Nitrile-sulfonated polyimide compound.
Embodiment 2
100 grams of portland cement, 10 grams of cellulose ether, 10 grams of polyoxyethylene polyoxy propyl alcohol amidogen ether, quaternary ammonium salt-modified sulfonation are gathered
Phosphonitrile -10 grams of sulfonated polyimide compound, 20 grams of beta-schardinger dextrin, 20 grams of corn stalk powder, 10 grams of KH-550, KH-560 10
Gram and 5 grams of addition mixers of starch in be sufficiently mixed 50 minutes after, discharging obtains, stir speed (S.S.) be 800 revs/min；
The preparation method of the quaternary ammonium salt-modified sulfonated phosphazene-sulfonated polyimide compound is：
（1）In 300 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.94 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.5 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 10 hours in 190 milliliters of acetonitriles, reaction knot
Shu Hou, solvent is centrifuged off, distinguishes washed product 5 times with deionized water and acetone, finally vacuum drying 25 is small at 50 DEG C
When obtain white polyphosphazene powder；
（2）In 100 milliliters of dry three-necked bottles, 1.6mmol 2,2 '-bis- (4- sulfonic benzos epoxides) biphenyl two is sequentially added
Amine, 12.5 milliliters of m-creso1 and 0.8 milliliter of triethylamines, lead to nitrogen protection and magnetic agitation；Treat 2,2 '-bis- (4- sulfonic benzos
Epoxide) after benzidine is completely dissolved, sequentially add the tetracarboxylic anhydrides of 1.55mmol 3,4,9,10-, 3.0mmol benzoic acid
And 0.6 milliliter of isoquinolin；After being stirred at room temperature 1 hour, heat up 80 DEG C and react 4 hours, 180 DEG C are reacted 20 hours；Reaction knot
Shu Hou, room temperature is down to, then adds 1 gram of above-mentioned gained white polyphosphazene powder and 0.3 gram of KH-560, lead to nitrogen protection and magnetic
After power stirs 1 hour, heat up 80 DEG C after reacting 4 hours, be down to room temperature, add the concentrated hydrochloric acid of 0.5 milliliter of mass fraction 37%,
Simultaneously magnetic agitation after 1 hour, heats up 100 DEG C after reacting 5 hours, is down to room temperature, and pour into 150mL methanol rapidly for logical nitrogen protection
In, obtain a large amount of solid precipitations；After washing the product repeatedly with methanol, simultaneously collected polymer, in vacuum drying oven, 60 DEG C are filtered
Dry 20 hours, obtain polyphosphazene-sulfonated polyimide compound；
（3）1 gram of above-mentioned polyphosphazene-sulfonated polyimide compound is added in 100 milliliters of three-neck flasks, adds 10 milliliters of matter
The concentrated sulfuric acid of fraction 98% is measured, is placed in 50 DEG C of water-baths, is reacted 15 hours under mechanical stirring, after reaction terminates, product is delayed
It is slow to pour into cold water, and be stirred continuously, unreacted sulfuric acid is centrifuged off, product is then washed with deionized 5 times, is finally existed
It is dried in vacuo at 50 DEG C 48 hours and obtains sulfonated phosphazene-sulfonated polyimide compound；
（4）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（3）Gained sulfonated phosphazene-sulfonated polyimide is compound
10 grams of thing, 1 gram of graphene oxide, 200 milliliters of dimethyl sulfoxide (DMSO), 0.5 gram of triethylamine, 2 grams of 1,6- dibromo-hexanes, silane coupler
3 grams of KH-550 and 3 grams of silane coupler KH-560, system temperature rise to 50 DEG C, after reacting 6 hours, add mass fraction
0.5 milliliter of 37% concentrated hydrochloric acid, continue after being reacted 1 hour at 50 DEG C, discharge in water, obtain fluffy solid, use deionized water
Wash the fluffy solid respectively with ethanol 3 times, be finally dried in vacuo 24 hours at 50 DEG C and obtain the poly- phosphorus of quaternary ammonium salt-modified sulfonation
Nitrile-sulfonated polyimide compound.
