CN116144210A - High-flash-point fireproof coating based on modified cage-type silsesquioxane and preparation method thereof - Google Patents
High-flash-point fireproof coating based on modified cage-type silsesquioxane and preparation method thereof Download PDFInfo
- Publication number
- CN116144210A CN116144210A CN202310137319.8A CN202310137319A CN116144210A CN 116144210 A CN116144210 A CN 116144210A CN 202310137319 A CN202310137319 A CN 202310137319A CN 116144210 A CN116144210 A CN 116144210A
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- Prior art keywords
- flame retardant
- modified cage
- nitrogen
- silsesquioxane
- silicon
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention discloses a high-flash-point fireproof coating based on modified cage-type silsesquioxane and a preparation method thereof, and belongs to the technical field of protective flame-retardant coatings. The invention relates to a modified cage silsesquioxane-based high-flash-point fireproof coating, which comprises the following components in parts by mass: 2-5 parts of modified cage type silsesquioxane, 5-15 parts of composite flame retardant, 1-3 parts of cobalt iso-octoate, 0.2-1 part of methyl ethyl ketone peroxide, 140-160 parts of epoxy resin and 90-110 parts of curing agent; the modified cage-type silsesquioxane has better hydrophobicity, can improve the hydrophobic effect of a coating material, contains silicon and nitrogen, has better flame retardant effect in cooperation with a composite flame retardant consisting of a silicon-containing flame retardant and a nitrogen-bromine organic frame material, improves the flash point of a coating, and solves the problems of poor thermal stability, uneven distribution and poor high-temperature resistance of the hydrophobic agent of the conventional fireproof coating.
Description
Technical Field
The invention belongs to the technical field of protective flame-retardant coatings, and particularly relates to a high-flash-point fireproof coating based on modified cage-type silsesquioxane and a preparation method thereof.
Background
The fireproof paint can be used for the surface of a flammable substrate, reduces the combustibility of the surface of a coated material, retards the rapid spread of fire and is used for improving the fire resistance limit of the coated material. The flame retardant is applied to the surface of a flammable substrate, can change the combustion characteristics of the surface of the material, and can block the rapid spread of fire; or to building elements to increase the fire resistance limit of the element. Conventional fireproof coatings are classified into halogen-based, organic phosphorus-based, halogen-phosphorus-based, nitrogen-based, silicon-based, aluminum-magnesium-based, molybdenum-based, and the like, depending on the kind of elements.
Epoxy resins are a common fire retardant coating matrix, the fire retardant effect of which is mainly derived from the flame retardant additives therein. The use of flame retardants can significantly delay the time to fire, thereby preventing the spread of flame. Phosphorus-containing monomers are widely used to improve the flame retardancy of epoxy resins, but in such systems phosphorus-containing compounds often generate acidic species, leading to early degradation of the polymer, leading to the formation of substantial ash, and thus affecting the hydrophobicity of the coating.
Silicon-containing compounds such as silica or silane coupling agents are often added to fire-retardant coatings, for example, chinese patent CN101939382a, which discloses a flame-retardant resin composition, flame-retardant fibers, flame-retardant fabrics and heat-resistant protective clothing, and which is excellent in flame retardancy by adding a small amount of flame-retardant additives without impairing the conventional mechanical properties. The flame-retardant resin composition comprises a resin as a matrix material and composite particles comprising 10 to 30% by weight of titanium dioxide and 70 to 90% by weight of silica as main components. However, when it is used as a flame retardant to improve the flame retardancy of a material, it is added as solid silica, and there is a problem of poor compatibility with an epoxy resin matrix. For example, chinese patent CN106751634A discloses a flame-retardant corrosion-resistant modified unsaturated polyester resin, which comprises raw materials of maleic anhydride, diethylene glycol, phosphoric acid, dicyclopentadiene, phthalic anhydride, maleic anhydride, propylene glycol, hydroquinone, styrene, propoxylated bisphenol A, toluene diisocyanate, modified phenolic resin, epoxy resin, isophthalic acid, oleic acid, benzotriazole, methyl ethyl ketone peroxide, cobalt isooctanoate, composite filler, composite flame retardant, silane coupling agent KH-550, toughening agent, curing agent, leveling agent, curing accelerator and deionized water according to parts by weight. When the silane coupling agent is added as a coupling agent, the problem of poor thermal stability exists in a single silane coupling agent, and the high-temperature flame retardance performance is not high.
Chinese patent publication No. CN111234615A, publication date 2020.06.05 discloses a composition for hydrophobic coating, hydrophobic coating and preparation method and application thereof, wherein the composition comprises matrix rubber, auxiliary agent, hydrophobic agent and solvent, the hydrophobic coating prepared from the composition is coated on a sealing ring and vulcanized, the hydrophobic coating can form a hydrophobic coating on the sealing ring to obtain a hydrophobic sealing ring, the hydrophobic sealing ring can be used as a door sealing ring of a washing machine, and the coating on the hydrophobic sealing ring is not easy to fall off when the door sealing ring of the washing machine is twisted and stretched, has good bonding force with the sealing ring, and has good hydrophobic performance. The hydrophobic performance of the fire-retardant paint is improved by adding the hydrophobic agent, and when the fire-retardant paint is applied to fire-retardant paint, the high-temperature resistance of the hydrophobic agent is poor and is not applicable.
Therefore, there is a need to develop a fire-retardant coating with high thermal stability, even distribution of silane coupling agent in the fire-retardant coating and high temperature resistance of hydrophobic agent.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems of poor thermal stability, uneven distribution and poor high-temperature resistance of a hydrophobe of a silane coupling agent in the existing fireproof coating, the invention provides the modified cage-type silsesquioxane-based high-flash-point fireproof coating and the preparation method thereof.
