A kind of slim dry powder fire-resistant coating for steel structure
Technical field
The invention belongs to technical field of coatings, more particularly to a kind of slim dry powder fire-resistant coating for steel structure.
Background technology
With the development of large- and-medium size cities, steel construction has become a critically important Application in Building material, and should
For in Standard Factory Room, large-scale stadium, airport, bridge, multi-storied garage and core building.But the critical-temperature of steel is
540 DEG C, fire resistance and brick mix structure is can not show a candle to, reach this temperature, its bearing capacity will reduce half or so.In general
In fire, 15min or so can reach this temperature, so as to cause caving in for building.This characteristic determines that steel construction is built
Corresponding fire prevention measure must be taken by building thing, it will usually in steel structure surface brushing fireproof coating to ensure its fire resistance.This
Outside, for core building, during such as nuclear power station, it is also desirable to which above-mentioned fireproof coating is provided simultaneously with the function of radiation proof, can so keep away
Exempt to use stereotype, both reduce cost, the generation of poisoning can be reduced again.
In the prior art, general to prepare fireproof coating using emulsion coatings, it is substantially prepared into using pure organic matter
Arrive, therefore anti-uv-ray is poor, weatherability is poor, and it is easily cracked after ultraviolet irradiates, fugitive color, Yi Huahua.In addition, because steel
Structure is different from the property of organic material, and the situation of expanding with heat and contract with cold differs, thus causes to apply charge level or lacquer painting and ftracture, come off etc. and show
As.Further, various emulsion coatings are containing the chemical substances such as ethylene glycol (antifreezing agent), ammoniacal liquor (pH value regulator), these materials
The pernicious gases such as VOC (VOC) and formaldehyde can be produced in work progress, environmental-protecting performance difference can be to people
Physical and mental health brings harmful effect.In addition, fireproof coating should also possess good wearability, to prevent external force from acting on, cause
The rupture of coating.
Hence it is highly desirable to the improvement for passing through formula, there is provided a kind of fire resisting is strong, good weatherability, wearability are strong, has anti-spoke
Penetrate performance and green slim dry powder fire-resistant coating for steel structure.
The content of the invention
In order to solve the above problems, one aspect of the present invention provides a kind of slim dry powder fire-resistant coating for steel structure, by weight
Amount ratio meter, including following component:
30 parts of white cement
Titanium dioxide 1-10 parts
Calcined kaolin 1-20 parts
Calcium carbonate 1-20 parts
Dimethyl silicone polymer 1-10 parts
Polymer modification graphene oxide 5-10 parts
Sulfonate polybenzimidazole is modified mesoporous silicon 5-10 parts
KH-560 2-10 parts
Drift-sand 0-0.1 parts;
The polymer modification graphene oxide is prepared by following methods:
(1)NTDA blocks the synthesis of poly- pyrrole throat prepolymer
In the three-necked bottle that 100mL is dried, the 3 of 10mmol is sequentially added, 3 '-diaminobenzidine DAB, 11mmol's
Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic acid anhydride NTDA, 22 mmol benzoic acid, 3mL isoquinolin and 40mLm- cresol, lead to nitrogen protection simultaneously
Magnetic agitation;After 2h, heat up 85 DEG C of reaction 6h, 190 °C of reaction 21h, reacts and is cooled to 70 DEG C after terminating and pours into rapidly
In 150mL methanol, a large amount of solid precipitations are obtained;After washing the product repeatedly with methanol, simultaneously collected polymer is filtered, is dried in vacuum
In case, 160 DEG C of 20 h of drying are stand-by;
(2) synthesis of amino-terminated sulfonated polyimide prepolymer
In the three-necked bottle that 100mL is dried, 1.6 mmol 2,2 '-bis- (4- sulfonic benzos epoxide) biphenyl two are sequentially added
Amine, 12.5 mL m-creso1 and 0.8 mL triethylamines, lead to nitrogen protection and magnetic agitation;Treat 2,2 '-bis- (4- sulfonic benzo oxygen
Base) after benzidine is completely dissolved, sequentially add the tetracarboxylic anhydrides of 1.5 mmol 3,4,9,10-, 3.0mmol benzoic acid with
And 0.6mL isoquinolin;After 1h is stirred at room temperature, heat up 80 DEG C of reactions 4h, 180 DEG C of reaction 20h;After reaction terminates, room temperature is down to,
Pending next step reaction;
(3) block copolymerization is reacted
It is pre- that the poly- pyrrole throat of NTDA end-blockings that 0.095 mmol steps (1) obtain is directly added into the reaction solution of step (2)
