A kind of thicker steel structure fireproofing radiation shielding coating
Technical field
The invention belongs to technical field of coatings, in particular, it relates to a kind of thicker steel structure fireproofing radiation shielding coating.
Background technology
Along with the development of process of industrialization, especially in the middle of the construction of large-and-medium size cities, steel construction is with its superiority of constructing quickly and easily, become a very important Application in Building material, steel structure as metal material is established, and is applied in Standard Factory Room, large-scale stadium, airport, bridge, multi-storied garage and core buildings more. But the fire performance of steel construction and far not as brick mix structure, the critical temperature of steel is 540 DEG C, reaches this temperature, about its supporting capacity will reduce half. In general fire, about 15min can reach this temperature, thus causes caving in of buildings. This characteristic determines steel construction must take corresponding measures for the prevention of fire, usually can at steel structure surface brushing fireproof coating to ensure its fire performance. In addition, for core buildings, during such as Nuclear power plants, also wish that above-mentioned fireproof coating possesses the function of radioprotective simultaneously, can avoid like this using stereotype, both reduce cost, poisoning generation can be reduced again.
The thicker steel structure fire-proof paint used in prior art, on the one hand, only can play some resistance to wind abrasions, together with well cannot cementing in steel construction, it may also be useful to the life-span is short, on the other hand, also not possess the function of radioprotective, it is difficult to be used in core buildings.
Hence, it is highly desirable to by the improvement of formula, it is provided that together with one well can be combined in steel construction basic unit so that it is the life-span is long, adhesive property is good and possesses excellent fire prevention, the coating of radiation proof function.
Summary of the invention
In order to solve the problem, an aspect of the present invention provides a kind of thicker steel structure fireproofing radiation shielding coating, is made up of powder and water, counts by weight proportion, and described powder and water ratio are 1:0.6-1:1.5; Described powder is counted by weight, comprises following composition:
Preferably, described powder and water ratio are 1:1.4; Described powder is counted by weight, comprises following composition:
In one embodiment, described fire-proof packing is one or more in pearlstone, expanded vermiculite, hollow glass micropearl, sepiolite; Preferably, described fire-proof packing is hollow glass micropearl.
In one embodiment, described main tackiness agent is one or both in silicate cement, high-alumina cement; Preferably, described main tackiness agent is high-alumina cement.
In one embodiment, described auxiliary binder is polyvinyl alcohol.
In one embodiment, described pair of amino polyethyleneglycol modified hyperbranched poly pyrrole throat is prepared from by following method:
(1) the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride is prepared
Completely dry there-necked flask adds three acid anhydrides of 1 mole and appropriate meta-cresol, stir under protection of inert gas, after three acid anhydrides dissolve completely, add the tetramine of 0.5��1.2 mole, after at room temperature stirring 30min, it is heated to 75��85 DEG C, reaction 3.5��4.5h, again at 175��185 DEG C, reaction 3.5��4.5h; Reaction is down to room temperature, is obtained the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride after terminating;
(2) the two polyethyleneglycol modified hyperbranched poly pyrrole throat of amino of preparation
In the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride that step (1) obtains, add two amino polyoxyethylene glycol of 0.3��2 mole, under protection of inert gas after stirring at room temperature 30min, it is heated to 75��85 DEG C, reaction 3.5��4.5h, then at 175��185 DEG C, reaction 3.5��4.5h; Reaction is down to room temperature, solution is poured in methyl alcohol after terminating, and has precipitation to precipitate out; After filtering after removing solvent with methyl alcohol repetitive scrubbing, in vacuum drying oven, at 50 DEG C, dry 22��24h, obtain two polyethyleneglycol modified hyperbranched poly pyrrole throat of amino.
