CN106866074A - A kind of high temperature resistant high-hardness water-proof wall covering and preparation method thereof - Google Patents
A kind of high temperature resistant high-hardness water-proof wall covering and preparation method thereof Download PDFInfo
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- CN106866074A CN106866074A CN201710113921.2A CN201710113921A CN106866074A CN 106866074 A CN106866074 A CN 106866074A CN 201710113921 A CN201710113921 A CN 201710113921A CN 106866074 A CN106866074 A CN 106866074A
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- polyetheramine
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00482—Coating or impregnation materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
Abstract
The invention discloses a kind of high temperature resistant high-hardness water-proof wall covering, it is included：Portland cement, montmorillonite, cellulose ether, polyoxyethylene polyoxy propyl alcohol amidogen ether, KH 560, polyquaternium modification sulphonation polyetheramine hyperbranched poly pyrrole throat copolymer, 1,3 dibromopropanes, graphene oxide and shitosan.The invention also discloses the preparation method of the high temperature resistant high-hardness water-proof wall covering.
Description
Technical field
The invention belongs to technical field of coatings, more particularly it relates to a kind of high temperature resistant high-hardness water-proof metope is applied
Material and preparation method thereof.
Background technology
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, interior/exterior decoration material on the market is big
Majority is organic material or organic/inorganic composite material, and they contain a large amount of volatile organic matters（VOC）, such as formaldehyde, benzene
Noxious material, after making moist easily colour fading, yellowing, it is mouldy, come off, and there is a problem of easily aging and inflammable potential safety hazard.Separately
Outward, big fire accident frequently occurs in recent years, and these all bring huge economic loss, therefore research peace to the country and people
Entirely, nontoxic, fire prevention, decorative effect are enriched, good weatherability, building and ornament materials with low cost turn into study hotspot, send out energetically
The need for opening up the demand and reality that such building and ornament materials are the epoch.
The content of the invention
The technical problem to be solved in the present invention be to provide a kind of nonpoisonous and tasteless, environmental protection, security it is good, with low cost,
Good weatherability, construction are simply, finishing effect is rich and varied, anti-microbial property is good, case hardness is high and high temperature resistant high-hardness water-proof wall
Coating materials and preparation method thereof.
In order to solve the above problems, one aspect of the present invention provides a kind of high temperature resistant high-hardness water-proof wall covering, with
Weight portion meter, its preparing raw material includes following components：
Portland cement 10-30 parts
Montmorillonite 5-10 parts
Cellulose ether 1-5 parts
3-10 parts of polyoxyethylene polyoxy propyl alcohol amidogen ether
KH-560 1-5 parts
Polyquaternium modification sulphonation polyetheramine -5-10 parts of hyperbranched poly pyrrole throat copolymer
1,3- dibromopropane 1-5 parts
Graphene oxide 1-10 parts
Shitosan 1-5 parts；
Preferably, described high temperature resistant high-hardness water-proof wall covering, in parts by weight, its preparing raw material includes following components：
25 parts of portland cement
6 parts of montmorillonite
3 parts of cellulose ether
8 parts of polyoxyethylene polyoxy propyl alcohol amidogen ether
4 parts of KH-560
Polyquaternium modification sulphonation polyetheramine -6 parts of hyperbranched poly pyrrole throat copolymer
1,3- 3 parts of dibromopropane
6 parts of graphene oxide
3 parts of shitosan；
In one embodiment, the preparation method of the polyquaternium modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer
For：
（1）Prepare polyquaternium
In the dry three-necked bottles of 1000ml, add 1,12- dibromo-dodecanes 0.1mol, Isosorbide-5-Nitrae-lupetazin 0.092mol with
And solvent dimethyl sulfoxide (DMSO) 80ml, after being reacted 5 hours at 50 DEG C, add N- methylimidazole 0.0025mol and N- methyl
Quinoline 0.0025mol, after being reacted 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium；
（2）Prepare amino-terminated polyetheramine
In the dry three-necked bottles of 1000mL, the benzylamine and 700 grams of diformazans of 95 grams epoxy resin E51,0.26mol are sequentially added
Base sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature,
And pour into rapidly in 2000mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration is simultaneously
Collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain amino-terminated polyetheramine；
（3）Prepare hyperbranched poly pyrrole throat
In the dry three-necked bottles of 100mL, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) acid anhydrides of benzene three are sequentially added
With 25ml metacresols, stir under nitrogen protection, after three acid anhydrides are completely dissolved, add the 3 of 0.006 mole, 3 '-benzidine
Amine, after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction terminates, it is down to
Room temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously received
Collection polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
（4）Prepare polyetheramine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of described amino-terminated polyetheramine, 0.6 gram of naphthalene anhydride end-blocking is sequentially added
The metacresol of hyperbranched poly pyrrole throat, the dimethyl sulfoxide (DMSO) of 10mL and 10mL, after stirring 60min under nitrogen protection, is heated to
80 DEG C, 4h is reacted, then at 185 DEG C, react 10h；After reaction terminates, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol, obtained
To a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 50 DEG C of dryings
24 hours, obtain final product polyetheramine-hyperbranched poly pyrrole throat copolymer；
（5）Prepare sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of the polyetheramine-hyperbranched poly pyrrole throat copolymer and 10mL is sequentially added
Mass fraction 98% the concentrated sulfuric acid, under nitrogen protection, at 40 DEG C stir 180min after, pour into frozen water, washed repeatedly with frozen water
After washing the product, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C of dryings obtain final product sulfonated polyether amine-hyperbranched for 24 hours
Poly- pyrrole throat copolymer；
（6）Prepare polyquaternium modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer
In 100ml three-necked bottles, step is added（1）0.2 gram of the polyquaternium for obtaining, step（5）The sulfonated polyether amine for obtaining-
0.5 gram of hyperbranched poly pyrrole throat copolymer, 0.2 gram of hexamethylene diamine, 0.05 gram of NaOH, deionized water 2mL and N, N- dimethyl
Formamide 50ml, after stirring at room temperature；After being reacted 10 hours at 60 DEG C, room temperature is down to, and pour into 2000mL first rapidly
In alcohol, a large amount of solids of sedimentation are obtained；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 60
DEG C drying 24 hours, obtains polyquaternium modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer.