Embodiment 3
By 100 grams of portland cement, 5 grams of cellulose ether, 6 grams of polyoxyethylene polyoxy propyl alcohol amidogen ether, the poly- phosphorus of quaternary ammonium salt-modified sulfonation
Nitrile -7 grams of sulfonated polyimide compound, 16 grams of beta-schardinger dextrin, 15 grams of corn stalk powder, 6 grams of KH-550,5 grams of KH-560 with
And after in 3 grams of addition mixers of starch being sufficiently mixed 50 minutes, discharging obtains, stir speed (S.S.) is 800 revs/min；
The preparation method of the quaternary ammonium salt-modified sulfonated phosphazene-sulfonated polyimide compound is：
（1）In 300 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.94 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.5 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 10 hours in 190 milliliters of acetonitriles, reaction knot
Shu Hou, solvent is centrifuged off, distinguishes washed product 5 times with deionized water and acetone, finally vacuum drying 25 is small at 50 DEG C
When obtain white polyphosphazene powder；
（2）In 100 milliliters of dry three-necked bottles, 1.6mmol 2,2 '-bis- (4- sulfonic benzos epoxides) biphenyl two is sequentially added
Amine, 12.5 milliliters of m-creso1 and 0.8 milliliter of triethylamines, lead to nitrogen protection and magnetic agitation；Treat 2,2 '-bis- (4- sulfonic benzos
Epoxide) after benzidine is completely dissolved, sequentially add the tetracarboxylic anhydrides of 1.55mmol 3,4,9,10-, 3.0mmol benzoic acid
And 0.6 milliliter of isoquinolin；After being stirred at room temperature 1 hour, heat up 80 DEG C and react 4 hours, 180 DEG C are reacted 20 hours；Reaction knot
Shu Hou, room temperature is down to, then adds 1 gram of above-mentioned gained white polyphosphazene powder and 0.3 gram of KH-560, lead to nitrogen protection and magnetic
After power stirs 1 hour, heat up 80 DEG C after reacting 4 hours, be down to room temperature, add the concentrated hydrochloric acid of 0.5 milliliter of mass fraction 37%,
Simultaneously magnetic agitation after 1 hour, heats up 100 DEG C after reacting 5 hours, is down to room temperature, and pour into 150mL methanol rapidly for logical nitrogen protection
In, obtain a large amount of solid precipitations；After washing the product repeatedly with methanol, simultaneously collected polymer, in vacuum drying oven, 60 DEG C are filtered
Dry 20 hours, obtain polyphosphazene-sulfonated polyimide compound；
（3）1 gram of above-mentioned polyphosphazene-sulfonated polyimide compound is added in 100 milliliters of three-neck flasks, adds 10 milliliters of matter
The concentrated sulfuric acid of fraction 98% is measured, is placed in 50 DEG C of water-baths, is reacted 15 hours under mechanical stirring, after reaction terminates, product is delayed
It is slow to pour into cold water, and be stirred continuously, unreacted sulfuric acid is centrifuged off, product is then washed with deionized 5 times, is finally existed
It is dried in vacuo at 50 DEG C 48 hours and obtains sulfonated phosphazene-sulfonated polyimide compound；
（4）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（3）Gained sulfonated phosphazene-sulfonated polyimide is compound
10 grams of thing, 1 gram of graphene oxide, 200 milliliters of dimethyl sulfoxide (DMSO), 0.5 gram of triethylamine, 2 grams of 1,6- dibromo-hexanes, silane coupler
3 grams of KH-550 and 3 grams of silane coupler KH-560, system temperature rise to 50 DEG C, after reacting 6 hours, add mass fraction
0.5 milliliter of 37% concentrated hydrochloric acid, continue after being reacted 1 hour at 50 DEG C, discharge in water, obtain fluffy solid, use deionized water
Wash the fluffy solid respectively with ethanol 3 times, be finally dried in vacuo 24 hours at 50 DEG C and obtain the poly- phosphorus of quaternary ammonium salt-modified sulfonation
Nitrile-sulfonated polyimide compound.
Embodiment 4
By 100 grams of portland cement, 5 grams of cellulose ether, 6 grams of polyoxyethylene polyoxy propyl alcohol amidogen ether, the poly- phosphorus of quaternary ammonium salt-modified sulfonation
Nitrile -7 grams of sulfonated polyimide compound, 16 grams of beta-schardinger dextrin, 15 grams of corn stalk powder, 6 grams of KH-550,5 grams of KH-560, shallow lake
After being sufficiently mixed 50 minutes in 3 grams of addition mixers of 3 grams of powder and sulfonated phosphazene modified nano-titanium dioxide, discharging obtains,
Stir speed (S.S.) is 800 revs/min；
The preparation method of the quaternary ammonium salt-modified sulfonated phosphazene-sulfonated polyimide compound is：
（1）In 300 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.94 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.5 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 10 hours in 190 milliliters of acetonitriles, reaction knot
Shu Hou, solvent is centrifuged off, distinguishes washed product 5 times with deionized water and acetone, finally vacuum drying 25 is small at 50 DEG C
When obtain white polyphosphazene powder；
（2）In 100 milliliters of dry three-necked bottles, 1.6mmol 2,2 '-bis- (4- sulfonic benzos epoxides) biphenyl two is sequentially added
Amine, 12.5 milliliters of m-creso1 and 0.8 milliliter of triethylamines, lead to nitrogen protection and magnetic agitation；Treat 2,2 '-bis- (4- sulfonic benzos
Epoxide) after benzidine is completely dissolved, sequentially add the tetracarboxylic anhydrides of 1.55mmol 3,4,9,10-, 3.0mmol benzoic acid
And 0.6 milliliter of isoquinolin；After being stirred at room temperature 1 hour, heat up 80 DEG C and react 4 hours, 180 DEG C are reacted 20 hours；Reaction knot
Shu Hou, room temperature is down to, then adds 1 gram of above-mentioned gained white polyphosphazene powder and 0.3 gram of KH-560, lead to nitrogen protection and magnetic
After power stirs 1 hour, heat up 80 DEG C after reacting 4 hours, be down to room temperature, add the concentrated hydrochloric acid of 0.5 milliliter of mass fraction 37%,
Simultaneously magnetic agitation after 1 hour, heats up 100 DEG C after reacting 5 hours, is down to room temperature, and pour into 150mL methanol rapidly for logical nitrogen protection
In, obtain a large amount of solid precipitations；After washing the product repeatedly with methanol, simultaneously collected polymer, in vacuum drying oven, 60 DEG C are filtered
Dry 20 hours, obtain polyphosphazene-sulfonated polyimide compound；