In one embodiment, described three acid anhydrides are 1,3,5-tri-(4-naphthyloxy-1,8-diacid) benzene three acid anhydride; The described tetramine for the preparation of the described pair of polyethyleneglycol modified hyperbranched poly pyrrole throat of amino is selected from 3,3 '-diaminobenzidine, 3,3 ', 4,4 '-tetramino phenyl ether, 3,3 ', 4,4 '-tetramino sulfobenzide, 3,3 ', 4,4 '-tetramino benzophenone, 1,2,4,5-tetramino benzene, 1,2, in 5,6-tetramino naphthalene any one or multiple; Preferably, described four tetramines for the preparation of the described pair of polyethyleneglycol modified hyperbranched poly pyrrole throat of amino are 3,3 ', 4,4 '-tetramino phenyl ether.
In one embodiment, the mean polymerisation degree of described pair of amino polyoxyethylene glycol be selected from 44,89,112,135,180,226,453,1135 and 2271 any one; Preferably, the mean polymerisation degree of described pair of amino polyoxyethylene glycol is 226.
In one embodiment, described polybenzimidazole modification Jie hole silicon is prepared from by following method:
(1) preparation of amino-terminated polybenzimidazole prepolymer
0.1 mole of tetramine is first dissolved in containing 85wt% Vanadium Pentoxide in FLAKES 1000 grams of polyphosphoric acid, then the diacid of 0.05��0.09 mole is joined in reaction solution, after reacting 15 hours at 220 DEG C, it is down to room temperature, precipitating, in water, then with ammonia neutralization, is filtered, vacuum-drying at 100 DEG C, obtains amino-terminated polybenzimidazole prepolymer;
(2) preparation of silane-modified Jie hole silicon
After the metal reaction container taking into account prolong with agitator, temperature of 1000mL adds deionized water 100mL, KH-5601g, under agitation add Jie hole silicon 20g slowly, after reacting 30 minutes under room temperature, obtain silane-modified Jie hole silicon by filtering;
(3) preparation of polybenzimidazole modification Jie hole silicon
The beaker of 300mL adds above-mentioned amino-terminated polybenzimidazole prepolymer 1.8g, dimethyl sulfoxide (DMSO) 150mL, after 70 DEG C of stirring and dissolving, adds above-mentioned silane-modified Jie hole silicon 15g and be warming up to 80 DEG C and be uniformly mixed 2 hours; Then mixture is poured in deionized water, and filter, filter cake is obtained polybenzimidazole modification Jie hole silicon for 4 hours 120 DEG C of vacuum-dryings.
In one embodiment, described diacid is selected oneself diacid, pentanedioic acid, pimelic acid, sebacic acid, dodecanedioic acid, terephthalic acid, m-phthalic acid, 2, in 2 '-biphenyl dicarboxylic acid, 4,4 '-biphenyl dicarboxylic acid and 5-amino m-phthalic acid any one or multiple; The described tetramine for the preparation of described polybenzimidazole modification Jie hole silicon is selected from 3,3 '-diaminobenzidine, 3,3 ', 4,4 '-tetramino phenyl ether, 3,3 ', 4,4 '-tetramino sulfobenzide, 3,3 ', 4,4 '-tetramino benzophenone, 1,2,4,5-tetramino benzene, 1,2, in 5,6-tetramino naphthalene any one or multiple; Preferably, the described tetramine for the preparation of described polybenzimidazole modification Jie hole silicon is 3,3 '-diaminobenzidine.
Compared with prior art, the useful effect of the present invention is:
1, poly-pyrrole throat has excellent weathering resistance, higher intensity and good flame retardant properties, but general poly-pyrrole throat does not have good processing characteristics, and other material in difficult and system is well compatible, by the modification of two amino polyoxyethylene glycol and selection dissaving structure, can effectively solve consistency and processing problems, in addition, the existence of a large amount of amino, can as the cross-linking set of system, greatly improve mechanical strength, hyperbranched special globosity, can so that coating has bigger internal volume, increase the distance between molecular chain, to improve fire prevention and shielding property further, thus provide the Advantageous Effects of the present invention.
2, polybenzimidazole has excellent weathering resistance and shielding property, by modification Jie hole silicon, it is possible to greatly improve its dispersion in system, and itself is also a kind of linking agent, it is possible to be perfectly distributed in coating, it is to increase intensity. In addition, Jie hole silicon has very strong adsorptive power, and self has a large amount of Micro porosities, can effectively reduce the conduction efficiency of energy, thus improves fire prevention and the radiation protection ability of coating further.