2. Technical proposal
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention discloses a modified cage type silsesquioxane-based high-flash-point fireproof coating which comprises the following components in parts by mass: comprises 2 to 5 parts of modified cage type silsesquioxane, 5 to 15 parts of composite flame retardant, 1 to 3 parts of cobalt iso-octoate, 0.2 to 1 part of methyl ethyl ketone peroxide, 140 to 160 parts of epoxy resin and 90 to 110 parts of curing agent; the modified cage-type silsesquioxane has better hydrophobicity, can improve the hydrophobic effect of a coating material, contains silicon and nitrogen, and has better flame retardant effect in cooperation with a composite flame retardant consisting of a silicon-containing flame retardant and a nitrogen-bromine organic frame material.
According to a further technical scheme, the chemical formula of the modified cage type silsesquioxane is as follows:
wherein ,
according to a further technical scheme, the reaction formula of the modified cage type silsesquioxane is as follows:
wherein ,
the modified cage type silsesquioxane is prepared by reacting amino cage type polysilsesquioxane with toluene diisocyanate, a catalyst is not required to be added in the whole reaction process, the reaction process is easy to control, and the risk is low.
According to a further technical scheme, the preparation process of the modified cage type silsesquioxane comprises the following steps of:
a. 1.0 to 3.0g of amination cage type polysilsesquioxane is dissolved in 20 to 30ml of toluene in a 100ml three-necked flask, and then is magnetically stirred for 30min at 200 to 300rpm at 20 to 30 ℃;
b. slowly adding 0.3-0.5 g toluene diisocyanate; then, magnetically stirring at 500-700 rpm for 30min at 10-30 ℃ to obtain a white solid product, wherein the amino group of the aminated cage-shaped polysilsesquioxane reacts with an-NCO group, the magnetic stirring is mainly easier to operate, the modified cage-shaped polysilsesquioxane is prepared by washing twice with ethanol and deionized water and then drying the product by a freeze dryer.
According to a further technical scheme, the composite flame retardant is a composite formed by a silicon-containing flame retardant and a nitrogen-bromine organic frame material, and the mass ratio of the silicon-containing flame retardant to the nitrogen-bromine organic frame material is 1: (1-2.5) the silicon-containing flame retardant is a compound prepared by crosslinking chloropropyl triethoxysilane and chloromethyl trimethoxysilane, and the nitrogen-bromine organic framework material is a compound prepared by 2, 5-dibromo-p-phenylenediamine and 2,4, 6-tris (4-formylphenoxy) -1,3, 5-triazine; the epoxy resin is epoxy resin 828 or epoxy resin 815 or epoxy resin C 14 H 20 O 4 。
According to a further technical scheme, the silicon-containing flame retardant is a compound prepared by crosslinking chloropropyl triethoxysilane and chloromethyl trimethoxysilane, and has the structural formula:
wherein m=n=10 to 200, chloropropyl triethoxysilane and chloromethyl trimethoxysilane are connected at intervals, and the values of m and n are adjusted by the reaction time.
The preparation process of the silicon-containing flame retardant comprises the following steps:
step a, putting chloropropyl triethoxysilane and chloromethyl trimethoxysilane into a container filled with a solvent, heating in a water bath, adding alkali liquor to adjust pH, and uniformly stirring;
b, transferring the mixed solution obtained in the step a into a reaction kettle, reacting at a certain temperature, and cooling to room temperature to obtain a mixture;
and c, centrifuging, filtering, washing and drying the mixture obtained in the step b to obtain the silicon-containing flame retardant.
Wherein the mass ratio of the chloropropyl triethoxysilane to the chloromethyl trimethoxysilane in the step a is (2-5): (15-25); the solvent is N, N-dimethylformamide or a mixed solvent containing N, N-dimethylformamide, and the mixed solvent containing N, N-dimethylformamide is a mixed solvent containing 3-5 mL of N, N-dimethylformamide, 3-5 mL of ethanol and 3-5 mL of deionized water; the temperature of the water bath heating is 40-50 ℃, the alkali liquor is ammonia water, sodium hydroxide or potassium hydroxide can be used, the concentration of the alkali liquor is 5-8 mol/L, preferably 15-20 mL of ammonia water, the pH value of the alkali liquor is adjusted to 7.8-8.6, the reaction is promoted, the reaction cannot be carried out if the pH value is too small, and a product with too large molecular weight is formed if the pH value is too large, so that the dispersion of the flame retardant is not facilitated.
In the step b, the reaction temperature is 120-140 ℃ and the reaction time is 24 hours.
And c, mixing the mixture obtained by the reaction with 2-3L of ethanol, stirring at 600rpm for 30min, vacuum filtering and washing the sample for 5 times, and drying at 80 ℃ for 24h, wherein the ethanol is used as a detergent to remove impurities.
The nitrogen-bromine organic framework material is a cyclic structure prepared from 2, 5-dibromo-p-phenylenediamine and 2,4, 6-tri (4-formylphenoxy) -1,3, 5-triazine, and the nitrogen-bromine organic framework material passes through-NH in the 2, 5-dibromo-p-phenylenediamine 2 Is obtained by reacting and connecting with-C=O in 2,4, 6-tri (4-formylphenoxy) -1,3, 5-triazine, and has the structural formula of
The single pore diameter of the nitrogen-bromine organic frame material prepared by the invention is about 100nm, the grain diameter formed by overlapping a plurality of pores is 1-4 mu m, the too large grain diameter influences the strength of the fireproof coating, the mechanical property of the composite material can not be effectively improved, and the too small grain diameter is easy to agglomerate and influences the dispersibility of the composite material.