Polymers and 4mL m-Creso1, after leading to nitrogen and 1h being stirred at room temperature, heat up 180 DEG C of reaction 20h;Reaction is cooled to 80 after terminating
DEG C and pour into rapidly in 150mL methanol, obtain a large amount of thread products;After washing the product repeatedly with methanol, filter and collect poly-
Compound, in vacuum drying oven, 130 DEG C of dry 10h obtain amino-terminated block copolymer;
(4)Above-mentioned amino-terminated block copolymer 3g, dimethyl sulfoxide (DMSO) 150mL are added in 200mL beaker, at 80 DEG C
After stirring and dissolving, add KH-560 5g, graphene oxide 10g and be warming up to 80 DEG C and be stirred 2 hours;Then by mixture
Pour into deionized water, and filter, filter cake is obtained into polymer modification graphene oxide in 4 hours in 120 DEG C of vacuum drying;
The preparation method that the sulfonate polybenzimidazole is modified mesoporous silicon is:
By 0.1 mole 3,3 '-diaminobenzidine is first dissolved in 1000 grams of poly phosphorus containing 86wt% phosphorus pentoxides
In acid, then the 5- sulfonic group M-phthalic acids of 0.05 mole of 5- amino isophthalic acids and 0.04 mole are added to instead
Answer in liquid, after 210 DEG C are reacted 15 hours, be down to room temperature, then precipitating is neutralized into water with ammoniacal liquor, filtering, at 120 DEG C
Vacuum drying, obtains amino-terminated sulfonate polybenzimidazole prepolymer;
Deionized water 100 is added in the 1000 mL metal reaction container with agitator, thermometer and condenser pipe
After mL, KH-560 1.5g, mesoporous silicon MCM-41 20g are slowly added under agitation, are passed through after reacting 30 minutes at room temperature
Filter obtains silane-modified mesoporous silicon;
The amino-terminated sulfonate polybenzimidazole prepolymer 1.8g, dimethyl sulfoxide (DMSO) are added in 300mL beaker
150mL, after 75 DEG C of stirring and dissolvings, add above-mentioned silane-modified mesoporous silicon 15g and be warming up to 80 DEG C and be stirred 3 hours;So
After pour the mixture into deionized water, and filter, in 110 DEG C of vacuum drying filter cake is obtained into polybenzimidazoles for 12 hours is modified
Mesoporous silicon.
Another aspect of the present invention provides a kind of preparation method of slim dry powder fire-resistant coating for steel structure, including:By institute
After being sufficiently mixed 10 minutes in the material component addition mixer stated, discharging obtains.
Compared with prior art, beneficial effects of the present invention are:
1st, poly- pyrrole throat has an excellent weatherability, higher intensity, good fire resistance and excellent wearability, but
That the poly- pyrrole throat of in general does not have a good processing characteristics, and difficult compatible well with the other materials in system, by with sulphur
Change the method for polyimide block polymerization, and sulfonic group introduced in side chain, compatibility and processing problems can be efficiently solved,
The presence of a large amount of amino, is also used as the crosslinking points of system, greatly improves mechanical strength, in addition, introducing phenylate knot in side chain
Structure, wearability can be both improved, can cause coating that there is the distance between larger internal volume, increase strand again, with
Fire protecting performance and capability of resistance to radiation are further improved, by modifying graphene oxide, adhesion strength can be improved.In addition, sulphur
Fluidized polymer has good flocculability, cohesive and thickening property, and a large amount of sulfonic presence can be significantly reduced in material
The content of free calcium hydroxide, plays the generation for the accumulation of salt in the surface soil phenomenon for suppressing cement mortar surface, sulfonic water imbibition, can be with
Prevent that system is excessively crisp, so as to provide the advantageous effects of the present invention.
4th, polybenzimidazoles has excellent alkali resistance, by sulfonation and modified mesoporous silicon, can greatly improve it in body
Dispersiveness in system, and itself be also a kind of crosslinking agent, it can perfectly be distributed in coating, improve intensity.In addition, it is situated between
Hole silicon itself has substantial amounts of Micro porosity, can effectively improve the radiation protection ability of system, so as to provide having for the present invention
Beneficial technique effect.
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to described further below.
Embodiment
The present invention is specifically described below by embodiment.It is necessarily pointed out that following examples are only used
In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of the invention described above, still fall within protection scope of the present invention.