3, Graphene itself as the main raw material of production radioprotective clothes, by adding graphene oxide, both can strengthen the radiation protection ability of coating, again can by a large amount of introducings of polar group, it is to increase the degree of crosslinking of system, thus improves cohesive strength.
It is easier to understand the above-mentioned of the application and other features, aspect and advantage with reference to following detailed explanation.
Embodiment
Below by embodiment, the present invention is specifically described. What be necessary to herein means out is; following examples are only for the invention will be further described; limiting the scope of the invention can not be interpreted as; the improvement of some non-intrinsically safes that the professional and technical personnel in this field makes according to the content of above-mentioned the present invention and adjustment, still belong to protection scope of the present invention.
Raw material:
All tetramines, diacid are all purchased from CTI, SigmaAldrich, AlfaAesar or SCRC, and directly use, it is not necessary to be further purified. Polyvinyl alcohol is purchased from Kuraray, and model is PVA-224. Hydrophilic silicon oxides (dry method aerosil), purchased from Shenyang chemical inc. Jie hole silicon is MCM-41 type, purchased from Nanjing Xian Feng nano material company limited. Epoxy silane coupling agent KH-560 is purchased from Chemical Reagent Co., Ltd., Sinopharm Group. Graphene oxide is purchased from Suzhou You Gao nano material company limited, and model is UG-S10. Other raw materials are all purchased from my fourth reagent company limited.
A1: pearlstone
A2: hollow glass micropearl
B1: silicate cement
B2: high-alumina cement
C1: polyvinyl alcohol
D1: wollastonite powder
E1: mica powder
F1: the polyethyleneglycol modified hyperbranched poly pyrrole throat of two amino, is prepared from by following method:
(1) the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride is prepared
Completely dry there-necked flask adds 1,3,5-tri-(the 4-naphthyloxy-1 of 1 mole, 8-diacid) benzene three acid anhydride and 2000ml meta-cresol, stir under nitrogen protection, after three acid anhydrides dissolve completely, add the 3 of 0.5 mole, 3 '-diaminobenzidine, after at room temperature stirring 30min, it is heated to 85 DEG C, reaction 3.5h, again at 185 DEG C, reaction 4.5h; Reaction is down to room temperature, is obtained the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride after terminating;
(2) the two polyethyleneglycol modified hyperbranched poly pyrrole throat of amino of preparation
In the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride that step (1) obtains, the mean polymerisation degree adding 2 moles is two amino polyoxyethylene glycol of 226, under nitrogen protection after stirring at room temperature 30min, it is heated to 85 DEG C, reaction 4.5h, then at 185 DEG C, reaction 4.5h; Reaction is down to room temperature, solution is poured in methyl alcohol after terminating, and has precipitation to precipitate out; After filtering after removing solvent with methyl alcohol repetitive scrubbing, in vacuum drying oven, dry 24h at 50 DEG C, obtain two polyethyleneglycol modified hyperbranched poly pyrrole throat of amino.
F2: the polyethyleneglycol modified hyperbranched poly pyrrole throat of two amino, is prepared from by following method:
(1) the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride is prepared
Completely dry there-necked flask adds 1,3,5-tri-(the 4-naphthyloxy-1 of 1 mole, 8-diacid) benzene three acid anhydride and 2000ml meta-cresol, stir under nitrogen protection, after three acid anhydrides dissolve completely, add the 3 of 1 mole, 3 '-diaminobenzidine, after at room temperature stirring 30min, it is heated to 85 DEG C, reaction 3.5h, again at 185 DEG C, reaction 4.5h; Reaction is down to room temperature, is obtained the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride after terminating;
(2) the two polyethyleneglycol modified hyperbranched poly pyrrole throat of amino of preparation
In the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride that step (1) obtains, the mean polymerisation degree adding 1 mole is two amino polyoxyethylene glycol of 226, under nitrogen protection after stirring at room temperature 30min, it is heated to 85 DEG C, reaction 4.5h, then at 185 DEG C, reaction 4.5h; Reaction is down to room temperature, solution is poured in methyl alcohol after terminating, and has precipitation to precipitate out; After filtering after removing solvent with methyl alcohol repetitive scrubbing, in vacuum drying oven, dry 24h at 50 DEG C, obtain two polyethyleneglycol modified hyperbranched poly pyrrole throat of amino.