In one embodiment, described high temperature resistant high-hardness water-proof wall covering, in parts by weight, its preparing raw material
Also include sulfonated polyether amine -1-5 parts of polybenzimidazoles block copolymer.
In one embodiment, the preparation method of the sulfonated polyether amine-polybenzimidazoles block copolymer is：
（1）Prepare epoxy-capped polyetheramine
In the dry three-necked bottles of 1000mL, sequentially add 100 grams epoxy resin E51,0.25mol benzylamine and 700 gram two
Methyl sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room
Temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously collected
Polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product epoxy-capped polyetheramine；
（2）Prepare amino-terminated polybenzimidazoles
1800 grams of polyphosphoric acids is weighed in the dry three-neck flasks of 3L, gas access, drying tube, gas vent and machine is connected
Tool agitator, is passed through nitrogen, 0.1 mole of 3,3'- diaminobenzidines is added after 5min, when tetramine is uniformly dispersed being dissolved in
After in polyphosphoric acids, 0.015 mole of 5- amino isophthalic acids and 0.08 mole of dodecanedioic acid is added, added afterwards
400 grams of phosphorus pentoxides start simultaneously at stirring and heat up to strengthen the absorption to reaction product water, 200 DEG C are warming up to, in the temperature
Lower reaction 20h；After question response system temperature is cooled to 150 DEG C, pour into deionized water, cyclic washing removal polyphosphoric acids；It
Product is poured into the sodium hydrate aqueous solution that mass fraction is 8% afterwards stirs 24h, removed with deionized water cyclic washing afterwards
NaOH, by products therefrom in the vacuum drying oven dry for standby at 60 DEG C, obtain final product amino-terminated polybenzimidazoles prepolymer；
（3）Prepare polyetheramine-polybenzimidazoles block copolymer
In the dry three-necked bottles of 100mL, 0.3 gram of described epoxy-capped polyetheramine, 1 gram described amino-terminated is sequentially added
The dimethyl sulfoxide (DMSO) of polybenzimidazoles prepolymer and 10mL, after stirring 60min under nitrogen protection, is heated to 80 DEG C, reaction
10h；After reaction terminates, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；Washed repeatedly with methyl alcohol
After washing the product, suction filtration and collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product polyetheramine-polybenzimidazoles
Block copolymer；
（4）Prepare sulfonated polyether amine-polybenzimidazoles block copolymer
In the dry three-necked bottles of 100mL, sequentially add 1 gram the polyetheramine-polybenzimidazoles block copolymer and
The concentrated sulfuric acid of the mass fraction 98% of 15mL, under nitrogen protection, after stirring 500min at 40 DEG C, pours into frozen water, anti-with frozen water
After the product is washed in after backwashing, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C of dryings obtain final product sulfonated polyether amine-poly- for 24 hours
Benzimidazole block copolymer.
In one embodiment, described high temperature resistant high-hardness water-proof wall covering, in parts by weight, its preparing raw material
Also comprising benzimidazole 1-3 parts of 2- (1,3- thiazole-4-yls) and epoxy-capped polyetheramine 10-15 parts of nano zine oxide of cladding.
Another aspect of the present invention provides a kind of preparation method of high temperature resistant high-hardness water-proof wall covering, including：Will be described
Material component is added after being sufficiently mixed 1-100 minutes in mixer, and discharging is obtained.
In one embodiment, the preparation method of described high temperature resistant high-hardness water-proof wall covering, it is characterised in that
The well-mixed time is 25 minutes.
In one embodiment, the preparation method of described high temperature resistant high-hardness water-proof wall covering, the mixer
Stir speed (S.S.) be 10 ~ 1000 revs/min；Preferably, the stir speed (S.S.) of the mixer is 600 revs/min.
Compared with prior art, beneficial effects of the present invention are：
1st, by the addition of single substance（That is the addition of polyquaternium modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer）Both
Excellent weatherability can be provided, intensity higher, good fire resistance and excellent anti-microbial property, and can rise again
Prevent system excessively crisp to plasticization, processing step can also be greatly reduced, so as to provide Advantageous Effects of the invention.
2nd, the addition of sulfonated polyether amine-polybenzimidazoles block copolymer can provide enough rigidity and improve crosslinking it is close
Degree, so as to improve the intensity of system, and can simultaneously improve weatherability and anti-flammability, so that there is provided Advantageous of the invention effect
Really.
3rd, the addition of 2- (1,3- thiazole-4-yls) benzimidazole can improve system rigidity and by with it is sulfonic from
The crosslink density of son crosslinking raising system, further, strengthens the intensity and water resistance of coating, so as to have there is provided of the invention
Beneficial technique effect.
Specific embodiment
Raw material:
3,3 '-diaminobenzidine is purchased from CTI, and directly uses, without being further purified.Portland cement is common conch
Board cement, purchased from the pure and fresh Cement Co., Ltd in Guangdong.Montmorillonite is purchased from Xinyang Pingqiao District Yu Long bentonites factory.Cellulose ether is selected
With sodium carboxymethylcellulose (CMC), purchased from Yi Bo Chemical Co., Ltd.s, model IL6.Polyoxyethylene polyoxy propyl alcohol amidogen ether
（BAPE defoamers）Purchased from Shanghai De Mao Chemical Co., Ltd.s.Styrene-acrylic emulsion is purchased from Henkel, and the trade mark is 1863.Epoxy silane is coupled
Agent KH-560 is purchased from Chemical Reagent Co., Ltd., Sinopharm Group.1,3,5- tri- (4- naphthoxy -1,8- diacid) acid anhydride of benzene three is according to special
It is prepared by method disclosed in sharp CN101270111B.Nano zine oxide（300 nanometers of average grain diameter）It is limited purchased from middle credit fine chemistry industry
Company.Other raw materials are purchased from Aladdin reagent Co., Ltd.