The invention also discloses a method for preparing the nitrogen-bromine organic frame material, which specifically comprises the following steps:
step a, dissolution: adding 2, 5-dibromo-p-phenylenediamine and 2,4, 6-tri (4-formylphenoxy) -1,3, 5-triazine into a solvent, uniformly mixing to obtain a mixed solution, and dispersing for 30min by adopting ultrasonic vibration, wherein the solvent is one or more of toluene, benzene and acetone, preferably toluene, benzene and acetone, and can be completely dissolved, and the adding amount of the solvent is preferably 20mL;
step b, adding acid: adding an acid solution into the mixed solution obtained in the step a, uniformly mixing, and dispersing for 30min by adopting ultrasonic oscillation preferably; wherein, the acid is preferably nitric acid, which is used for providing acidic conditions and promoting the reaction process, sulfuric acid and acetic acid can be used besides nitric acid, and the addition amount of the acid is preferably 10mL;
step c, reaction: b, transferring the mixture obtained in the step b into a reaction kettle, and reacting at a certain temperature;
and d, cooling, centrifuging, washing for 3 times, and drying to obtain the nitrogen-bromine organic frame material.
Wherein the mass ratio of the 2, 5-dibromo-p-phenylenediamine to the 2,4, 6-tri (4-formylphenoxy) -1,3, 5-triazine in the step a is as follows: (1.0-1.5): (1.5-1.9).
Still further, the molar ratio of the acid to 2, 5-dibromo-p-phenylenediamine in step b is 1: (1.8-2.9), wherein the acid is one or more of nitric acid, sulfuric acid and acetic acid, and the preferable concentration is 0.2mol/L.
In a further technical scheme, the reaction temperature in the step c is 150-160 ℃ and the reaction time is 24-36 h.
In a further technical scheme, in the step d, the drying temperature is 50 ℃, and the drying time is 24 hours.
According to a further technical scheme, the curing agent comprises one or more of aliphatic amine, aromatic amine, aminopolyamide and dicyandiamide, and when the curing agent is a mixture of the aliphatic amine, the aromatic amine, the aminopolyamide and the dicyandiamide, the mass ratio is 1:1:2:2.
in the prior art, a silicon-containing flame retardant is often used for improving the flame retardance of a material, and in order to solve the problem of poor thermal stability of a single silane coupling agent, a cross-linked polymer obtained by reacting two silane coupling agents is used as the flame retardant, the silane coupling agent forms a cross-linked network formed by combining Si-O bonds, the prepared silicon-containing flame retardant is excellent in thermal stability, the thermal decomposition temperature reaches 300 ℃, si-C bonds and Si-O bonds still exist in analysis of a carbon layer after combustion, thermal oxidation does not occur, and a more stable carbon layer is formed.
In addition, the conventional silane coupling agent is liquid, and the liquid silane coupling agent reacts with the epoxy resin at high temperature in the using process to influence the stability of the epoxy resin in the application process.
In addition, chloropropyl triethoxy silane and chloromethyl trimethoxy silane containing Cl element are used as raw materials, and part of Cl with flame retardant effect is still reserved after crosslinking.
The nitrogen-bromine organic frame has a large number of benzene ring structures, and electron cloud on the benzene ring and lone pair electrons on a silicon-containing flame retardant chain form conjugation, so that a more stable carbon layer is formed, the impact resistance of the fireproof coating is improved, and the service life of the fireproof coating is prolonged.
In addition, the nitrogen-bromine organic frame and the silicon-containing flame retardant have good compatibility with epoxy resin, and are favorable for uniform dispersion of components.
Based on the above, however, the inventors have surprisingly found that the use of 2,4, 6-tris (4-formylphenoxy) -1,3, 5-triazine is comprisedThe 2, 5-dibromo-p-phenylenediamine contains bromine and nitrogen, provides a nitrogen source and a bromine source with higher content, and bromine is used in the flame retardant to decompose and generate hydrogen bromide, the hydrogen bromide acts with a chain reaction active substance HO in flame to eliminate active free radicals generated by combustion reaction, so that the chain reaction of combustion is slowed down or stopped, the purpose of flame retardance is achieved, and ammonia and N are easy to release after the nitrogen flame retardant is decomposed by heating 2 The formation of the flame-retardant gas and the endothermic reaction of the conversion of the flame retardant bring most of heat productivity, reduce the surface temperature of the polymer, and can react with oxygen in the air to form water and nitrogen oxides, so that the excellent flame retardance effect is achieved while the oxygen on the surface layer of the raw material is consumed. Furthermore, the granular silicon-containing flame retardant is used as an inorganic filler to be filled in the coating, so that the strength of the resin can be enhanced, the problem of brittleness of the epoxy resin is solved, and the N generated in the use process is improved 2 Build N for thermal decomposition 2 Atmosphere favorable for the silane coupling agent to generate SiO 2 And carbon residue can form a compact isolation layer on the surface of the matrix to isolate heat, oxygen and combustible gas, and the contained Cl can capture free radicals to interrupt combustion reaction, so that the problem of flammability is solved.
The invention also discloses a preparation process of the fireproof paint, which comprises the following steps:
step A, adding modified cage-type silsesquioxane, a silicon-containing flame retardant and a nitrogen-bromine organic frame material into epoxy resin, stirring, adding a proper amount of dispersing agent, and uniformly mixing to obtain a mixture a;
step B, adding cobalt iso-octoate and methyl ethyl ketone peroxide into the mixture a, and uniformly stirring to obtain a mixture B;
and C, adding the curing agent into the mixture b, and uniformly mixing to obtain the fireproof coating containing the silicon flame retardant.