F3: the polyethyleneglycol modified hyperbranched poly pyrrole throat of two amino, is prepared from by following method:
(1) the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride is prepared
Completely dry there-necked flask adds 1,3,5-tri-(the 4-naphthyloxy-1 of 1 mole, 8-diacid) benzene three acid anhydride and 2000ml meta-cresol, stir, under nitrogen protection after three acid anhydrides dissolve completely, add 3,3 ', the 4 of 1 mole, 4 '-tetramino phenyl ether, after at room temperature stirring 30min, it is heated to 85 DEG C, reaction 3.5h, again at 185 DEG C, reaction 4.5h; Reaction is down to room temperature, is obtained the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride after terminating;
(2) the two polyethyleneglycol modified hyperbranched poly pyrrole throat of amino of preparation
In the terminated hyperbranched poly-pyrrole throat solution of naphthalene acid anhydride that step (1) obtains, the mean polymerisation degree adding 1 mole is two amino polyoxyethylene glycol of 226, under nitrogen protection after stirring at room temperature 30min, it is heated to 85 DEG C, reaction 4.5h, then at 185 DEG C, reaction 4.5h; Reaction is down to room temperature, solution is poured in methyl alcohol after terminating, and has precipitation to precipitate out; After filtering after removing solvent with methyl alcohol repetitive scrubbing, in vacuum drying oven, dry 24h at 50 DEG C, obtain two polyethyleneglycol modified hyperbranched poly pyrrole throat of amino.
G1: hydrophilic silicon oxides (dry method aerosil)
G2: Jie hole silicon
G3: polybenzimidazole modification Jie hole silicon, is prepared from by following method:
(1) preparation of amino-terminated polybenzimidazole prepolymer
By 0.1 mole 3,3 ', 4,4 '-tetramino phenyl ether is first dissolved in containing 85wt% Vanadium Pentoxide in FLAKES 1000 grams of polyphosphoric acid, then the terephthalic acid of 0.05 mole is joined in reaction solution, after reacting 15 hours at 220 DEG C, being down to room temperature, precipitating is in water, then with ammonia neutralization, filtering, vacuum-drying at 100 DEG C, obtains amino-terminated polybenzimidazole prepolymer;
(2) preparation of silane-modified Jie hole silicon
After the metal reaction container taking into account prolong with agitator, temperature of 1000mL adds deionized water 100mL, KH-5601g, under agitation add Jie hole silicon MCM-4120g slowly, after reacting 30 minutes under room temperature, obtain silane-modified Jie hole silicon by filtering;
(3) preparation of polybenzimidazole modification Jie hole silicon
The beaker of 300mL adds above-mentioned amino-terminated polybenzimidazole prepolymer 1.8g, dimethyl sulfoxide (DMSO) 150mL, after 70 DEG C of stirring and dissolving, adds above-mentioned silane-modified Jie hole silicon 15g and be warming up to 80 DEG C and be uniformly mixed 2 hours; Then mixture is poured in deionized water, and filter, filter cake is obtained polybenzimidazole modification Jie hole silicon for 4 hours 120 DEG C of vacuum-dryings.