Embodiment 1
By 25 grams of portland cement, 6 grams of montmorillonite, 3 grams of cellulose ether, 8 grams of polyoxyethylene polyoxy propyl alcohol amidogen ether, KH-560
4 grams, polyquaternium modification sulphonation polyetheramine -6 grams of hyperbranched poly pyrrole throat copolymer, 3 grams of 1,3- dibromopropanes, graphene oxide
After being sufficiently mixed 25 minutes in 6 grams and 3 grams of addition mixers of shitosan, discharging is obtained, and stir speed (S.S.) is 600 revs/min；
The preparation method of the polyquaternium modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is：
（1）Prepare polyquaternium
In the dry three-necked bottles of 1000ml, add 1,12- dibromo-dodecanes 0.1mol, Isosorbide-5-Nitrae-lupetazin 0.092mol with
And solvent dimethyl sulfoxide (DMSO) 80ml, after being reacted 5 hours at 50 DEG C, add N- methylimidazole 0.0025mol and N- methyl
Quinoline 0.0025mol, after being reacted 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium；
（2）Prepare amino-terminated polyetheramine
In the dry three-necked bottles of 1000mL, the benzylamine and 700 grams of diformazans of 95 grams epoxy resin E51,0.26mol are sequentially added
Base sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature,
And pour into rapidly in 2000mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration is simultaneously
Collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain amino-terminated polyetheramine；
（3）Prepare hyperbranched poly pyrrole throat
In the dry three-necked bottles of 100mL, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) acid anhydrides of benzene three are sequentially added
With 25ml metacresols, stir under nitrogen protection, after three acid anhydrides are completely dissolved, add the 3 of 0.006 mole, 3 '-benzidine
Amine, after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction terminates, it is down to
Room temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously received
Collection polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
（4）Prepare polyetheramine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of described amino-terminated polyetheramine, 0.6 gram of naphthalene anhydride end-blocking is sequentially added
The metacresol of hyperbranched poly pyrrole throat, the dimethyl sulfoxide (DMSO) of 10mL and 10mL, after stirring 60min under nitrogen protection, is heated to
80 DEG C, 4h is reacted, then at 185 DEG C, react 10h；After reaction terminates, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol, obtained
To a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 50 DEG C of dryings
24 hours, obtain final product polyetheramine-hyperbranched poly pyrrole throat copolymer；
（5）Prepare sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of the polyetheramine-hyperbranched poly pyrrole throat copolymer and 10mL is sequentially added
Mass fraction 98% the concentrated sulfuric acid, under nitrogen protection, at 40 DEG C stir 180min after, pour into frozen water, washed repeatedly with frozen water
After washing the product, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C of dryings obtain final product sulfonated polyether amine-hyperbranched for 24 hours
Poly- pyrrole throat copolymer；
（6）Prepare polyquaternium modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer
In 100ml three-necked bottles, step is added（1）0.2 gram of the polyquaternium for obtaining, step（5）The sulfonated polyether amine for obtaining-
0.5 gram of hyperbranched poly pyrrole throat copolymer, 0.2 gram of hexamethylene diamine, 0.05 gram of NaOH, deionized water 2mL and N, N- dimethyl
Formamide 50ml, after stirring at room temperature；After being reacted 10 hours at 60 DEG C, room temperature is down to, and pour into 2000mL first rapidly
In alcohol, a large amount of solids of sedimentation are obtained；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 60
DEG C drying 24 hours, obtains polyquaternium modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer.
Embodiment 2
By 25 grams of portland cement, 6 grams of montmorillonite, 3 grams of cellulose ether, 8 grams of polyoxyethylene polyoxy propyl alcohol amidogen ether, KH-560
4 grams, polyquaternium modified polyether amine -6 grams of hyperbranched poly pyrrole throat copolymer, 3 grams of 1,3- dibromopropanes, 6 grams of graphene oxide
And after in 3 grams of addition mixers of shitosan being sufficiently mixed 25 minutes, discharging is obtained, stir speed (S.S.) is 600 revs/min；
The preparation method of the polyquaternium modified polyether amine-hyperbranched poly pyrrole throat copolymer is：
（1）Prepare polyquaternium
In the dry three-necked bottles of 1000ml, add 1,12- dibromo-dodecanes 0.1mol, Isosorbide-5-Nitrae-lupetazin 0.092mol with
And solvent dimethyl sulfoxide (DMSO) 80ml, after being reacted 5 hours at 50 DEG C, add N- methylimidazole 0.0025mol and N- methyl
Quinoline 0.0025mol, after being reacted 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium；
（2）Prepare amino-terminated polyetheramine
In the dry three-necked bottles of 1000mL, the benzylamine and 700 grams of diformazans of 95 grams epoxy resin E51,0.26mol are sequentially added
Base sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature,
And pour into rapidly in 2000mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration is simultaneously
Collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain amino-terminated polyetheramine；
（3）Prepare hyperbranched poly pyrrole throat
In the dry three-necked bottles of 100mL, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) acid anhydrides of benzene three are sequentially added
With 25ml metacresols, stir under nitrogen protection, after three acid anhydrides are completely dissolved, add the 3 of 0.006 mole, 3 '-benzidine
Amine, after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction terminates, it is down to
Room temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously received
Collection polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
（4）Prepare polyetheramine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of described amino-terminated polyetheramine, 0.6 gram of naphthalene anhydride end-blocking is sequentially added
The metacresol of hyperbranched poly pyrrole throat, the dimethyl sulfoxide (DMSO) of 10mL and 10mL, after stirring 60min under nitrogen protection, is heated to
80 DEG C, 4h is reacted, then at 185 DEG C, react 10h；After reaction terminates, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol, obtained
To a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 50 DEG C of dryings
24 hours, obtain final product polyetheramine-hyperbranched poly pyrrole throat copolymer；
（5）Prepare polyquaternium modified polyether amine-hyperbranched poly pyrrole throat copolymer
In 100ml three-necked bottles, step is added（1）0.2 gram of the polyquaternium for obtaining, step（4）Polyetheramine-the over-expense for obtaining
Change poly- 0.5 gram of pyrrole throat copolymer, 0.2 gram of hexamethylene diamine, 0.05 gram of NaOH, deionized water 2mL and N, N- dimethyl formyl
Amine 50ml, after stirring at room temperature；After being reacted 10 hours at 60 DEG C, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol,
Obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C are done
Dry 24 hours, obtain polyquaternium modified polyether amine-hyperbranched poly pyrrole throat copolymer.