In the step A, the modified cage-type silsesquioxane, the silicon-containing flame retardant, the nitrogen-bromine organic frame material and the epoxy resin are vigorously stirred in a high-speed homogenizer for 30-50 min, and then a proper amount of dispersing agent is added, and the mixture is subjected to 150-170W ultrasonic treatment for 15-25 min, wherein the dispersing agent can be toluene or dimethylbenzene, so that the mixture can be dispersed, and the adding amount is 25% of the using amount of the epoxy resin; the mixture a is prepared after ultrasonic treatment for 15-25 min at 150-170W; and B, stirring the mixture B in the step B for 30 min.
In addition, the inventor tries to analyze the physical characteristics of the silicon-containing flame retardant and the nitrogen-bromine organic frame material, introduce the nitrogen-bromine organic frame material as a carrier of the silicon-containing flame retardant, utilize the characteristic that the nitrogen-bromine organic frame has porosity to take the nitrogen-bromine organic frame as a carbon skeleton of a carbon layer, and insert chain structures of the modified cage-type silsesquioxane and the silicon-containing flame retardant into holes of the nitrogen-bromine organic frame material to form a more compact and more uniformly distributed carbon layer, thereby being beneficial to isolating heat and combustible matters, avoiding the problem of poor consistency of the flame-retardant coating caused by the uneven distribution of the carbon layer, simultaneously being beneficial to the slow release effect of the modified cage-type silsesquioxane, being beneficial to the slow release of the hydrophobicity, being beneficial to the slow release of the combustible gas, and increasing the thickness of the carbon layer.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the silicon-containing flame retardant and the nitrogen-bromine organic frame material are used as the composite flame retardant, the silicon-containing flame retardant is a cross-linked product obtained by the reaction of two silane coupling agents and is used as the flame retardant, a cross-linked network formed by Si-O bond combination is formed, the thermal stability of a product crosslinked by the silane coupling agent is excellent, a more stable carbon layer is formed, and the product exists in the form of solid particles, so that the flash point of the fireproof coating can be effectively improved, and the storage and transportation of materials are facilitated; the nitrogen-bromine organic framework material is selected from 2,4, 6-tri (4-formylphenoxy) -1,3, 5-triazine and 2, 5-dibromo-p-phenylenediamine as substrates, and uses-C=O and-NH 2 The prepared nitrogen-bromine organic frame has a ring structure, is favorable for adsorbing silicon-containing compounds and combustible substances, and has benzene rings in the nitrogen-bromine organic frame materialThe electron cloud and the lone pair electrons on the silicon-containing flame retardant chain form conjugation, so that a more stable carbon layer is formed, and the impact strength and the service life of the fireproof paint are effectively improved;
(2) According to the invention, the flame retardant effect of the flame retardant auxiliary is improved by adding the modified cage-type silsesquioxane, and the silicon and the nitrogen contained in the modified cage-type silsesquioxane are synergistic, so that the nitrogen content in the coating can be improved, nitrogen-containing gas can be generated by decomposition in thermal decomposition, the concentration of the combustible gas is diluted, and the thickness of the carbon layer is increased. The research of the inventor shows that the addition of the cage-type silsesquioxane is a method for obtaining the surface roughness, the flame retardance of the cage-type silsesquioxane composite material is improved when the addition amount is low, but the flammability of the composite material is usually negatively affected by the high addition amount, so that the cage-type silsesquioxane composite material needs to be modified to improve the flame retardance of the composite material while maintaining the excellent hydrophobic property;
(3) The invention selects the chloropropyl triethoxy silane and chloromethyl trimethoxy silane containing Cl element, improves the thermal stability of the compound through crosslinking, retains a certain content of Cl after thermal decomposition, improves the flame retardant property, and the modified cage-type silsesquioxane has good hydrophobicity, counteracts the water repellency caused by a small amount of ash, and achieves the organic unification of the hydrophobicity and the flame retardance of the coating in cooperation with the two, thus obtaining the coating mixed formula with good superhydrophobicity and flame retardance;
(4) The nitrogen-bromine organic frame and the silicon-containing flame retardant have good compatibility with epoxy resin, and are favorable for uniform dispersion of components.
Drawings
The technical solution of the present invention will be described in further detail below with reference to the accompanying drawings and examples, but it should be understood that these drawings are designed for the purpose of illustration only and thus are not limiting the scope of the present invention. Moreover, unless specifically indicated otherwise, the drawings are intended to conceptually illustrate the structural configurations described herein and are not necessarily drawn to scale.
FIG. 1 is a schematic structural diagram of a silicon-containing flame retardant according to example 1 of the present invention;
FIG. 2 is a reaction scheme for preparing a silicon-containing flame retardant according to example 1 of the present invention;
FIG. 3 is a schematic structural diagram of a nitrogen-bromine organic frame material according to example 1 of the present invention;
FIG. 4 is a TG plot of nitrogen-bromine organic frame material of example 1 of the present invention;
FIG. 5 is a schematic representation of the chemical formula of a modified cage silsesquioxane of example 1 of the present invention;
FIG. 6 is a reaction scheme for preparing a modified cage silsesquioxane of example 1 of the present invention;
fig. 7 is a comparison of the fire protection effect of the fire retardant coating of the present invention.
Detailed Description
The following detailed description of exemplary embodiments of the invention refers to the accompanying drawings, which form a part hereof, and in which are shown by way of illustration exemplary embodiments in which the invention may be practiced. While these exemplary embodiments are described in sufficient detail to enable those skilled in the art to practice the invention, it is to be understood that other embodiments may be realized and that various changes to the invention may be made without departing from the spirit and scope of the invention. The following more detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is merely illustrative and not limiting of the invention's features and characteristics in order to set forth the best mode of carrying out the invention and to sufficiently enable those skilled in the art to practice the invention. Accordingly, the scope of the invention is limited only by the attached claims.