Raw material:
All tetramines, diacid are purchased from CTI, Sigma Aldrich, Alfa Aesar or SCRC, and directly use, nothing
It need to be further purified.Mesoporous silicon is MCM-41 types, purchased from Nanjing Xian Feng nano materials Co., Ltd.Epoxy silane coupling agent KH-
560 are purchased from Chemical Reagent Co., Ltd., Sinopharm Group.Graphene oxide is purchased from Suzhou You Gao nano materials Co., Ltd, model
UG-S10.Other raw materials are purchased from Aladdin reagent Co., Ltd.
A1:White cement
B1:Titanium dioxide
C1:Calcined kaolin
D1:Calcium carbonate
E1:Dimethyl silicone polymer
F1:Polymer modification graphene oxide, is prepared by following methods:
(1)NTDA blocks the synthesis of poly- pyrrole throat prepolymer
In the three-necked bottle that 100mL is dried, the 3 of 10mmol is sequentially added, 3 '-diaminobenzidine DAB, 11mmol's
Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic acid anhydride NTDA, 22 mmol benzoic acid, 3mL isoquinolin and 40mLm- cresol, lead to nitrogen protection simultaneously
Magnetic agitation;After 2h, heat up 85 DEG C of reaction 6h, 190 °C of reaction 21h, reacts and is cooled to 70 DEG C after terminating and pours into rapidly
In 150mL methanol, a large amount of solid precipitations are obtained;After washing the product repeatedly with methanol, simultaneously collected polymer is filtered, is dried in vacuum
In case, 160 DEG C of 20 h of drying are stand-by;
(2) synthesis of amino-terminated sulfonated polyimide prepolymer
In the three-necked bottle that 100mL is dried, 1.6 mmol 2,2 '-bis- (4- sulfonic benzos epoxide) biphenyl two are sequentially added
Amine, 12.5 mL m-creso1 and 0.8 mL triethylamines, lead to nitrogen protection and magnetic agitation;Treat 2,2 '-bis- (4- sulfonic benzo oxygen
Base) after benzidine is completely dissolved, sequentially add the tetracarboxylic anhydrides of 1.5 mmol 3,4,9,10-, 3.0mmol benzoic acid with
And 0.6mL isoquinolin;After 1h is stirred at room temperature, heat up 80 DEG C of reactions 4h, 180 DEG C of reaction 20h;After reaction terminates, room temperature is down to,
Pending next step reaction;
(3) block copolymerization is reacted
It is pre- that the poly- pyrrole throat of NTDA end-blockings that 0.095 mmol steps (1) obtain is directly added into the reaction solution of step (2)
Polymers and 4mL m-Creso1, after leading to nitrogen and 1h being stirred at room temperature, heat up 180 DEG C of reaction 20h;Reaction is cooled to 80 after terminating
DEG C and pour into rapidly in 150mL methanol, obtain a large amount of thread products;After washing the product repeatedly with methanol, filter and collect poly-
Compound, in vacuum drying oven, 130 DEG C of dry 10h obtain amino-terminated block copolymer;
(4)Above-mentioned amino-terminated block copolymer 3g, dimethyl sulfoxide (DMSO) 150mL are added in 200mL beaker, at 80 DEG C
After stirring and dissolving, add KH-560 5g, graphene oxide 10g and be warming up to 80 DEG C and be stirred 2 hours;Then by mixture
Pour into deionized water, and filter, filter cake is obtained into polymer modification graphene oxide in 4 hours in 120 DEG C of vacuum drying.