（3）1 gram of above-mentioned polyphosphazene-sulfonated polyimide compound is added in 100 milliliters of three-neck flasks, adds 10 milliliters of matter
The concentrated sulfuric acid of fraction 98% is measured, is placed in 50 DEG C of water-baths, is reacted 15 hours under mechanical stirring, after reaction terminates, product is delayed
It is slow to pour into cold water, and be stirred continuously, unreacted sulfuric acid is centrifuged off, product is then washed with deionized 5 times, is finally existed
It is dried in vacuo at 50 DEG C 48 hours and obtains sulfonated phosphazene-sulfonated polyimide compound；
（4）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（3）Gained sulfonated phosphazene-sulfonated polyimide is compound
10 grams of thing, 1 gram of graphene oxide, 200 milliliters of dimethyl sulfoxide (DMSO), 0.5 gram of triethylamine, 2 grams of 1,6- dibromo-hexanes, silane coupler
3 grams of KH-550 and 3 grams of silane coupler KH-560, system temperature rise to 50 DEG C, after reacting 6 hours, add mass fraction
0.5 milliliter of 37% concentrated hydrochloric acid, continue after being reacted 1 hour at 50 DEG C, discharge in water, obtain fluffy solid, use deionized water
Wash the fluffy solid respectively with ethanol 3 times, be finally dried in vacuo 24 hours at 50 DEG C and obtain the poly- phosphorus of quaternary ammonium salt-modified sulfonation
Nitrile-sulfonated polyimide compound；
The preparation method of the sulfonated phosphazene modified nano-titanium dioxide is：
In 250 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.92 gram 4,4 '-dihydroxydiphenylsulisomer is dissolved in
In 200 milliliters of acetonitriles, 1.3 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 4 hours, after reaction terminates, from
The heart removes solvent, distinguishes washed product 5 times with deionized water and acetone, is finally dried in vacuo 18 hours at 50 DEG C and obtains white
Polyphosphazene powder；
0.6 gram of above-mentioned white polyphosphazene powder is added in 100 milliliters of three-neck flasks, adds 10 milliliters of mass fractions 98%
The concentrated sulfuric acid, it is placed in 50 DEG C of water-baths, reacts 15 hours under mechanical stirring, after reaction terminates, product is slowly poured into cold water
In, and be stirred continuously, unreacted sulfuric acid is centrifuged off, product is then washed with deionized 5 times, finally the vacuum at 50 DEG C
Dry 48 hours and obtain sulfonated phosphazene powder；
0.7 gram of above-mentioned sulfonated phosphazene powder, 0.07 gram of epoxy resin E51, average grain diameter are added in 50 milliliters of three-neck flasks
For 0.5 gram of 150 nanometers of 3 grams of nano titanium oxide, 0.2 gram of silane resin acceptor kh-550 and silane coupler KH-560 with
And 10 milliliters of dimethyl sulfoxide (DMSO)s, heat up 120 DEG C after reacting 2 hours, be down to room temperature and slowly pour into product in cold water, and constantly
Stirring, is then washed with deionized product 5 times, and it is to obtain sulfonated phosphazene to change that 48 hours are finally dried in vacuo at 50 DEG C
Property nano titanium oxide.
Embodiment 5
By 100 grams of portland cement, 5 grams of cellulose ether, 6 grams of polyoxyethylene polyoxy propyl alcohol amidogen ether, the poly- phosphorus of quaternary ammonium salt-modified sulfonation
Nitrile -7 grams of sulfonated polyimide compound, 16 grams of beta-schardinger dextrin, 15 grams of corn stalk powder, 6 grams of KH-550,5 grams of KH-560, shallow lake
In 3 grams of powder, 3 grams of sulfonated phosphazene modified nano-titanium dioxide and N, N'- diimidazole base 5 grams of addition mixers of oxalamide
After being sufficiently mixed 50 minutes, discharging obtains, and stir speed (S.S.) is 800 revs/min；
The preparation method of the quaternary ammonium salt-modified sulfonated phosphazene-sulfonated polyimide compound is：
（1）In 300 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.94 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.5 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 10 hours in 190 milliliters of acetonitriles, reaction knot
Shu Hou, solvent is centrifuged off, distinguishes washed product 5 times with deionized water and acetone, finally vacuum drying 25 is small at 50 DEG C
When obtain white polyphosphazene powder；
（2）In 100 milliliters of dry three-necked bottles, 1.6mmol 2,2 '-bis- (4- sulfonic benzos epoxides) biphenyl two is sequentially added
Amine, 12.5 milliliters of m-creso1 and 0.8 milliliter of triethylamines, lead to nitrogen protection and magnetic agitation；Treat 2,2 '-bis- (4- sulfonic benzos
Epoxide) after benzidine is completely dissolved, sequentially add the tetracarboxylic anhydrides of 1.55mmol 3,4,9,10-, 3.0mmol benzoic acid
And 0.6 milliliter of isoquinolin；After being stirred at room temperature 1 hour, heat up 80 DEG C and react 4 hours, 180 DEG C are reacted 20 hours；Reaction knot
Shu Hou, room temperature is down to, then adds 1 gram of above-mentioned gained white polyphosphazene powder and 0.3 gram of KH-560, lead to nitrogen protection and magnetic
After power stirs 1 hour, heat up 80 DEG C after reacting 4 hours, be down to room temperature, add the concentrated hydrochloric acid of 0.5 milliliter of mass fraction 37%,
Simultaneously magnetic agitation after 1 hour, heats up 100 DEG C after reacting 5 hours, is down to room temperature, and pour into 150mL methanol rapidly for logical nitrogen protection
In, obtain a large amount of solid precipitations；After washing the product repeatedly with methanol, simultaneously collected polymer, in vacuum drying oven, 60 DEG C are filtered
Dry 20 hours, obtain polyphosphazene-sulfonated polyimide compound；
（3）1 gram of above-mentioned polyphosphazene-sulfonated polyimide compound is added in 100 milliliters of three-neck flasks, adds 10 milliliters of matter
The concentrated sulfuric acid of fraction 98% is measured, is placed in 50 DEG C of water-baths, is reacted 15 hours under mechanical stirring, after reaction terminates, product is delayed
It is slow to pour into cold water, and be stirred continuously, unreacted sulfuric acid is centrifuged off, product is then washed with deionized 5 times, is finally existed
It is dried in vacuo at 50 DEG C 48 hours and obtains sulfonated phosphazene-sulfonated polyimide compound；