According to the specification of national standard GB/T13690-92 'classification and sign of common dangerous chemicals', liquid with flash point lower than 60 ℃ is dangerous, and potential safety hazards exist in the transportation and storage processes, so that the application of the paint diluent as a market commodity is limited. Thus, the invention will flash point (closed)>The epoxy resin of the present invention is epoxy resin 828 (molecular formula C 54 H 60 O 9 Flash point 78 ℃ C.) or epoxy 815 (molecular formula C 25 H 35 ClO 5 Flash point 192.4 ℃), epoxy resin (C) 14 H 20 O 4 The flash point is 118.3 ℃), other types of epoxy resins with flash points higher than 60 ℃ can be used for the fireproof coating, and the flash point of the fireproof coating is hardly affected due to the small addition amount of methyl ethyl ketone peroxide; and aliphatic amine (flash point more than 140 ℃), aromatic amine (flash point more than 100 ℃), aminopolyamide (flash point 110 ℃) and dicyandiamide (flash point 92.8 ℃), the flash points of the prepared fireproof paint are all above 60 ℃, and the fireproof paint is high-flash point fireproof paint.
Example 1
As shown in fig. 1 to 7, the modified cage silsesquioxane-based high-flash-point fireproof coating of the present embodiment includes the following components in parts by mass: 2 parts of modified cage type silsesquioxane, 5 parts of composite flame retardant, 1 part of cobalt iso-octoate, 0.2 part of methyl ethyl ketone peroxide, 140 parts of epoxy resin, 90 parts of curing agent, wherein the epoxy resin is epoxy resin 828 (the molecular formula is C 54 H 60 O 9 The flash point is 78 ℃), the composite flame retardant is a composite formed by a silicon-containing flame retardant and a nitrogen-bromine organic frame material, and the mass ratio of the silicon-containing flame retardant to the nitrogen-bromine organic frame material is 1:1.
in this embodiment, the curing agent is an aliphatic amine.
The chemical formula and the reaction formula of the modified cage type silsesquioxane are shown in fig. 5 and 6 respectively; wherein,
the modified cage type silsesquioxane is prepared by reacting amino cage type polysilsesquioxane with toluene diisocyanate, a catalyst is not required to be added in the whole reaction process, the reaction process is easy to control, and the risk is low; the preparation process of the modified cage type silsesquioxane comprises the following steps:
a. 1.0g of aminated cage-like polysilsesquioxane was dissolved in 20ml of toluene in a 100ml three-necked flask, followed by magnetic stirring at 200rpm for 30min at 20 ℃;
b. slowly adding 0.3g toluene diisocyanate; then, the mixture is magnetically stirred at 500rpm for 30min at 10 ℃ to obtain a white solid product, amino groups of the aminated cage-type polysilsesquioxane react with-NCO groups, the magnetic stirring is mainly easier to operate, the mixture is washed twice by ethanol and deionized water, and then the mixture is dried by a freeze dryer to obtain the modified cage-type polysilsesquioxane. The vacuum freeze dryer is used for drying, the conversion rate is over 95 percent, and compared with the common drying, the conversion rate is higher, and oxidation can occur in the common drying process, so that the influence on the product performance and the conversion rate due to oxidation in the drying process is avoided as much as possible by selecting a vacuum freeze drying mode.
In this embodiment, the structural formula and the reaction formula of the silicon-containing flame retardant are shown in fig. 1 and 2, respectively, and the preparation process comprises the following steps:
a. 2g of chloropropyl triethoxysilane and 15g of chloromethyl trimethoxysilane are placed in a three-necked flask which is filled with 200mLN, N-dimethylformamide, heated to 45℃in a water bath and 15mL of ammonia water (5 mol/L) are added, the pH is adjusted to 7.8, and stirring is carried out for half an hour;
b. transferring the mixed solution into a reaction kettle, maintaining the temperature at 120 ℃ for 24 hours, and then cooling to room temperature;
c. mixing with 2L ethanol, stirring at 600rpm for 30min, vacuum filtering and washing the sample for 5 times, and drying at 80 ℃ for 24h to obtain the silicon-containing flame retardant.
In this embodiment, the structural formula of the nitrogen-bromine organic framework material is shown in fig. 3, and the preparation process includes the following steps:
step a, dissolution: 1.0g of 2, 5-dibromo-p-phenylenediamine and 1.5g of 2,4, 6-tris (4-formylphenoxy) -1,3, 5-triazine were added to 20mL of toluene, followed by dispersion by ultrasonic vibration for 30min;
step b, adding acid: adding 10mL of nitric acid solution (0.2 mol/L) into the mixed solution obtained in the step a, and then carrying out ultrasonic vibration for 30min;
step c, reaction: b, transferring the mixture obtained in the step b into a reaction kettle, and placing the reaction kettle in an environment of 150 ℃ for 24 hours;
and d, cooling, centrifuging and washing 3 times by using toluene, and then drying in a drying oven at 50 ℃ for 24 hours to obtain the nitrogen-bromine organic frame material. As can be seen from the TG graph shown in FIG. 4, the prepared nitrogen-bromine organic frame material does not decompose at 0-300 ℃, the decomposition is accelerated at more than 300 ℃, the mass of the nitrogen-bromine organic frame material is the residual ash after more than 600 ℃, and compared with the traditional flame retardant material, the thermal decomposition temperature of the nitrogen-bromine organic frame material is improved by about 100 ℃.
In this embodiment, the preparation process of the fireproof coating comprises the following steps:
A. adding a silicon-containing flame retardant and a nitrogen-bromine organic frame material into epoxy resin, then vigorously stirring in a high-speed homogenizer for 30min, adding toluene accounting for 25% of the epoxy resin, and performing 150W ultrasonic treatment for 15min to obtain a mixture a;
B. adding cobalt iso-octoate and methyl ethyl ketone peroxide into the mixture a, and stirring for 30min to obtain a mixture b;
C. and adding the curing agent into the mixture b, and uniformly mixing to obtain the fireproof coating containing the silicon flame retardant.