Embodiment 3
By 25 grams of portland cement, 6 grams of montmorillonite, 3 grams of cellulose ether, 8 grams of polyoxyethylene polyoxy propyl alcohol amidogen ether, KH-560
4 grams, sulfonated polyether amine -6 grams of hyperbranched poly pyrrole throat copolymer, 3 grams of 1,3- dibromopropanes, 6 grams of graphene oxide and shell gather
After being sufficiently mixed 25 minutes in sugared 3 grams of addition mixers, discharging is obtained, and stir speed (S.S.) is 600 revs/min；
The preparation method of the sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer is：
（1）Prepare amino-terminated polyetheramine
In the dry three-necked bottles of 1000mL, the benzylamine and 700 grams of diformazans of 95 grams epoxy resin E51,0.26mol are sequentially added
Base sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature,
And pour into rapidly in 2000mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration is simultaneously
Collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain amino-terminated polyetheramine；
（2）Prepare hyperbranched poly pyrrole throat
In the dry three-necked bottles of 100mL, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) acid anhydrides of benzene three are sequentially added
With 25ml metacresols, stir under nitrogen protection, after three acid anhydrides are completely dissolved, add the 3 of 0.006 mole, 3 '-benzidine
Amine, after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction terminates, it is down to
Room temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously received
Collection polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
（3）Prepare polyetheramine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of described amino-terminated polyetheramine, 0.6 gram of naphthalene anhydride end-blocking is sequentially added
The metacresol of hyperbranched poly pyrrole throat, the dimethyl sulfoxide (DMSO) of 10mL and 10mL, after stirring 60min under nitrogen protection, is heated to
80 DEG C, 4h is reacted, then at 185 DEG C, react 10h；After reaction terminates, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol, obtained
To a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 50 DEG C of dryings
24 hours, obtain final product polyetheramine-hyperbranched poly pyrrole throat copolymer；
（4）Prepare sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of the polyetheramine-hyperbranched poly pyrrole throat copolymer and 10mL is sequentially added
Mass fraction 98% the concentrated sulfuric acid, under nitrogen protection, at 40 DEG C stir 180min after, pour into frozen water, washed repeatedly with frozen water
After washing the product, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C of dryings obtain final product sulfonated polyether amine-hyperbranched for 24 hours
Poly- pyrrole throat copolymer.
Embodiment 4
By 25 grams of portland cement, 6 grams of montmorillonite, 3 grams of cellulose ether, 8 grams of polyoxyethylene polyoxy propyl alcohol amidogen ether, KH-560
3 grams of 4 grams, 3 grams of polyetheramine, 3 grams of hyperbranched poly pyrrole throat, 3 grams of 1,3- dibromopropanes, 6 grams of graphene oxide and shitosan add
Entering after be sufficiently mixed in mixer 25 minutes, discharging is obtained, stir speed (S.S.) is 600 revs/min；
The preparation method of the polyetheramine is：
In the dry three-necked bottles of 1000mL, the benzylamine and 700 grams of diformazans of 95 grams epoxy resin E51,0.26mol are sequentially added
Base sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature,
And pour into rapidly in 2000mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration is simultaneously
Collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain amino-terminated polyetheramine；
The preparation method of the hyperbranched poly pyrrole throat is：
In the dry three-necked bottles of 100mL, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) acid anhydrides of benzene three are sequentially added
With 25ml metacresols, stir under nitrogen protection, after three acid anhydrides are completely dissolved, add the 3 of 0.006 mole, 3 '-benzidine
Amine, after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction terminates, it is down to
Room temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously received
Collection polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride.