（4）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（3）Gained sulfonated phosphazene-sulfonated polyimide is compound
10 grams of thing, 1 gram of graphene oxide, 200 milliliters of dimethyl sulfoxide (DMSO), 0.5 gram of triethylamine, 2 grams of 1,6- dibromo-hexanes, silane coupler
3 grams of KH-550 and 3 grams of silane coupler KH-560, system temperature rise to 50 DEG C, after reacting 6 hours, add mass fraction
0.5 milliliter of 37% concentrated hydrochloric acid, continue after being reacted 1 hour at 50 DEG C, discharge in water, obtain fluffy solid, use deionized water
Wash the fluffy solid respectively with ethanol 3 times, be finally dried in vacuo 24 hours at 50 DEG C and obtain the poly- phosphorus of quaternary ammonium salt-modified sulfonation
Nitrile-sulfonated polyimide compound；
The preparation method of the sulfonated phosphazene modified nano-titanium dioxide is：
In 250 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.92 gram 4,4 '-dihydroxydiphenylsulisomer is dissolved in
In 200 milliliters of acetonitriles, 1.3 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 4 hours, after reaction terminates, from
The heart removes solvent, distinguishes washed product 5 times with deionized water and acetone, is finally dried in vacuo 18 hours at 50 DEG C and obtains white
Polyphosphazene powder；
0.6 gram of above-mentioned white polyphosphazene powder is added in 100 milliliters of three-neck flasks, adds 10 milliliters of mass fractions 98%
The concentrated sulfuric acid, it is placed in 50 DEG C of water-baths, reacts 15 hours under mechanical stirring, after reaction terminates, product is slowly poured into cold water
In, and be stirred continuously, unreacted sulfuric acid is centrifuged off, product is then washed with deionized 5 times, finally the vacuum at 50 DEG C
Dry 48 hours and obtain sulfonated phosphazene powder；
0.7 gram of above-mentioned sulfonated phosphazene powder, 0.07 gram of epoxy resin E51, average grain diameter are added in 50 milliliters of three-neck flasks
For 0.5 gram of 150 nanometers of 3 grams of nano titanium oxide, 0.2 gram of silane resin acceptor kh-550 and silane coupler KH-560 with
And 10 milliliters of dimethyl sulfoxide (DMSO)s, heat up 120 DEG C after reacting 2 hours, be down to room temperature and slowly pour into product in cold water, and constantly
Stirring, is then washed with deionized product 5 times, and it is to obtain sulfonated phosphazene to change that 48 hours are finally dried in vacuo at 50 DEG C
Property nano titanium oxide.
Comparative example 1
By 100 grams of portland cement, 5 grams of cellulose ether, 6 grams of polyoxyethylene polyoxy propyl alcohol amidogen ether, 16 grams of beta-schardinger dextrin, corn
15 grams of powder of straw, 6 grams of KH-550,5 grams of KH-560, be sufficiently mixed 50 minutes in 3 grams of addition mixers of starch after, discharge
Arrive, stir speed (S.S.) is 800 revs/min.
Comparative example 2
100 grams of portland cement, 5 grams of cellulose ether, 6 grams of polyoxyethylene polyoxy propyl alcohol amidogen ether, sulfonated phosphazene-sulfonation are gathered
7 grams of acid imide compound, 16 grams of beta-schardinger dextrin, 15 grams of corn stalk powder, 6 grams of KH-550,5 grams of KH-560,3 grams of starch, sulphur
Change in 3 grams of polyphosphazene modified nano-titanium dioxide and N, N'- diimidazole base 5 grams of addition mixers of oxalamide and be sufficiently mixed 50
After minute, discharging obtains, and stir speed (S.S.) is 800 revs/min；
The preparation method of the sulfonated phosphazene-sulfonated polyimide compound is：
（1）In 300 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.94 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.5 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 10 hours in 190 milliliters of acetonitriles, reaction knot
Shu Hou, solvent is centrifuged off, distinguishes washed product 5 times with deionized water and acetone, finally vacuum drying 25 is small at 50 DEG C
When obtain white polyphosphazene powder；
（2）In 100 milliliters of dry three-necked bottles, 1.6mmol 2,2 '-bis- (4- sulfonic benzos epoxides) biphenyl two is sequentially added
Amine, 12.5 milliliters of m-creso1 and 0.8 milliliter of triethylamines, lead to nitrogen protection and magnetic agitation；Treat 2,2 '-bis- (4- sulfonic benzos
Epoxide) after benzidine is completely dissolved, sequentially add the tetracarboxylic anhydrides of 1.55mmol 3,4,9,10-, 3.0mmol benzoic acid
And 0.6 milliliter of isoquinolin；After being stirred at room temperature 1 hour, heat up 80 DEG C and react 4 hours, 180 DEG C are reacted 20 hours；Reaction knot
Shu Hou, room temperature is down to, then adds 1 gram of above-mentioned gained white polyphosphazene powder and 0.3 gram of KH-560, lead to nitrogen protection and magnetic
After power stirs 1 hour, heat up 80 DEG C after reacting 4 hours, be down to room temperature, add the concentrated hydrochloric acid of 0.5 milliliter of mass fraction 37%,
Simultaneously magnetic agitation after 1 hour, heats up 100 DEG C after reacting 5 hours, is down to room temperature, and pour into 150mL methanol rapidly for logical nitrogen protection
In, obtain a large amount of solid precipitations；After washing the product repeatedly with methanol, simultaneously collected polymer, in vacuum drying oven, 60 DEG C are filtered
Dry 20 hours, obtain polyphosphazene-sulfonated polyimide compound；
（3）1 gram of above-mentioned polyphosphazene-sulfonated polyimide compound is added in 100 milliliters of three-neck flasks, adds 10 milliliters of matter
The concentrated sulfuric acid of fraction 98% is measured, is placed in 50 DEG C of water-baths, is reacted 15 hours under mechanical stirring, after reaction terminates, product is delayed
It is slow to pour into cold water, and be stirred continuously, unreacted sulfuric acid is centrifuged off, product is then washed with deionized 5 times, is finally existed
It is dried in vacuo at 50 DEG C 48 hours and obtains sulfonated phosphazene-sulfonated polyimide compound；
The preparation method of the sulfonated phosphazene modified nano-titanium dioxide is：
In 250 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.92 gram 4,4 '-dihydroxydiphenylsulisomer is dissolved in
In 200 milliliters of acetonitriles, 1.3 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 4 hours, after reaction terminates, from