Example 2
The basic components and steps of the modified cage silsesquioxane-based high-flash-point fireproof coating and the preparation method thereof in the embodiment are the same as those in the embodiment 1, and the difference or improvement is that: the high-flash-point fireproof coating comprises the following components in parts by mass: 3 parts of modified cage type silsesquioxane, 12 parts of composite flame retardant, 2 parts of cobalt iso-octoate, 0.5 part of methyl ethyl ketone peroxide, 150 parts of epoxy resin, 100 parts of curing agent, wherein the epoxy resin is epoxy resin 815 (the molecular formula is C 25 H 35 ClO 5 The flash point is 192.4 ℃), the composite flame retardant is a composite formed by a silicon-containing flame retardant and a nitrogen-bromine organic frame material, and the mass ratio of the silicon-containing flame retardant to the nitrogen-bromine organic frame material is 1:1.5.
in this embodiment, the curing agent is an aromatic amine.
In this example, the modified cage silsesquioxane was prepared as follows:
a. 2.0g of aminated cage-like polysilsesquioxane was dissolved in 25ml of toluene in a 100ml three-necked flask and then magnetically stirred at 250rpm for 30min at 25 ℃;
b. slowly adding 0.4g toluene diisocyanate; then, the mixture was magnetically stirred at 600rpm for 30min at 20℃to obtain a white solid product, modified cage silsesquioxane.
In this embodiment, the preparation process of the silicon-containing flame retardant includes the following steps:
a. 3g of chloropropyl triethoxysilane and 20g of chloromethyl trimethoxysilane are placed in a three-necked flask which is filled with 250mLN, N-dimethylformamide, heated to 45℃in a water bath and 15mL of ammonia water (8 mol/L) are added, the pH is adjusted to 8.1, and stirring is carried out for half an hour;
b. transferring the mixed solution into a reaction kettle, maintaining the temperature at 140 ℃ for 24 hours, and then cooling to room temperature;
c. mixing with 3L ethanol, stirring at 600rpm for 30min, vacuum filtering and washing the sample for 5 times, and drying at 80 ℃ for 24h to obtain the silicon-containing flame retardant.
In this embodiment, the preparation process of the nitrogen-bromine organic frame material includes the following steps:
step a, dissolution: 1.3g 2, 5-dibromo-p-phenylenediamine and 1.6g 2,4, 6-tri (4-formylphenoxy) -1,3, 5-triazine were added to 20mL toluene, followed by dispersion by ultrasonic vibration for 30min;
step b, adding acid: adding 10mL of nitric acid solution (0.2 mol/L) into the mixed solution obtained in the step a, and then carrying out ultrasonic vibration for 30min;
step c, reaction: b, transferring the mixture obtained in the step b into a reaction kettle, and placing the reaction kettle in an environment of 150 ℃ for 24 hours;
and d, cooling, centrifuging and washing 3 times by using toluene, and then drying in a drying oven at 50 ℃ for 24 hours to obtain the nitrogen-bromine organic frame material.
In this embodiment, the preparation process of the fireproof coating comprises the following steps:
A. adding modified cage-type silsesquioxane, a silicon-containing flame retardant and a nitrogen-bromine organic frame material into epoxy resin, then vigorously stirring in a high-speed homogenizer for 40min, adding toluene accounting for 25% of the epoxy resin, and performing ultrasonic treatment at 170W for 15min to obtain a mixture a;
B. adding cobalt iso-octoate and methyl ethyl ketone peroxide into the mixture, and stirring for 30min to obtain a mixture b;
C. and adding the curing agent into the mixture, and uniformly mixing to obtain the fireproof coating containing the silicon flame retardant.
Example 3
The modified cage-type silsesquioxane-based compound of the embodimentThe basic components and steps of the high-flash-point fireproof coating are the same as those of the embodiment 1, and the difference or improvement is that the high-flash-point fireproof coating comprises the following components in parts by mass: 5 parts of modified cage type silsesquioxane, 15 parts of composite flame retardant, 3 parts of cobalt iso-octoate, 1 part of methyl ethyl ketone peroxide, 160 parts of epoxy resin, 110 parts of curing agent, wherein the epoxy resin is epoxy resin (C) 14 H 20 O 4 The flash point is 118.3 ℃, the composite flame retardant is a composite formed by a silicon-containing flame retardant and a nitrogen-bromine organic frame material, and the mass ratio of the silicon-containing flame retardant to the nitrogen-bromine organic frame material is 1:2.5.
in the embodiment, the curing agent is a mixture of aliphatic amine, aromatic amine, aminopolyamide and dicyandiamide, and the mass ratio is 1:1:2:2.
in this example, the modified cage silsesquioxane was prepared as follows:
a. 3.0g of aminated cage-like polysilsesquioxane was dissolved in 30ml of toluene in a 100ml three-necked flask, followed by magnetic stirring at 300rpm for 30min at 30 ℃;
b. slowly adding 0.5g toluene diisocyanate; then, the mixture is magnetically stirred at 700rpm for 30min at 30 ℃ to obtain the white solid product modified cage type silsesquioxane.
In this embodiment, the preparation process of the silicon-containing flame retardant includes the following steps:
a. 5g of chloropropyl triethoxysilane and 25g of chloromethyl trimethoxysilane are placed in a three-necked flask which is filled with 300mLN, N-dimethylformamide, heated to 45℃in a water bath and then 20mL of ammonia water (8 mol/L) are added, the pH is adjusted to 8.6, and stirring is carried out for half an hour;
b. transferring the mixed solution into a reaction kettle, maintaining the temperature at 140 ℃ for 24 hours, and then cooling to room temperature;
c. mixing with 3L ethanol, stirring at 600rpm for 30min, vacuum filtering and washing the sample for 5 times, and drying at 80 ℃ for 24h to obtain the silicon-containing flame retardant.