G4: polybenzimidazole modification Jie hole silicon, is prepared from by following method:
(1) preparation of amino-terminated polybenzimidazole prepolymer
By 0.1 mole 3,3 '-diaminobenzidine is first dissolved in containing 85wt% Vanadium Pentoxide in FLAKES 1000 grams of polyphosphoric acid, then the 5-amino m-phthalic acid of 0.09 mole is joined in reaction solution, after reacting 15 hours at 220 DEG C, being down to room temperature, precipitating is in water, then with ammonia neutralization, filtering, vacuum-drying at 100 DEG C, obtains amino-terminated polybenzimidazole prepolymer;
(2) preparation of silane-modified Jie hole silicon
After the metal reaction container taking into account prolong with agitator, temperature of 1000mL adds deionized water 100mL, KH-5601g, under agitation add Jie hole silicon MCM-4120g slowly, after reacting 30 minutes under room temperature, obtain silane-modified Jie hole silicon by filtering;
(3) preparation of polybenzimidazole modification Jie hole silicon
The beaker of 300mL adds above-mentioned amino-terminated polybenzimidazole prepolymer 1.8g, dimethyl sulfoxide (DMSO) 150mL, after 70 DEG C of stirring and dissolving, adds above-mentioned silane-modified Jie hole silicon 15g and be warming up to 80 DEG C and be uniformly mixed 2 hours; Then mixture is poured in deionized water, and filter, filter cake is obtained polybenzimidazole modification Jie hole silicon for 4 hours 120 DEG C of vacuum-dryings.
H1:KH-560
I1: graphene oxide
Embodiment 1
By weight, 35 parts of B1,3 parts of C1 are added in agravic blender, open fly cutter, to avoid, bonding occurs, prevent from stirring inequality, churning time is 3 minutes, close fly cutter, then add 5 parts of D1,7 parts of E1,8 parts of F1,8 parts of G1,5 parts of H1 and 5 part of I1, continue to stir, churning time is 3 minutes, adds 20 parts of A1; Continuing to stir, churning time is: 2 minutes, metering packing discharging. By powder stirring evenly after, the ratio being 1:0.6 according to the ratio of powder with water stirs evenly, by weight, can use.
Embodiment 2
By weight, 45 parts of B2,8 parts of C1 are added in agravic blender, open fly cutter, to avoid, bonding occurs, prevent from stirring inequality, churning time is 3 minutes, close fly cutter, then add 15 parts of D1,15 parts of E1,15 parts of F1,15 parts of G1,15 parts of H1 and 15 part of I1, continue to stir, churning time is 3 minutes, adds 50 parts of A2; Continuing to stir, churning time is: 2 minutes, metering packing discharging. By powder stirring evenly after, the ratio being 1:1.5 according to the ratio of powder with water stirs evenly, by weight, can use.
Embodiment 3
By weight, 40 parts of B2,6 parts of C1 are added in agravic blender, open fly cutter, to avoid, bonding occurs, prevent from stirring inequality, churning time is 3 minutes, close fly cutter, then add 10 parts of D1,10 parts of E1,9 parts of F1,10 parts of G1,12 parts of H1 and 10 part of I1, continue to stir, churning time is 3 minutes, adds 45 parts of A2; Continuing to stir, churning time is: 2 minutes, metering packing discharging. By powder stirring evenly after, the ratio being 1:1.4 according to the ratio of powder with water stirs evenly, by weight, can use.
Embodiment 4
By weight, 40 parts of B2,6 parts of C1 are added in agravic blender, open fly cutter, to avoid, bonding occurs, prevent from stirring inequality, churning time is 3 minutes, close fly cutter, then add 10 parts of D1,10 parts of E1,9 parts of F2,10 parts of G2,12 parts of H1 and 10 part of I1, continue to stir, churning time is 3 minutes, adds 45 parts of A2; Continuing to stir, churning time is: 2 minutes, metering packing discharging. By powder stirring evenly after, the ratio being 1:1.4 according to the ratio of powder with water stirs evenly, by weight, can use.
Embodiment 5
By weight, 40 parts of B2,6 parts of C1 are added in agravic blender, open fly cutter, to avoid, bonding occurs, prevent from stirring inequality, churning time is 3 minutes, close fly cutter, then add 10 parts of D1,10 parts of E1,9 parts of F3,10 parts of G3,12 parts of H1 and 10 part of I1, continue to stir, churning time is 3 minutes, adds 45 parts of A2; Continuing to stir, churning time is: 2 minutes, metering packing discharging. By powder stirring evenly after, the ratio being 1:1.4 according to the ratio of powder with water stirs evenly, by weight, can use.