The heart removes solvent, distinguishes washed product 5 times with deionized water and acetone, is finally dried in vacuo 18 hours at 50 DEG C and obtains white
Polyphosphazene powder；
0.6 gram of above-mentioned white polyphosphazene powder is added in 100 milliliters of three-neck flasks, adds 10 milliliters of mass fractions 98%
The concentrated sulfuric acid, it is placed in 50 DEG C of water-baths, reacts 15 hours under mechanical stirring, after reaction terminates, product is slowly poured into cold water
In, and be stirred continuously, unreacted sulfuric acid is centrifuged off, product is then washed with deionized 5 times, finally the vacuum at 50 DEG C
Dry 48 hours and obtain sulfonated phosphazene powder；
0.7 gram of above-mentioned sulfonated phosphazene powder, 0.07 gram of epoxy resin E51, average grain diameter are added in 50 milliliters of three-neck flasks
For 0.5 gram of 150 nanometers of 3 grams of nano titanium oxide, 0.2 gram of silane resin acceptor kh-550 and silane coupler KH-560 with
And 10 milliliters of dimethyl sulfoxide (DMSO)s, heat up 120 DEG C after reacting 2 hours, be down to room temperature and slowly pour into product in cold water, and constantly
Stirring, is then washed with deionized product 5 times, and it is to obtain sulfonated phosphazene to change that 48 hours are finally dried in vacuo at 50 DEG C
Property nano titanium oxide.
Comparative example 3
By 100 grams of portland cement, 5 grams of cellulose ether, 6 grams of polyoxyethylene polyoxy propyl alcohol amidogen ether, quaternary ammonium salt-modified polyphosphazene-
7 grams of sulfonated polyimide compound, 16 grams of beta-schardinger dextrin, 15 grams of corn stalk powder, 6 grams of KH-550,5 grams of KH-560, starch
In 3 grams, 3 grams of sulfonated phosphazene modified nano-titanium dioxide and N, N'- diimidazole base 5 grams of addition mixers of oxalamide fully
After mixing 50 minutes, discharging obtains, and stir speed (S.S.) is 800 revs/min；
The preparation method of the quaternary ammonium salt-modified polyphosphazene-sulfonated polyimide compound is：
（1）In 300 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.94 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.5 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 10 hours in 190 milliliters of acetonitriles, reaction knot
Shu Hou, solvent is centrifuged off, distinguishes washed product 5 times with deionized water and acetone, finally vacuum drying 25 is small at 50 DEG C
When obtain white polyphosphazene powder；
（2）In 100 milliliters of dry three-necked bottles, 1.6mmol 2,2 '-bis- (4- sulfonic benzos epoxides) biphenyl two is sequentially added
Amine, 12.5 milliliters of m-creso1 and 0.8 milliliter of triethylamines, lead to nitrogen protection and magnetic agitation；Treat 2,2 '-bis- (4- sulfonic benzos
Epoxide) after benzidine is completely dissolved, sequentially add the tetracarboxylic anhydrides of 1.55mmol 3,4,9,10-, 3.0mmol benzoic acid
And 0.6 milliliter of isoquinolin；After being stirred at room temperature 1 hour, heat up 80 DEG C and react 4 hours, 180 DEG C are reacted 20 hours；Reaction knot
Shu Hou, room temperature is down to, then adds 1 gram of above-mentioned gained white polyphosphazene powder and 0.3 gram of KH-560, lead to nitrogen protection and magnetic
After power stirs 1 hour, heat up 80 DEG C after reacting 4 hours, be down to room temperature, add the concentrated hydrochloric acid of 0.5 milliliter of mass fraction 37%,
Simultaneously magnetic agitation after 1 hour, heats up 100 DEG C after reacting 5 hours, is down to room temperature, and pour into 150mL methanol rapidly for logical nitrogen protection
In, obtain a large amount of solid precipitations；After washing the product repeatedly with methanol, simultaneously collected polymer, in vacuum drying oven, 60 DEG C are filtered
Dry 20 hours, obtain polyphosphazene-sulfonated polyimide compound；
（3）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（3）Gained polyphosphazene-sulfonated polyimide compound 10
Gram, 1 gram of graphene oxide, 200 milliliters of dimethyl sulfoxide (DMSO), 0.5 gram of triethylamine, 2 grams of 1,6- dibromo-hexanes, silane coupler KH-
550 3 grams and silane coupler KH-560 3 grams, system temperature rises to 50 DEG C, after reacting 6 hours, adds mass fraction 37%
0.5 milliliter of concentrated hydrochloric acid, continue after being reacted 1 hour at 50 DEG C, discharge in water, obtain fluffy solid, with deionized water and
Ethanol washs the fluffy solid 3 times respectively, is finally dried in vacuo 24 hours at 50 DEG C and obtains quaternary ammonium salt-modified polyphosphazene-sulphur
Change polyimides compound；
The preparation method of the sulfonated phosphazene modified nano-titanium dioxide is：
In 250 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.92 gram 4,4 '-dihydroxydiphenylsulisomer is dissolved in
In 200 milliliters of acetonitriles, 1.3 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 4 hours, after reaction terminates, from
The heart removes solvent, distinguishes washed product 5 times with deionized water and acetone, is finally dried in vacuo 18 hours at 50 DEG C and obtains white
Polyphosphazene powder；
0.6 gram of above-mentioned white polyphosphazene powder is added in 100 milliliters of three-neck flasks, adds 10 milliliters of mass fractions 98%
The concentrated sulfuric acid, it is placed in 50 DEG C of water-baths, reacts 15 hours under mechanical stirring, after reaction terminates, product is slowly poured into cold water
In, and be stirred continuously, unreacted sulfuric acid is centrifuged off, product is then washed with deionized 5 times, finally the vacuum at 50 DEG C
Dry 48 hours and obtain sulfonated phosphazene powder；
0.7 gram of above-mentioned sulfonated phosphazene powder, 0.07 gram of epoxy resin E51, average grain diameter are added in 50 milliliters of three-neck flasks
For 0.5 gram of 150 nanometers of 3 grams of nano titanium oxide, 0.2 gram of silane resin acceptor kh-550 and silane coupler KH-560 with
And 10 milliliters of dimethyl sulfoxide (DMSO)s, heat up 120 DEG C after reacting 2 hours, be down to room temperature and slowly pour into product in cold water, and constantly
Stirring, is then washed with deionized product 5 times, and it is to obtain sulfonated phosphazene to change that 48 hours are finally dried in vacuo at 50 DEG C
Property nano titanium oxide.