In this embodiment, the preparation process of the nitrogen-bromine organic frame material includes the following steps:
step a, dissolution: 1.5g 2, 5-dibromo-p-phenylenediamine and 1.9g 2,4, 6-tri (4-formylphenoxy) -1,3, 5-triazine were added to 20mL toluene, followed by dispersion by ultrasonic vibration for 30min;
step b, adding acid: adding 10mL of nitric acid solution (0.2 mol/L) into the mixed solution obtained in the step a, and then carrying out ultrasonic vibration for 30min;
step c, reaction: b, transferring the mixture obtained in the step b into a reaction kettle, and placing the reaction kettle in 160 ℃ environment for 36h;
and d, cooling, centrifuging and washing 3 times by using toluene, and then drying in a drying oven at 50 ℃ for 24 hours to obtain the nitrogen-bromine organic frame material.
In this embodiment, the preparation process of the fireproof coating comprises the following steps:
A. adding modified cage-type silsesquioxane, a silicon-containing flame retardant and a nitrogen-bromine organic frame material into epoxy resin, then vigorously stirring in a high-speed homogenizer for 50min, adding toluene accounting for 25% of the epoxy resin, and performing ultrasonic treatment at 170W for 25min to obtain a mixture a;
B. adding cobalt iso-octoate and methyl ethyl ketone peroxide into the mixture a, and stirring for 30min to obtain a mixture b;
C. and adding the curing agent into the mixture b, and uniformly mixing to obtain the fireproof coating containing the silicon flame retardant.
Comparative example 1
The fireproof coating of the comparative example comprises the following components in parts by weight: 160 parts of epoxy resin and 110 parts of curing agent, wherein the curing agent is aliphatic amine.
And adding the curing agent into the epoxy resin, and mixing to obtain the epoxy resin coating.
Comparative example 2
The fireproof coating comprises the following components in parts by weight: 15 parts of silicon-containing flame retardant, 160 parts of epoxy resin and 110 parts of curing agent; the curing agent is an aromatic amine.
And adding the curing agent into the epoxy resin, and mixing to obtain the epoxy resin coating.
Comparative example 3
The fireproof coating comprises the following components in parts by weight: 15 parts of nitrogen-bromine organic frame material, 160 parts of epoxy resin and 110 parts of curing agent.
The curing agent is a mixture of aliphatic amine, aromatic amine, aminopolyamide and dicyandiamide, and the mass ratio is 1:1:2:2.
and adding the curing agent into the epoxy resin, and mixing to obtain the epoxy resin coating.
The requirements of national standard and industry standard on various parameters of the fireproof paint are used as comparison, and the comparison is carried out with various parameters of the high flash point fireproof paint prepared in the examples 1-3, namely an impact resistance-paint film impact resistance measuring method GB/T1732-1993; maximum heat release rate-ISO 5660-1/2/3/4-2002; the method for testing the weight loss and the residual quantity of the decomposed residue ratio-GB/T27761-2011 thermogravimetric analyzer comprises the steps of measuring a flash point of GB/T261-2008 by a binsyl-Martin closed cup method, and measuring a water contact angle (water contact angle: measurement of a contact angle between a GB/T30693-2014 plastic film and water); the corresponding detection results are shown in table 1:
table 1 results of measurements of parameters of the fire-retardant coating of comparative example and of the experimental examples 1 to 3
As can be seen from Table 1, the coatings prepared in examples 1-3 have impact resistance similar to that of the comparative examples, and the coatings prepared in examples 1-3 have a maximum heat release rate less than that of the comparative examples, and the coatings prepared in examples 1-3 have a decomposition residue ratio greater than that of the comparative examples, so that the flame retardant properties of the coatings prepared in the invention are superior and the mechanical properties thereof are not impaired. The flash points of the fireproof coatings of the examples 1-3 are all more than 60 ℃, meet the requirements of the hazardous chemical safety management regulations on the identification of non-hazardous chemicals, belong to the non-hazardous chemicals, and are beneficial to the storage and transportation of the fireproof coatings. The fireproof paint prepared in the embodiment 1-3 is introduced with nitrogen-bromine organic frame material as a carrier of the silicon-containing flame retardant, the nitrogen-bromine organic frame material is utilized to be used as a carbon skeleton of a carbon layer by utilizing the characteristic that the nitrogen-bromine organic frame has porosity, and meanwhile, chain structures of the modified cage-type silsesquioxane and the silicon-containing flame retardant are inserted into holes of the nitrogen-bromine organic frame material to form a more compact and uniformly distributed carbon layer, thereby being beneficial to isolating heat and combustible matters, avoiding the problem of poor consistency of the fireproof paint caused by uneven distribution of the carbon layer, being beneficial to loading of the silicon-containing compound and adsorption of the combustible matters, being beneficial to slow release effect of the modified cage-type silsesquioxane, being uniformly released by hydrophobicity, and slowly releasing the concentration of combustible gas, as shown in figure 7, and increasing the thickness of the carbon layer on the surface. In example 3, the amount of the modified cage-type silsesquioxane added was large, and the index of hydrophobicity of the modified cage-type silsesquioxane exhibited the best performance.
The foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (13)
1. The high-flash-point fireproof coating based on the modified cage type silsesquioxane is characterized by comprising 2-5 parts of modified cage type silsesquioxane, 5-15 parts of composite flame retardant, 1-3 parts of cobalt isooctanoate, 0.2-1 part of methyl ethyl ketone peroxide, 140-160 parts of epoxy resin and 90-110 parts of curing agent; the modified cage type silsesquioxane has a hydrophobic function.