Embodiment 5
By 25 grams of portland cement, 6 grams of montmorillonite, 3 grams of cellulose ether, 8 grams of polyoxyethylene polyoxy propyl alcohol amidogen ether, KH-560
4 grams, 6 grams of styrene-acrylic emulsion, 3 grams of 1,3- dibromopropanes, in 3 grams of addition mixers of 6 grams of graphene oxide and shitosan fully
After mixing 25 minutes, discharging is obtained, and stir speed (S.S.) is 600 revs/min；
Embodiment 6
By 25 grams of portland cement, 6 grams of montmorillonite, 3 grams of cellulose ether, 8 grams of polyoxyethylene polyoxy propyl alcohol amidogen ether, KH-560
4 grams, polyquaternium modification sulphonation polyetheramine -6 grams of hyperbranched poly pyrrole throat copolymer, 3 grams of 1,3- dibromopropanes, graphene oxide
25 points are sufficiently mixed in 6 grams, 3 grams of shitosan and sulfonated polyether amine -3 grams of polybenzimidazoles block copolymer addition mixer
Zhong Hou, discharging is obtained, and stir speed (S.S.) is 600 revs/min；
The preparation method of the polyquaternium modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is：
（1）Prepare polyquaternium
In the dry three-necked bottles of 1000ml, add 1,12- dibromo-dodecanes 0.1mol, Isosorbide-5-Nitrae-lupetazin 0.092mol with
And solvent dimethyl sulfoxide (DMSO) 80ml, after being reacted 5 hours at 50 DEG C, add N- methylimidazole 0.0025mol and N- methyl
Quinoline 0.0025mol, after being reacted 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium；
（2）Prepare amino-terminated polyetheramine
In the dry three-necked bottles of 1000mL, the benzylamine and 700 grams of diformazans of 95 grams epoxy resin E51,0.26mol are sequentially added
Base sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature,
And pour into rapidly in 2000mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration is simultaneously
Collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain amino-terminated polyetheramine；
（3）Prepare hyperbranched poly pyrrole throat
In the dry three-necked bottles of 100mL, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) acid anhydrides of benzene three are sequentially added
With 25ml metacresols, stir under nitrogen protection, after three acid anhydrides are completely dissolved, add the 3 of 0.006 mole, 3 '-benzidine
Amine, after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction terminates, it is down to
Room temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously received
Collection polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
（4）Prepare polyetheramine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of described amino-terminated polyetheramine, 0.6 gram of naphthalene anhydride end-blocking is sequentially added
The metacresol of hyperbranched poly pyrrole throat, the dimethyl sulfoxide (DMSO) of 10mL and 10mL, after stirring 60min under nitrogen protection, is heated to
80 DEG C, 4h is reacted, then at 185 DEG C, react 10h；After reaction terminates, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol, obtained
To a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 50 DEG C of dryings
24 hours, obtain final product polyetheramine-hyperbranched poly pyrrole throat copolymer；
（5）Prepare sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of the polyetheramine-hyperbranched poly pyrrole throat copolymer and 10mL is sequentially added
Mass fraction 98% the concentrated sulfuric acid, under nitrogen protection, at 40 DEG C stir 180min after, pour into frozen water, washed repeatedly with frozen water
After washing the product, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C of dryings obtain final product sulfonated polyether amine-hyperbranched for 24 hours
Poly- pyrrole throat copolymer；
（6）Prepare polyquaternium modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer
In 100ml three-necked bottles, step is added（1）0.2 gram of the polyquaternium for obtaining, step（5）The sulfonated polyether amine for obtaining-
0.5 gram of hyperbranched poly pyrrole throat copolymer, 0.2 gram of hexamethylene diamine, 0.05 gram of NaOH, deionized water 2mL and N, N- dimethyl
Formamide 50ml, after stirring at room temperature；After being reacted 10 hours at 60 DEG C, room temperature is down to, and pour into 2000mL first rapidly
In alcohol, a large amount of solids of sedimentation are obtained；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 60
DEG C drying 24 hours, obtains polyquaternium modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer；
The preparation method of the sulfonated polyether amine-polybenzimidazoles block copolymer is：
（1）Prepare epoxy-capped polyetheramine
In the dry three-necked bottles of 1000mL, sequentially add 100 grams epoxy resin E51,0.25mol benzylamine and 700 gram two
Methyl sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room
Temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously collected
Polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product epoxy-capped polyetheramine；
（2）Prepare amino-terminated polybenzimidazoles
1800 grams of polyphosphoric acids is weighed in the dry three-neck flasks of 3L, gas access, drying tube, gas vent and machine is connected
Tool agitator, is passed through nitrogen, 0.1 mole of 3,3'- diaminobenzidines is added after 5min, when tetramine is uniformly dispersed being dissolved in
After in polyphosphoric acids, 0.015 mole of 5- amino isophthalic acids and 0.08 mole of dodecanedioic acid is added, added afterwards
400 grams of phosphorus pentoxides start simultaneously at stirring and heat up to strengthen the absorption to reaction product water, 200 DEG C are warming up to, in the temperature
Lower reaction 20h；After question response system temperature is cooled to 150 DEG C, pour into deionized water, cyclic washing removal polyphosphoric acids；It
Product is poured into the sodium hydrate aqueous solution that mass fraction is 8% afterwards stirs 24h, removed with deionized water cyclic washing afterwards
NaOH, by products therefrom in the vacuum drying oven dry for standby at 60 DEG C, obtain final product amino-terminated polybenzimidazoles prepolymer；
（3）Prepare polyetheramine-polybenzimidazoles block copolymer
In the dry three-necked bottles of 100mL, 0.3 gram of described epoxy-capped polyetheramine, 1 gram described amino-terminated is sequentially added
The dimethyl sulfoxide (DMSO) of polybenzimidazoles prepolymer and 10mL, after stirring 60min under nitrogen protection, is heated to 80 DEG C, reaction
10h；After reaction terminates, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；Washed repeatedly with methyl alcohol
After washing the product, suction filtration and collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product polyetheramine-polybenzimidazoles
Block copolymer；
（4）Prepare sulfonated polyether amine-polybenzimidazoles block copolymer
In the dry three-necked bottles of 100mL, sequentially add 1 gram the polyetheramine-polybenzimidazoles block copolymer and
The concentrated sulfuric acid of the mass fraction 98% of 15mL, under nitrogen protection, after stirring 500min at 40 DEG C, pours into frozen water, anti-with frozen water
After the product is washed in after backwashing, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C of dryings obtain final product sulfonated polyether amine-poly- for 24 hours
Benzimidazole block copolymer.