Comparative example 4
By 100 grams of portland cement, 5 grams of cellulose ether, 6 grams of polyoxyethylene polyoxy propyl alcohol amidogen ether, the poly- phosphorus of quaternary ammonium salt-modified sulfonation
Nitrile -7 grams of sulfonated polyimide compound, 16 grams of beta-schardinger dextrin, 15 grams of corn stalk powder, 6 grams of KH-550,5 grams of KH-560, shallow lake
In 3 grams of powder, 3 grams of polyphosphazene modified nano-titanium dioxide and N, N'- diimidazole base 5 grams of addition mixers of oxalamide fully
After mixing 50 minutes, discharging obtains, and stir speed (S.S.) is 800 revs/min；
The preparation method of the quaternary ammonium salt-modified sulfonated phosphazene-sulfonated polyimide compound is：
（1）In 300 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.94 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.5 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 10 hours in 190 milliliters of acetonitriles, reaction knot
Shu Hou, solvent is centrifuged off, distinguishes washed product 5 times with deionized water and acetone, finally vacuum drying 25 is small at 50 DEG C
When obtain white polyphosphazene powder；
（2）In 100 milliliters of dry three-necked bottles, 1.6mmol 2,2 '-bis- (4- sulfonic benzos epoxides) biphenyl two is sequentially added
Amine, 12.5 milliliters of m-creso1 and 0.8 milliliter of triethylamines, lead to nitrogen protection and magnetic agitation；Treat 2,2 '-bis- (4- sulfonic benzos
Epoxide) after benzidine is completely dissolved, sequentially add the tetracarboxylic anhydrides of 1.55mmol 3,4,9,10-, 3.0mmol benzoic acid
And 0.6 milliliter of isoquinolin；After being stirred at room temperature 1 hour, heat up 80 DEG C and react 4 hours, 180 DEG C are reacted 20 hours；Reaction knot
Shu Hou, room temperature is down to, then adds 1 gram of above-mentioned gained white polyphosphazene powder and 0.3 gram of KH-560, lead to nitrogen protection and magnetic
After power stirs 1 hour, heat up 80 DEG C after reacting 4 hours, be down to room temperature, add the concentrated hydrochloric acid of 0.5 milliliter of mass fraction 37%,
Simultaneously magnetic agitation after 1 hour, heats up 100 DEG C after reacting 5 hours, is down to room temperature, and pour into 150mL methanol rapidly for logical nitrogen protection
In, obtain a large amount of solid precipitations；After washing the product repeatedly with methanol, simultaneously collected polymer, in vacuum drying oven, 60 DEG C are filtered
Dry 20 hours, obtain polyphosphazene-sulfonated polyimide compound；
（3）1 gram of above-mentioned polyphosphazene-sulfonated polyimide compound is added in 100 milliliters of three-neck flasks, adds 10 milliliters of matter
The concentrated sulfuric acid of fraction 98% is measured, is placed in 50 DEG C of water-baths, is reacted 15 hours under mechanical stirring, after reaction terminates, product is delayed
It is slow to pour into cold water, and be stirred continuously, unreacted sulfuric acid is centrifuged off, product is then washed with deionized 5 times, is finally existed
It is dried in vacuo at 50 DEG C 48 hours and obtains sulfonated phosphazene-sulfonated polyimide compound；
（4）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（3）Gained sulfonated phosphazene-sulfonated polyimide is compound
10 grams of thing, 1 gram of graphene oxide, 200 milliliters of dimethyl sulfoxide (DMSO), 0.5 gram of triethylamine, 2 grams of 1,6- dibromo-hexanes, silane coupler
3 grams of KH-550 and 3 grams of silane coupler KH-560, system temperature rise to 50 DEG C, after reacting 6 hours, add mass fraction
0.5 milliliter of 37% concentrated hydrochloric acid, continue after being reacted 1 hour at 50 DEG C, discharge in water, obtain fluffy solid, use deionized water
Wash the fluffy solid respectively with ethanol 3 times, be finally dried in vacuo 24 hours at 50 DEG C and obtain the poly- phosphorus of quaternary ammonium salt-modified sulfonation
Nitrile-sulfonated polyimide compound；
The preparation method of the polyphosphazene modified nano-titanium dioxide is：
In 250 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.92 gram 4,4 '-dihydroxydiphenylsulisomer is dissolved in
In 200 milliliters of acetonitriles, 1.3 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 4 hours, after reaction terminates, from
The heart removes solvent, distinguishes washed product 5 times with deionized water and acetone, is finally dried in vacuo 18 hours at 50 DEG C and obtains white
Polyphosphazene powder；
0.7 gram of above-mentioned polyphosphazene powder, 0.07 gram of epoxy resin E51, average grain diameter are added in 50 milliliters of three-neck flasks is
150 nanometers of 0.5 gram of 3 grams of nano titanium oxide, 0.2 gram of silane resin acceptor kh-550 and silane coupler KH-560 and
10 milliliters of dimethyl sulfoxide (DMSO)s, heat up 120 DEG C after reacting 2 hours, be down to room temperature and slowly pour into product in cold water, and constantly stir
Mix, product is then washed with deionized 5 times, be finally dried in vacuo at 50 DEG C 48 hours and obtain polyphosphazene modified Nano
Titanium dioxide.