F2:Polymer modification graphene oxide, is prepared by following methods:
(1)NTDA blocks the synthesis of poly- pyrrole throat prepolymer
In the three-necked bottle that 100mL is dried, the 3 of 10mmol is sequentially added, 3 '-diaminobenzidine DAB, 11mmol's
Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic acid anhydride NTDA, 22 mmol benzoic acid, 3mL isoquinolin and 40mLm- cresol, lead to nitrogen protection simultaneously
Magnetic agitation;After 2h, heat up 85 DEG C of reaction 6h, 190 °C of reaction 21h, reacts and is cooled to 70 DEG C after terminating and pours into rapidly
In 150mL methanol, a large amount of solid precipitations are obtained;After washing the product repeatedly with methanol, simultaneously collected polymer is filtered, is dried in vacuum
In case, 160 DEG C of 20 h of drying are stand-by;
(2) synthesis of amino-terminated sulfonated polyimide prepolymer
In the three-necked bottle that 100mL is dried, 1.6 mmol 4,4 '-two (4- amino-benzene oxygens) biphenyl -3 are sequentially added, 3 '
Disulfonic acid aniline, 12.5 mL m-creso1 and 0.8 mL triethylamines, lead to nitrogen protection and magnetic agitation;Treat 2,2 '-bis- (4- sulphurs
Acidic group phenoxy group) after benzidine is completely dissolved, sequentially add 1.5 mmol Isosorbide-5-Nitraes, 5,8-naphthalenetetracarbacidic acidic acid anhydride NTDA,
3.0mmol benzoic acid and 0.6mL isoquinolin;After 1h is stirred at room temperature, heat up 80 DEG C of reactions 4h, 180 DEG C of reaction 20h;Reaction knot
Shu Hou, it is down to room temperature, pending next step reaction;
(3) block copolymerization is reacted
It is pre- that the poly- pyrrole throat of NTDA end-blockings that 0.095 mmol steps (1) obtain is directly added into the reaction solution of step (2)
Polymers and 4mL m-Creso1, after leading to nitrogen and 1h being stirred at room temperature, heat up 180 DEG C of reaction 20h;Reaction is cooled to 80 after terminating
DEG C and pour into rapidly in 150mL methanol, obtain a large amount of thread products;After washing the product repeatedly with methanol, filter and collect poly-
Compound, in vacuum drying oven, 130 DEG C of dry 10h obtain amino-terminated block copolymer;
(4)Above-mentioned amino-terminated block copolymer 3g, dimethyl sulfoxide (DMSO) 150mL are added in 200mL beaker, at 80 DEG C
After stirring and dissolving, add KH-560 5g, graphene oxide 10g and be warming up to 80 DEG C and be stirred 2 hours;Then by mixture
Pour into deionized water, and filter, filter cake is obtained into polymer modification graphene oxide in 4 hours in 120 DEG C of vacuum drying.
G1:Sulfonate polybenzimidazole is modified mesoporous silicon, and its preparation method is:
By 0.1 mole 3,3 '-diaminobenzidine is first dissolved in 1000 grams of poly phosphorus containing 86wt% phosphorus pentoxides
In acid, then the 5- sulfonic group M-phthalic acids of 0.05 mole of 5- amino isophthalic acids and 0.04 mole are added to instead
Answer in liquid, after 210 DEG C are reacted 15 hours, be down to room temperature, then precipitating is neutralized into water with ammoniacal liquor, filtering, at 120 DEG C
Vacuum drying, obtains amino-terminated sulfonate polybenzimidazole prepolymer;
Deionized water 100 is added in the 1000 mL metal reaction container with agitator, thermometer and condenser pipe
After mL, KH-560 1.5g, mesoporous silicon MCM-41 20g are slowly added under agitation, are passed through after reacting 30 minutes at room temperature
Filter obtains silane-modified mesoporous silicon;
The amino-terminated sulfonate polybenzimidazole prepolymer 1.8g, dimethyl sulfoxide (DMSO) are added in 300mL beaker
150mL, after 75 DEG C of stirring and dissolvings, add above-mentioned silane-modified mesoporous silicon 15g and be warming up to 80 DEG C and be stirred 3 hours;So
After pour the mixture into deionized water, and filter, in 110 DEG C of vacuum drying filter cake is obtained into polybenzimidazoles for 12 hours is modified
Mesoporous silicon.
G2:Sulfonate polybenzimidazole is modified mesoporous silicon, and its preparation method is:
By 0.1 mole 3,3 '-diaminobenzidine is first dissolved in 1000 grams of poly phosphorus containing 86wt% phosphorus pentoxides
In acid, then 0.09 mole of 5- amino isophthalic acids are added in reaction solution, after 210 DEG C are reacted 15 hours, are down to
Then room temperature, precipitating are neutralized into water with ammoniacal liquor, filtering, be dried in vacuo at 120 DEG C, obtain amino-terminated sulfonated polyphenyl simultaneously
Imidazoles prepolymer;
Deionized water 100 is added in the 1000 mL metal reaction container with agitator, thermometer and condenser pipe
After mL, KH-560 1.5g, mesoporous silicon MCM-41 20g are slowly added under agitation, are passed through after reacting 30 minutes at room temperature
Filter obtains silane-modified mesoporous silicon;
The amino-terminated sulfonate polybenzimidazole prepolymer 1.8g, dimethyl sulfoxide (DMSO) are added in 300mL beaker
150mL, after 75 DEG C of stirring and dissolvings, add above-mentioned silane-modified mesoporous silicon 15g and be warming up to 80 DEG C and be stirred 3 hours;So
After pour the mixture into deionized water, and filter, in 110 DEG C of vacuum drying filter cake is obtained into polybenzimidazoles for 12 hours is modified
Mesoporous silicon.