Embodiment 6
By weight, 40 parts of B2,6 parts of C1 are added in agravic blender, open fly cutter, to avoid, bonding occurs, prevent from stirring inequality, churning time is 3 minutes, close fly cutter, then add 10 parts of D1,10 parts of E1,9 parts of F3,10 parts of G4,12 parts of H1 and 10 part of I1, continue to stir, churning time is 3 minutes, adds 45 parts of A2; Continuing to stir, churning time is: 2 minutes, metering packing discharging. By powder stirring evenly after, the ratio being 1:1.4 according to the ratio of powder with water stirs evenly, by weight, can use.
Comparative example 1
By weight, 40 parts of B2,6 parts of C1 are added in agravic blender, open fly cutter, to avoid, bonding occurs, prevent from stirring inequality, churning time is 3 minutes, close fly cutter, then add 10 parts of D1,10 parts of E1,9 parts of F3,12 parts of H1 and 10 part of I1, continue to stir, churning time is 3 minutes, adds 45 parts of A2; Continuing to stir, churning time is: 2 minutes, metering packing discharging. By powder stirring evenly after, the ratio being 1:1.4 according to the ratio of powder with water stirs evenly, by weight, can use.
Comparative example 2
By weight, 40 parts of B2,6 parts of C1 are added in agravic blender, open fly cutter, to avoid, bonding occurs, prevent from stirring inequality, churning time is 3 minutes, close fly cutter, then add 10 parts of D1,10 parts of E1,10 parts of G4,12 parts of H1 and 10 part of I1, continue to stir, churning time is 3 minutes, adds 45 parts of A2; Continuing to stir, churning time is: 2 minutes, metering packing discharging. By powder stirring evenly after, the ratio being 1:1.4 according to the ratio of powder with water stirs evenly, by weight, can use.
Comparative example 3
By weight, 40 parts of B2,6 parts of C1 are added in agravic blender, opens fly cutter, to avoid, bonding occurs, preventing from stirring inequality, churning time is 3 minutes, closes fly cutter, then adds 10 parts of D1,10 parts of E1 and 12 part of H1, continuing to stir, churning time is 3 minutes, adds 45 parts of A2; Continuing to stir, churning time is: 2 minutes, metering packing discharging. By powder stirring evenly after, the ratio being 1:1.4 according to the ratio of powder with water stirs evenly, by weight, can use.
Testing method
According to GB/14907-2002 standard testing, it is specially:
1, state verification: observe the dispersion of coating and whether have caking
2, surface drying time answers��24h
3, splitting resistance: allow appearance 1��3 crackle, its width answers��1mm
4, cohesive strength >=0.04Mpa
5, ultimate compression strength >=0.5Mpa
6, dry density��650Kg/m2
7, alkali resistance: after 360h, coating does not ftracture, plays layer, obscission
8, acid resistance: after 360h, coating does not ftracture, plays layer, obscission
9, fire endurance: coat-thickness is 25mm, test fire endurance/h
Test result is in table 1.
Table 1
Above data can be found out, compared with the fireproof coating not using two polyethyleneglycol modified hyperbranched poly pyrrole throat of amino, polybenzimidazole modification Jie hole silicon and graphene oxide, the fireproof coating of the present invention has obvious better properties, because herein is provided the Advantageous Effects of the present invention.
Aforesaid example is only explanation property, for explaining some features of feature of the present disclosure. Appended claim is intended to the scope wide as far as possible that requirement it is contemplated that, and the embodiment presented herein is only the explanation of enforcement mode of selection of the combination according to all possible embodiment. Therefore, the claim that the purpose of applicant is appended is not illustrated the selectional restriction of the example of the feature of the present invention. And progress in science and technology waits form do not considered at present due to the inaccurate reason of language performance possible for jljl or son replacement, and these changes also should be interpreted as being covered by appended claim in the conceived case.