Embodiment 7
By 25 grams of portland cement, 6 grams of montmorillonite, 3 grams of cellulose ether, 8 grams of polyoxyethylene polyoxy propyl alcohol amidogen ether, KH-560
4 grams, polyquaternium modification sulphonation polyetheramine -6 grams of hyperbranched poly pyrrole throat copolymer, 3 grams of 1,3- dibromopropanes, graphene oxide
6 grams, 3 grams of shitosan, sulfonated polyether amine -3 grams of polybenzimidazoles block copolymer, 2- (1,3- thiazole-4-yls) benzimidazole 2
Gram and epoxy-capped polyetheramine cladding 10 grams of addition mixers of nano zine oxide in be sufficiently mixed 25 minutes after, discharging is obtained,
Stir speed (S.S.) is 600 revs/min；
The preparation method of the polyquaternium modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer is：
（1）Prepare polyquaternium
In the dry three-necked bottles of 1000ml, add 1,12- dibromo-dodecanes 0.1mol, Isosorbide-5-Nitrae-lupetazin 0.092mol with
And solvent dimethyl sulfoxide (DMSO) 80ml, after being reacted 5 hours at 50 DEG C, add N- methylimidazole 0.0025mol and N- methyl
Quinoline 0.0025mol, after being reacted 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium；
（2）Prepare amino-terminated polyetheramine
In the dry three-necked bottles of 1000mL, the benzylamine and 700 grams of diformazans of 95 grams epoxy resin E51,0.26mol are sequentially added
Base sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature,
And pour into rapidly in 2000mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration is simultaneously
Collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain amino-terminated polyetheramine；
（3）Prepare hyperbranched poly pyrrole throat
In the dry three-necked bottles of 100mL, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) acid anhydrides of benzene three are sequentially added
With 25ml metacresols, stir under nitrogen protection, after three acid anhydrides are completely dissolved, add the 3 of 0.006 mole, 3 '-benzidine
Amine, after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction terminates, it is down to
Room temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously received
Collection polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
（4）Prepare polyetheramine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of described amino-terminated polyetheramine, 0.6 gram of naphthalene anhydride end-blocking is sequentially added
The metacresol of hyperbranched poly pyrrole throat, the dimethyl sulfoxide (DMSO) of 10mL and 10mL, after stirring 60min under nitrogen protection, is heated to
80 DEG C, 4h is reacted, then at 185 DEG C, react 10h；After reaction terminates, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol, obtained
To a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 50 DEG C of dryings
24 hours, obtain final product polyetheramine-hyperbranched poly pyrrole throat copolymer；
（5）Prepare sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of the polyetheramine-hyperbranched poly pyrrole throat copolymer and 10mL is sequentially added
Mass fraction 98% the concentrated sulfuric acid, under nitrogen protection, at 40 DEG C stir 180min after, pour into frozen water, washed repeatedly with frozen water
After washing the product, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C of dryings obtain final product sulfonated polyether amine-hyperbranched for 24 hours
Poly- pyrrole throat copolymer；
（6）Prepare polyquaternium modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer
In 100ml three-necked bottles, step is added（1）0.2 gram of the polyquaternium for obtaining, step（5）The sulfonated polyether amine for obtaining-
0.5 gram of hyperbranched poly pyrrole throat copolymer, 0.2 gram of hexamethylene diamine, 0.05 gram of NaOH, deionized water 2mL and N, N- dimethyl
Formamide 50ml, after stirring at room temperature；After being reacted 10 hours at 60 DEG C, room temperature is down to, and pour into 2000mL first rapidly
In alcohol, a large amount of solids of sedimentation are obtained；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 60
DEG C drying 24 hours, obtains polyquaternium modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer；
The preparation method of the sulfonated polyether amine-polybenzimidazoles block copolymer is：
（1）Prepare epoxy-capped polyetheramine
In the dry three-necked bottles of 1000mL, sequentially add 100 grams epoxy resin E51,0.25mol benzylamine and 700 gram two
Methyl sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room
Temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously collected
Polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product epoxy-capped polyetheramine；
（2）Prepare amino-terminated polybenzimidazoles
1800 grams of polyphosphoric acids is weighed in the dry three-neck flasks of 3L, gas access, drying tube, gas vent and machine is connected
Tool agitator, is passed through nitrogen, 0.1 mole of 3,3'- diaminobenzidines is added after 5min, when tetramine is uniformly dispersed being dissolved in
After in polyphosphoric acids, 0.015 mole of 5- amino isophthalic acids and 0.08 mole of dodecanedioic acid is added, added afterwards
400 grams of phosphorus pentoxides start simultaneously at stirring and heat up to strengthen the absorption to reaction product water, 200 DEG C are warming up to, in the temperature
Lower reaction 20h；After question response system temperature is cooled to 150 DEG C, pour into deionized water, cyclic washing removal polyphosphoric acids；It
Product is poured into the sodium hydrate aqueous solution that mass fraction is 8% afterwards stirs 24h, removed with deionized water cyclic washing afterwards
NaOH, by products therefrom in the vacuum drying oven dry for standby at 60 DEG C, obtain final product amino-terminated polybenzimidazoles prepolymer；
（3）Prepare polyetheramine-polybenzimidazoles block copolymer
In the dry three-necked bottles of 100mL, 0.3 gram of described epoxy-capped polyetheramine, 1 gram described amino-terminated is sequentially added
The dimethyl sulfoxide (DMSO) of polybenzimidazoles prepolymer and 10mL, after stirring 60min under nitrogen protection, is heated to 80 DEG C, reaction
10h；After reaction terminates, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；Washed repeatedly with methyl alcohol
After washing the product, suction filtration and collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product polyetheramine-polybenzimidazoles
Block copolymer；
（4）Prepare sulfonated polyether amine-polybenzimidazoles block copolymer
In the dry three-necked bottles of 100mL, sequentially add 1 gram the polyetheramine-polybenzimidazoles block copolymer and
The concentrated sulfuric acid of the mass fraction 98% of 15mL, under nitrogen protection, after stirring 500min at 40 DEG C, pours into frozen water, anti-with frozen water
After the product is washed in after backwashing, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C of dryings obtain final product sulfonated polyether amine-poly- for 24 hours
Benzimidazole block copolymer；
The epoxy-capped polyetheramine cladding nano zine oxide is prepared from by following methods：
In the dry three-necked bottles of 3L, the benzylamine and 400 grams of dimethyl of 100 grams epoxy resin E51,0.25mol are sequentially added
Sulfoxide, leads to nitrogen protection and magnetic agitation；After 2h is stirred at room temperature, heat up 80 DEG C of reaction 6h, is down to room temperature, is subsequently adding 600 grams
Dimethyl sulfoxide (DMSO) and 300 grams of nano zine oxides, after 2h is stirred at room temperature, suction filtration simultaneously obtains solid product, is washed repeatedly with deionized water
After washing the product, suction filtration simultaneously collects product, and in vacuum drying oven, 60 DEG C of dryings 24 hours obtain epoxy-capped polyetheramine cladding
Nano zine oxide.