Method of testing
Clean metope, it is ensured that wall is firm, by the coating electrostatic spraying of any one of embodiment 1 ~ 7 on interior wall, completes construction.
According to JC/T 2083-2011 standard testings, it is specially：
1st, dry powder：Whether lump
2nd, surface drying time answers≤2h
3rd, appearance of film：It is whether normal
4th, alkali resistance：≥48h
5th, abrasion resistance：>=500 times
6th, adhesion strength/MPa：Normal condition, >=0.5
7th, application property：Whether scratch, brush or spray and be accessible.
According to JC/T 2177-2013 standard testings hygroscopic capacities and moisture releasing amount, it is specially：
Hygroscopic capacity：23 DEG C, 75%RH, 24h, answer >=40.
Antibiotic rate is tested according to GB 18581.
Test result is shown in Table 1, table 2.
Table 1
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Application property | Can be with | Can be with | Can be with | Can be with | Can be with |
| Surface drying time | 1.3h | 1.5h | 1.1h | 0.8 h | 0.5h |
| Appearance of film | Normally | Normally | Normally | Normally | Normally |
| Alkali resistance | 213 | 225h | 297h | 338 | 365h |
| Abrasion resistance | 2002 times | 1987 times | 2479 times | 2760 | 3129 times |
| Adhesion strength | 1.23 | 1.22 | 1.35 | 1.58 | 1.71 |
| Antibiotic rate | 97% | 98% | 98% | 99% | 98% |
| Fire resistance period | 7.0h | 6.9h | 7.2h | 8.1 | 8.5h |
Table 1
| Test event | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Application property | Cannot | Can be with | Can be with | Can be with |
| Surface drying time | - | 2.5h | 2.9h | 1.9 h |
| Appearance of film | - | Normally | Normally | Normally |
| Alkali resistance | - | 169h | 134h | 200h |
| Abrasion resistance | - | 1657 times | 1389 times | 1888 times |
| Adhesion strength | - | 1.04 | 0.89 | 1.15 |
| Antibiotic rate | - | - | 98% | 99% |
| Fire resistance period | - | 5.5h | 4.8h | 6.0 |
Claims (7)
1. a kind of stalk is modified wall powdery paints, it is characterised in that in parts by weight, its preparing raw material includes following components：
100 parts of portland cement
Cellulose ether 1-10 parts
Polyoxyethylene polyoxy propyl alcohol amidogen ether 1-10 parts
Quaternary ammonium salt-modified sulfonated phosphazene-sulfonated polyimide compound 5-10 parts
Beta-schardinger dextrin 10-20 parts
Corn stalk powder 10-20 parts
KH-550 1-10 parts
KH-560 1-10 parts
Starch 1-5 parts.
2. stalk according to claim 1 is modified wall powdery paints, it is characterised in that in parts by weight, it prepares former
Material includes following components：
100 parts of portland cement
Cellulose ether 3-8 parts
Polyoxyethylene polyoxy propyl alcohol amidogen ether 2-9 parts
Quaternary ammonium salt-modified sulfonated phosphazene-sulfonated polyimide compound 6-9 parts
Beta-schardinger dextrin 15-18 parts
Corn stalk powder 12-17 parts
KH-550 3-8 parts
KH-560 3-7 parts
Starch 2-4 parts.
3. stalk according to claim 2 is modified wall powdery paints, it is characterised in that in parts by weight, it prepares former
Material includes following components：
100 parts of portland cement
5 parts of cellulose ether
6 parts of polyoxyethylene polyoxy propyl alcohol amidogen ether
Quaternary ammonium salt-modified sulfonated phosphazene -7 parts of sulfonated polyimide compound
16 parts of beta-schardinger dextrin
15 parts of corn stalk powder
6 parts of KH-550
5 parts of KH-560
3 parts of starch.