H1:KH-560
I1:Drift-sand
Embodiment 1
By weight, by 30 parts of A1,8 parts of B1,12 parts of C1,15 parts of D1,8 parts of E1,8 parts of F1,7 parts of G1,8 parts of H1 and
0.05 part of I1, add in mixer and be sufficiently mixed 10 minutes, discharge to obtain dry powder paint.By weight, powder and water are pressed 1:
After 0.5 ratio stirs, coated on steel construction, construction is completed.
Embodiment 2
By weight, by 30 parts of A1,8 parts of B1,12 parts of C1,15 parts of D1,8 parts of E1,8 parts of F2,7 parts of G1,8 parts of H1 and
0.05 part of I1, add in mixer and be sufficiently mixed 10 minutes, discharge to obtain dry powder paint.By weight, powder and water are pressed 1:
After 0.5 ratio stirs, coated on steel construction, construction is completed.
Embodiment 3
By weight, by 30 parts of A1,8 parts of B1,12 parts of C1,15 parts of D1,8 parts of E1,8 parts of F1,7 parts of G2,8 parts of H1 and
0.05 part of I1, add in mixer and be sufficiently mixed 10 minutes, discharge to obtain dry powder paint.By weight, powder and water are pressed 1:
After 0.5 ratio stirs, coated on steel construction, construction is completed.
Comparative example 1
By weight, by 30 parts of A1,8 parts of B1,12 parts of C1,15 parts of D1,8 parts of E1,7 parts of G2,8 parts H1 and 0.05 part
I1, add in mixer and be sufficiently mixed 10 minutes, discharge to obtain dry powder paint.By weight, powder and water are pressed 1:0.5 ratio
After example stirs, coated on steel construction, construction is completed.
Comparative example 2
By weight, by 30 parts of A1,8 parts of B1,12 parts of C1,15 parts of D1,8 parts of E1,8 parts of F1,8 parts H1 and 0.05 part
I1, add in mixer and be sufficiently mixed 10 minutes, discharge to obtain dry powder paint.By weight, powder and water are pressed 1:0.5 ratio
After example stirs, coated on steel construction, construction is completed.
Comparative example 3
By weight, by 30 parts of A1,8 parts of B1,12 parts of C1,15 parts of D1,8 parts of E1,8 parts of H1 and 0.05 part of I1, add
It is sufficiently mixed in mixer 10 minutes, discharge to obtain dry powder paint.By weight, powder and water are pressed 1:0.5 ratio stirring
After uniformly, coated on steel construction, construction is completed.
Method of testing
Antifriction performance:By standard GB/T1768-79, (89, method of testing is to use alcohol wear-resistant tester, adds 500g weights
Counterweight, the alcohol of 99.7% concentration is infiltrated with white cotton, is rubbed back and forth, number when recording ink starts to destroy.
Other performance, according to GB/14907-2002 standard testings, it is specially:
1st, surface drying time answers≤12h
2nd, crack resistance:Allow the Crack of appearance 1 ~ 3, its width answers≤0.5mm
3rd, adhesion strength >=0.15Mpa
4th, water resistance:After 24h, coating does not ftracture, aliquation, obscission
5th, cold-hot cyclicity/number:After 15 times, coating does not ftracture, aliquation, obscission
6th, fire endurance:Coating layer thickness is 5mm, and fire endurance is not less than 1h
Test result is shown in Table 1.
Table 1
Data above can be seen that to be situated between with being modified without using polymer modification graphene oxide and sulfonate polybenzimidazole
The coating of hole silicon is compared, and coating of the invention has obvious better performance, thus provides the advantageous effects of the present invention.
Foregoing example is merely illustrative, some features of the feature for explaining the disclosure.Appended claim
It is intended to require the scope as wide as possible being contemplated that, and embodiments as presented herein is only according to all possible embodiment
Combination selection embodiment explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention
Feature example selectional restriction.And the progress in science and technology will not formed due to the inaccuracy of language performance and not
The possible equivalent or son being presently considered are replaced, and these changes should also be interpreted by appended in the conceived case
Claim covers.