Method of testing
Cleaning metope, it is ensured that wall is firm, by 100 grams of the coating of any one of embodiment 1 ~ 7,40 grams of deionized water and dimethyl
After 10 grams of sulfoxide is sufficiently mixed, batch upper wall is put down, complete construction.
According to JC/T 2083-2011 standard testings, 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, 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 1
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Application property | Can be with | Can be with | Can be with | Cannot | Can be with | Can be with | Can be with |
| Surface drying time | 1.1h | 1.7h | 0.8h | - | 2.4h | 0.9h | 0.3h |
| Appearance of film | Normally | Normally | Normally | It is abnormal | Normally | Normally | Normally |
| Alkali resistance | 193 | 177h | 220h | - | 41h | 288h | 421h |
| Abrasion resistance | 1638 times | 1355 times | 1909 times | - | 498 times | 2169 times | 2322 times |
| Adhesion strength | 0.99 | 0.76 | 1.15 | - | 0.49 | 1.30 | 1.99 |
| Antibiotic rate | 96% | 97% | 0 | - | 0 | 98% | 99% |
| Fire resistance period | 6.3h | 6.5h | 6.2h | - | 1.5 h | 6.9h | 9.8h |
Data above can be seen that gathers with polyquaternium modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer, sulfonation is not used
Ether amines-polybenzimidazoles block copolymer, 2- (1,3- thiazole-4-yls) benzimidazoles and epoxy-capped polyetheramine cladding nanometer
The coating of zinc oxide is compared, and coating of the invention has obvious better performance, is thus provided that Advantageous effect of the invention
Really.
Claims (10)
1. a kind of high temperature resistant high-hardness water-proof wall covering, it is characterised in that in parts by weight, its preparing raw material is included with the following group
Point：
Portland cement 10-30 parts
Montmorillonite 5-10 parts
Cellulose ether 1-5 parts
3-10 parts of polyoxyethylene polyoxy propyl alcohol amidogen ether
KH-560 1-5 parts
Polyquaternium modification sulphonation polyetheramine -5-10 parts of hyperbranched poly pyrrole throat copolymer
1,3- dibromopropane 1-5 parts
Graphene oxide 1-10 parts
Shitosan 1-5 parts.
2. high temperature resistant high-hardness water-proof wall covering according to claim 1, it is characterised in that in parts by weight, its system
Standby raw material includes following components：
25 parts of portland cement
6 parts of montmorillonite
3 parts of cellulose ether
8 parts of polyoxyethylene polyoxy propyl alcohol amidogen ether
4 parts of KH-560
Polyquaternium modification sulphonation polyetheramine -6 parts of hyperbranched poly pyrrole throat copolymer
1,3- 3 parts of dibromopropane
6 parts of graphene oxide
3 parts of shitosan.
3. high temperature resistant high-hardness water-proof wall covering according to claim 1, it is characterised in that the polyquaternium is modified
The preparation method of sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer is：
（1）Prepare polyquaternium
In the dry three-necked bottles of 1000ml, add 1,12- dibromo-dodecanes 0.1mol, Isosorbide-5-Nitrae-lupetazin 0.092mol with
And solvent dimethyl sulfoxide (DMSO) 80ml, after being reacted 5 hours at 50 DEG C, add N- methylimidazole 0.0025mol and N- methyl
Quinoline 0.0025mol, after being reacted 5 hours at 50 DEG C, vacuum distillation removal solvent obtains polyquaternium；
（2）Prepare amino-terminated polyetheramine
In the dry three-necked bottles of 1000mL, the benzylamine and 700 grams of diformazans of 95 grams epoxy resin E51,0.26mol are sequentially added
Base sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room temperature,
And pour into rapidly in 2000mL deionized waters, obtain a large amount of solids of sedimentation；With after the deionized water cyclic washing product, suction filtration is simultaneously
Collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain amino-terminated polyetheramine；
（3）Prepare hyperbranched poly pyrrole throat
In the dry three-necked bottles of 100mL, the 1 of 0.01 mole, 3,5- tri- (4- naphthoxy -1,8- diacid) acid anhydrides of benzene three are sequentially added
With 25ml metacresols, stir under nitrogen protection, after three acid anhydrides are completely dissolved, add the 3 of 0.006 mole, 3 '-benzidine
Amine, after 60min is stirred at room temperature, is heated to 80 DEG C, reacts 4h, then at 185 DEG C, reacts 10h；After reaction terminates, it is down to
Room temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously received
Collection polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product the terminated hyperbranched poly- pyrrole throat of naphthalene anhydride；
（4）Prepare polyetheramine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of described amino-terminated polyetheramine, 0.6 gram of naphthalene anhydride end-blocking is sequentially added
The metacresol of hyperbranched poly pyrrole throat, the dimethyl sulfoxide (DMSO) of 10mL and 10mL, after stirring 60min under nitrogen protection, is heated to
80 DEG C, 4h is reacted, then at 185 DEG C, react 10h；After reaction terminates, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol, obtained
To a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 50 DEG C of dryings
24 hours, obtain final product polyetheramine-hyperbranched poly pyrrole throat copolymer；
（5）Prepare sulfonated polyether amine-hyperbranched poly pyrrole throat copolymer
In the dry three-necked bottles of 100mL, 1 gram of the polyetheramine-hyperbranched poly pyrrole throat copolymer and 10mL is sequentially added
Mass fraction 98% the concentrated sulfuric acid, under nitrogen protection, at 40 DEG C stir 180min after, pour into frozen water, washed repeatedly with frozen water
After washing the product, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C of dryings obtain final product sulfonated polyether amine-hyperbranched for 24 hours
Poly- pyrrole throat copolymer；
（6）Prepare polyquaternium modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer
In 100ml three-necked bottles, step is added（1）0.2 gram of the polyquaternium for obtaining, step（5）The sulfonated polyether amine for obtaining-
0.5 gram of hyperbranched poly pyrrole throat copolymer, 0.2 gram of hexamethylene diamine, 0.05 gram of NaOH, deionized water 2mL and N, N- dimethyl
Formamide 50ml, after stirring at room temperature；After being reacted 10 hours at 60 DEG C, room temperature is down to, and pour into 2000mL first rapidly
In alcohol, a large amount of solids of sedimentation are obtained；With after the methyl alcohol cyclic washing product, suction filtration and collected polymer, in vacuum drying oven, 60
DEG C drying 24 hours, obtains polyquaternium modification sulphonation polyetheramine-hyperbranched poly pyrrole throat copolymer.