4. the stalk according to claim any one of 1-3 is modified wall powdery paints, it is characterised in that the quaternary ammonium salt changes
The preparation method of property sulfonated phosphazene-sulfonated polyimide compound is：
（1）In 300 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.94 gram 4,4 '-dihydroxydiphenylsulisomer is molten
Then solution adds 1.5 milliliters of triethylamines, is placed in 50 DEG C of ultrasonic water baths and reacts 10 hours in 190 milliliters of acetonitriles, reaction knot
Shu Hou, solvent is centrifuged off, distinguishes washed product 5 times with deionized water and acetone, finally vacuum drying 25 is small at 50 DEG C
When obtain white polyphosphazene powder；
（2）In 100 milliliters of dry three-necked bottles, 1.6mmol 2,2 '-bis- (4- sulfonic benzos epoxides) biphenyl two is sequentially added
Amine, 12.5 milliliters of m-creso1 and 0.8 milliliter of triethylamines, lead to nitrogen protection and magnetic agitation；Treat 2,2 '-bis- (4- sulfonic benzos
Epoxide) after benzidine is completely dissolved, sequentially add the tetracarboxylic anhydrides of 1.55mmol 3,4,9,10-, 3.0mmol benzoic acid
And 0.6 milliliter of isoquinolin；After being stirred at room temperature 1 hour, heat up 80 DEG C and react 4 hours, 180 DEG C are reacted 20 hours；Reaction knot
Shu Hou, room temperature is down to, then adds 1 gram of above-mentioned gained white polyphosphazene powder and 0.3 gram of KH-560, lead to nitrogen protection and magnetic
After power stirs 1 hour, heat up 80 DEG C after reacting 4 hours, be down to room temperature, add the concentrated hydrochloric acid of 0.5 milliliter of mass fraction 37%,
Simultaneously magnetic agitation after 1 hour, heats up 100 DEG C after reacting 5 hours, is down to room temperature, and pour into 150mL methanol rapidly for logical nitrogen protection
In, obtain a large amount of solid precipitations；After washing the product repeatedly with methanol, simultaneously collected polymer, in vacuum drying oven, 60 DEG C are filtered
Dry 20 hours, obtain polyphosphazene-sulfonated polyimide compound；
（3）1 gram of above-mentioned polyphosphazene-sulfonated polyimide compound is added in 100 milliliters of three-neck flasks, adds 10 milliliters of matter
The concentrated sulfuric acid of fraction 98% is measured, is placed in 50 DEG C of water-baths, is reacted 15 hours under mechanical stirring, after reaction terminates, product is delayed
It is slow to pour into cold water, and be stirred continuously, unreacted sulfuric acid is centrifuged off, product is then washed with deionized 5 times, is finally existed
It is dried in vacuo at 50 DEG C 48 hours and obtains sulfonated phosphazene-sulfonated polyimide compound；
（4）In 250 milliliters of round-bottomed flasks, above-mentioned steps are sequentially added（3）Gained sulfonated phosphazene-sulfonated polyimide is compound
10 grams of thing, 1 gram of graphene oxide, 200 milliliters of dimethyl sulfoxide (DMSO), 0.5 gram of triethylamine, 2 grams of 1,6- dibromo-hexanes, silane coupler
3 grams of KH-550 and 3 grams of silane coupler KH-560, system temperature rise to 50 DEG C, after reacting 6 hours, add mass fraction
0.5 milliliter of 37% concentrated hydrochloric acid, continue after being reacted 1 hour at 50 DEG C, discharge in water, obtain fluffy solid, use deionized water
Wash the fluffy solid respectively with ethanol 3 times, be finally dried in vacuo 24 hours at 50 DEG C and obtain the poly- phosphorus of quaternary ammonium salt-modified sulfonation
Nitrile-sulfonated polyimide compound.
5. the stalk according to claim any one of 1-3 is modified wall powdery paints, it is characterised in that in parts by weight,
Its preparing raw material also includes sulfonated phosphazene modified nano-titanium dioxide 1-5 parts.
6. stalk according to claim 4 is modified wall powdery paints, it is characterised in that the sulfonated phosphazene is modified and received
Rice titanium dioxide preparation method be：
In 250 milliliters of round-bottomed flasks, by 0.41 gram of hexachlorocyclotriph,sphazene and 0.92 gram 4,4 '-dihydroxydiphenylsulisomer is dissolved in
In 200 milliliters of acetonitriles, 1.3 milliliters of triethylamines are then added, is placed in 50 DEG C of ultrasonic water baths and reacts 4 hours, after reaction terminates, from
The heart removes solvent, distinguishes washed product 5 times with deionized water and acetone, is finally dried in vacuo 18 hours at 50 DEG C and obtains white
Polyphosphazene powder；
0.6 gram of above-mentioned white polyphosphazene powder is added in 100 milliliters of three-neck flasks, adds 10 milliliters of mass fractions 98%
The concentrated sulfuric acid, it is placed in 50 DEG C of water-baths, reacts 15 hours under mechanical stirring, after reaction terminates, product is slowly poured into cold water
In, and be stirred continuously, unreacted sulfuric acid is centrifuged off, product is then washed with deionized 5 times, finally the vacuum at 50 DEG C
Dry 48 hours and obtain sulfonated phosphazene powder；
0.7 gram of above-mentioned sulfonated phosphazene powder, 0.07 gram of epoxy resin E51, average grain diameter are added in 50 milliliters of three-neck flasks
For 0.5 gram of 150 nanometers of 3 grams of nano titanium oxide, 0.2 gram of silane resin acceptor kh-550 and silane coupler KH-560 with
And 10 milliliters of dimethyl sulfoxide (DMSO)s, heat up 120 DEG C after reacting 2 hours, be down to room temperature and slowly pour into product in cold water, and constantly
Stirring, is then washed with deionized product 5 times, and it is to obtain sulfonated phosphazene to change that 48 hours are finally dried in vacuo at 50 DEG C
Property nano titanium oxide.
7. stalk according to claim 6 is modified wall powdery paints, it is characterised in that in parts by weight, it prepares former
Material also includes N, N'- diimidazole base oxalamide 1-10 parts.
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| CN111328809A (en) * | 2020-02-24 | 2020-06-26 | 暨南大学 | Quaternary ammonium salt-loaded polyphosphazene composite antibacterial agent and preparation method and application thereof |
| CN114014810A (en) * | 2021-10-09 | 2022-02-08 | 上海敏尧科技有限公司 | Imidization rate accelerator, resin composition, and preparation method and application thereof |
| CN115785454A (en) * | 2022-12-13 | 2023-03-14 | 万华化学集团股份有限公司 | Stain-resistant polymer, stain-resistant TPU composite material containing stain-resistant polymer, and preparation method and application of stain-resistant TPU composite material |
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Application publication date: 20180119 |