2. The modified cage silsesquioxane based high flash point fire retardant coating of claim 1 wherein the modified cage silsesquioxane has the formula:
wherein ,
3. the modified cage silsesquioxane based high flash point fire retardant coating of claim 2 wherein the modified cage silsesquioxane has the following reaction formula:
4. the modified cage silsesquioxane-based high flash point fire retardant coating of claim 3 wherein the modified cage silsesquioxane is prepared by the process of:
a. 1.0 to 3.0g of amination cage type polysilsesquioxane is dissolved in 20 to 30ml of toluene in a 100ml three-necked flask, and then is magnetically stirred for 30min at 200 to 300rpm at 20 to 30 ℃;
b. slowly adding 0.3-0.5 g toluene diisocyanate; then, magnetically stirring for 30min at 500-700 rpm at 10-30 ℃ to obtain a white solid product, washing twice with ethanol and deionized water, and then drying with a freeze dryer to obtain the modified cage-type silsesquioxane.
5. The modified cage silsesquioxane based high flash point fire retardant coating of any of claims 1 to 4 wherein the composite flame retardant is a composite of a silicon containing flame retardant and a nitrogen bromine containing organic frame material in a mass ratio of 1: (1-2.5) the silicon-containing flame retardant is a compound prepared by crosslinking chloropropyl triethoxysilane and chloromethyl trimethoxysilane, and the nitrogen-bromine organic framework material is a compound prepared by 2, 5-dibromo-p-phenylenediamine and 2,4, 6-tris (4-formylphenoxy) -1,3, 5-triazine; the epoxy resin is epoxy resin 828 or epoxy resin 815 or epoxy resin C 14 H 20 O 4 。
6. The modified cage silsesquioxane based high flash fire retardant coating of claim 5 wherein the silicon containing flame retardant has the structural formula:
wherein m=n=10 to 200;
the structural formula of the nitrogen-bromine organic framework is
7. The modified cage silsesquioxane based high flash point fire retardant coating of claim 6 wherein the nitrogen-bromine organic framework material has a pore size of 100nm and a particle size of 1-4 μm.
8. The modified cage silsesquioxane based high flash point fire retardant coating of claim 7 wherein the method of preparing the silicon containing flame retardant comprises the steps of:
step a, adding chloropropyl triethoxysilane and chloromethyl trimethoxysilane into a solvent, heating in a water bath, adding alkali liquor to adjust pH, and stirring for half an hour;
b, heating the mixed solution obtained in the step a for reacting for a period of time, and then cooling to room temperature to obtain a mixture;
and c, centrifuging, vacuum filtering, washing and drying the mixture obtained in the step b to obtain the silicon-containing flame retardant.
9. The modified cage silsesquioxane-based high flash point fire retardant coating according to claim 8, wherein in step a, the mass ratio of chloropropyl triethoxysilane to chloromethyl trimethoxysilane is (2-5): (15-25), heating in water bath at 40-50 ℃, wherein the pH is 7.8-8.6, and the alkali liquor is one or more of ammonia water, sodium hydroxide or potassium hydroxide; the reaction temperature in the step b is 120-140 ℃ and the reaction time is 24 hours.
10. The modified cage silsesquioxane-based high flash point fire retardant coating according to claim 9, wherein the preparation method of the nitrogen-bromine organic frame material specifically comprises the following steps:
step a, dissolution: adding 2, 5-dibromo-p-phenylenediamine and 2,4, 6-tri (4-formylphenoxy) -1,3, 5-triazine into a solvent, and uniformly mixing to obtain a mixed solution;
step b, adding acid: adding an acid solution into the mixed solution obtained in the step a, and uniformly mixing to obtain a mixture;
step c, reaction: reacting the mixture obtained in the step b at a certain temperature;
and d, cooling, centrifuging, washing for 3 times, and drying to obtain the nitrogen-bromine organic frame material.
11. The modified cage silsesquioxane based high flash point fire retardant coating of claim 10 wherein the mass ratio of 2, 5-dibromo-p-phenylenediamine to 2,4, 6-tris (4-formylphenoxy) -1,3, 5-triazine in step a is: (1.0-1.5): (1.5-1.9); the molar ratio of acid to 2, 5-dibromo-p-phenylenediamine in step b is 1: (1.8-2.9); in the step c, the reaction temperature is 150-160 ℃ and the reaction time is 24-36 h.
12. A process for preparing a modified cage silsesquioxane based high flash point fire retardant coating as defined in any one of claims 1 to 11, comprising the steps of:
step A, adding modified cage-type silsesquioxane, a silicon-containing flame retardant and a nitrogen-bromine organic frame material into epoxy resin, stirring, adding a proper amount of dispersing agent, and uniformly mixing to obtain a mixture a;
step B, adding cobalt iso-octoate and methyl ethyl ketone peroxide into the mixture a, and uniformly stirring to obtain a mixture B;
and C, adding the curing agent into the mixture b, and uniformly mixing to obtain the fireproof coating containing the silicon flame retardant.
13. The preparation method of the modified cage type silsesquioxane-based high-flash-point fireproof coating according to claim 12, wherein in the step A, the modified cage type silsesquioxane, a silicon-containing flame retardant, a nitrogen-bromine organic frame material and epoxy resin are vigorously stirred in a high-speed homogenizer for 30-50 min, the dispersing agent is toluene or xylene, the adding amount of the dispersing agent is 25% of the using amount of the epoxy resin, and the mixture a is prepared after ultrasonic treatment for 15-25 min at 150-170W; and B, stirring the mixture B in the step B for 30 min.
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