4. high temperature resistant high-hardness water-proof wall covering according to claim 1, it is characterised in that in parts by weight, its system
Standby raw material also includes sulfonated polyether amine -1-5 parts of polybenzimidazoles block copolymer.
5. high temperature resistant high-hardness water-proof wall covering according to claim 4, it is characterised in that the sulfonated polyether amine-
The preparation method of polybenzimidazoles block copolymer is：
（1）Prepare epoxy-capped polyetheramine
In the dry three-necked bottles of 1000mL, sequentially add 100 grams epoxy resin E51,0.25mol benzylamine and 700 gram two
Methyl sulfoxide, leads to nitrogen protection and magnetic agitation；After 1h is stirred at room temperature, heat up 95 DEG C of reaction 6h, after reaction terminates, is down to room
Temperature, and pour into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；With after the methyl alcohol cyclic washing product, suction filtration is simultaneously collected
Polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product epoxy-capped polyetheramine；
（2）Prepare amino-terminated polybenzimidazoles
1800 grams of polyphosphoric acids is weighed in the dry three-neck flasks of 3L, gas access, drying tube, gas vent and machine is connected
Tool agitator, is passed through nitrogen, 0.1 mole of 3,3'- diaminobenzidines is added after 5min, when tetramine is uniformly dispersed being dissolved in
After in polyphosphoric acids, 0.015 mole of 5- amino isophthalic acids and 0.08 mole of dodecanedioic acid is added, added afterwards
400 grams of phosphorus pentoxides start simultaneously at stirring and heat up to strengthen the absorption to reaction product water, 200 DEG C are warming up to, in the temperature
Lower reaction 20h；After question response system temperature is cooled to 150 DEG C, pour into deionized water, cyclic washing removal polyphosphoric acids；It
Product is poured into the sodium hydrate aqueous solution that mass fraction is 8% afterwards stirs 24h, removed with deionized water cyclic washing afterwards
NaOH, by products therefrom in the vacuum drying oven dry for standby at 60 DEG C, obtain final product amino-terminated polybenzimidazoles prepolymer；
（3）Prepare polyetheramine-polybenzimidazoles block copolymer
In the dry three-necked bottles of 100mL, 0.3 gram of described epoxy-capped polyetheramine, 1 gram described amino-terminated is sequentially added
The dimethyl sulfoxide (DMSO) of polybenzimidazoles prepolymer and 10mL, after stirring 60min under nitrogen protection, is heated to 80 DEG C, reaction
10h；After reaction terminates, room temperature is down to, and poured into rapidly in 2000mL methyl alcohol, obtain a large amount of solids of sedimentation；Washed repeatedly with methyl alcohol
After washing the product, suction filtration and collected polymer, in vacuum drying oven, 50 DEG C of dryings 24 hours obtain final product polyetheramine-polybenzimidazoles
Block copolymer；
（4）Prepare sulfonated polyether amine-polybenzimidazoles block copolymer
In the dry three-necked bottles of 100mL, sequentially add 1 gram the polyetheramine-polybenzimidazoles block copolymer and
The concentrated sulfuric acid of the mass fraction 98% of 15mL, under nitrogen protection, after stirring 500min at 40 DEG C, pours into frozen water, anti-with frozen water
After the product is washed in after backwashing, suction filtration and collected polymer, in vacuum drying oven, 60 DEG C of dryings obtain final product sulfonated polyether amine-poly- for 24 hours
Benzimidazole block copolymer.
6. high temperature resistant high-hardness water-proof wall covering according to claim 5, it is characterised in that in parts by weight, its system
Standby raw material is also comprising benzimidazole 1-3 parts of 2- (1,3- thiazole-4-yls) and epoxy-capped polyetheramine cladding nano zine oxide
10-15 parts.
7. a kind of preparation method of high temperature resistant high-hardness water-proof wall covering, including：By the thing described in claim any one of 1-6
Material composition is added after being sufficiently mixed 1-100 minutes in mixer, and discharging is obtained.
8. the preparation method of high temperature resistant high-hardness water-proof wall covering according to claim 7, it is characterised in that described to fill
The time for dividing mixing is 25 minutes.
9. the preparation method of high temperature resistant high-hardness water-proof wall covering according to claim 7, it is characterised in that described to stir
The stir speed (S.S.) for mixing machine is 10 ~ 1000 revs/min.
10. the preparation method of high temperature resistant high-hardness water-proof wall covering according to claim 9, it is characterised in that described
The stir speed (S.S.) of mixer is 600 revs/min.
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| CN107492409A (en) * | 2017-08-28 | 2017-12-19 | 王迅 | A kind of Insulating A High-Voltage transmission of electricity power cable |
| CN108069668A (en) * | 2017-12-15 | 2018-05-25 | 福建金戈铁甲建材有限公司 | Features backwater presses impervious marine glue paste paint |
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| CN108069668A (en) * | 2017-12-15 | 2018-05-25 | 福建金戈铁甲建材有限公司 | Features backwater presses impervious marine glue paste paint |
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