CN113444212B - Carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer and preparation method and application thereof - Google Patents

Carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer and preparation method and application thereof Download PDF

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CN113444212B
CN113444212B CN202110760530.6A CN202110760530A CN113444212B CN 113444212 B CN113444212 B CN 113444212B CN 202110760530 A CN202110760530 A CN 202110760530A CN 113444212 B CN113444212 B CN 113444212B
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zirconium dioxide
silsesquioxane
carboxyl
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张文超
张文远
杨荣杰
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Beijing Institute of Technology BIT
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Abstract

The invention relates to the technical field of organic-inorganic hybrid materials, in particular to a carboxyl-containing silsesquioxane coated zirconium dioxide porous polymer and a preparation method and application thereof. The preparation method comprises the steps of firstly, carrying out polymerization reaction on the surface of nano zirconium dioxide by utilizing polyvinyl silsesquioxane in the presence of a first free radical initiator and a pore-foaming agent to obtain a vinyl silsesquioxane-containing coated zirconium dioxide polymer, and then carrying out click reaction on a mercapto acid compound and a vinyl to obtain a carboxyl silsesquioxane-containing coated zirconium dioxide porous polymer. According to the preparation method, the carboxyl-containing silsesquioxane is successfully coated on the surface of the zirconium dioxide, so that the problems of agglomeration and poor pore structure are solved.

Description

Carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer and preparation method and application thereof
Technical Field
The invention relates to the technical field of organic-inorganic hybrid materials, in particular to a carboxyl-containing silsesquioxane coated zirconium dioxide porous polymer and a preparation method and application thereof.
Background
Zirconium dioxide has excellent heat resistance and corrosion resistance, is widely applied, and is one of the most promising functional materials in the century. However, the performance and application of the conventional zirconium dioxide are limited by poor thermal stability, small specific surface area, underdeveloped pores, easy agglomeration and the like.
The above problems are currently mainly ameliorated by surface modification of the zirconium dioxide. Polyhedral oligomeric silsesquioxane (POSS) is a silsesquioxane with the general formula (RSiO)1.5)nThe POSS has excellent performances such as low density, good gas permeability, heat resistance, flame retardance, good radiation resistance and the like, and can be used for research in many fields by virtue of the excellent performances of the POSS, particularly in the aspect of preparing a novel organic-inorganic hybrid material by a modified polymer. However, the surface chemical stability of zirconium dioxide is high, and it is difficult to modify the surface of zirconium dioxide with POSS.
Disclosure of Invention
The invention aims to provide a carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer, and a preparation method and application thereof. According to the preparation method, the carboxyl-containing silsesquioxane is successfully coated on the surface of the zirconium dioxide, so that the problem of poor pore structure is solved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of carboxyl-containing silsesquioxane coated zirconium dioxide porous polymer, which comprises the following steps:
mixing polyvinyl cage-type silsesquioxane, nano zirconium dioxide, a pore-foaming agent, a first free radical initiator and a first organic solvent, and carrying out polymerization reaction to obtain a vinyl-containing silsesquioxane-coated zirconium dioxide polymer;
and mixing the vinyl-containing silsesquioxane coated zirconium dioxide polymer, a mercapto acid compound, a second free radical initiator and a second organic solvent, and carrying out click reaction to obtain the carboxyl-containing silsesquioxane coated zirconium dioxide porous polymer.
Preferably, the polyvinyl cage silsesquioxane is octavinyl cage silsesquioxane, decavinyl cage silsesquioxane or dodecavinyl cage silsesquioxane.
Preferably, the pore-forming agent is polyethylene glycol.
Preferably, the first and second free radical initiators are independently azobisisobutyl and/or azobisisoheptonitrile.
Preferably, the dosage ratio of the polyvinyl cage-type silsesquioxane to the pore-forming agent to the nano zirconium dioxide to the first radical initiator is 1g (20-30) mL: 1g (0.01-0.02 g).
Preferably, the temperature of the polymerization reaction is 42-82 ℃, and the time is 12-36 h.
Preferably, the mercapto acid compound is thioglycolic acid or mercaptopropionic acid;
the mass ratio of the vinyl-containing silsesquioxane coated zirconium dioxide polymer to the second radical initiator to the mercapto acid compound is 1: (0.01-0.03): (3-4).
Preferably, the temperature of the click reaction is 50-70 ℃, and the time is 6-12 h.
The invention also provides a carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer prepared by the preparation method in the technical scheme, which comprises zirconium dioxide and a carboxyl-containing silsesquioxane polymer;
the structural unit in the carboxyl-containing silsesquioxane polymer has a structure shown as a formula I:
Figure GDA0003216747680000021
wherein n is 1 or 2;
the zirconium dioxide is encapsulated in the network of the carboxyl-containing silsesquioxane polymer.
The invention also provides application of the carboxyl-containing silsesquioxane coated zirconium dioxide porous polymer in the technical scheme in the flame retardant field.
The invention provides a preparation method of carboxyl-containing silsesquioxane coated zirconium dioxide porous polymer, which comprises the following steps: mixing polyvinyl cage-type silsesquioxane, nano zirconium dioxide, a pore-foaming agent, a first free radical initiator and a first organic solvent, and carrying out polymerization reaction to obtain a vinyl-containing silsesquioxane-coated zirconium dioxide polymer; and mixing the vinyl-containing silsesquioxane coated zirconium dioxide polymer, a mercapto acid compound, a second free radical initiator and a second organic solvent, and carrying out click reaction to obtain the carboxyl-containing silsesquioxane coated zirconium dioxide porous polymer. The preparation method comprises the steps of firstly, carrying out polymerization reaction on the surface of nano zirconium dioxide by utilizing polyvinyl silsesquioxane in the presence of a first free radical initiator and a pore-foaming agent to obtain a vinyl silsesquioxane-containing coated zirconium dioxide polymer, and then carrying out click reaction on a mercapto acid compound and a vinyl to obtain a carboxyl silsesquioxane-containing coated zirconium dioxide porous polymer. According to the invention, the carboxyl-containing silsesquioxane is coated on the surface of the zirconium dioxide, so that the problem of poor pore structure of the zirconium dioxide is well solved.
Drawings
FIG. 1 is a chart of the infrared spectrum of a vinyl-containing silsesquioxane-coated zirconium dioxide polymer prepared in example 1;
FIG. 2 shows an IR spectrum of a carboxyl-group-containing silsesquioxane-coated zirconium dioxide porous polymer prepared in example 1;
FIG. 3 is a solid silicon nuclear magnetic spectrum of the vinyl-containing silsesquioxane coated zirconia polymer prepared in example 2;
FIG. 4 is a solid silicon nuclear magnetic spectrum of the carboxyl-containing silsesquioxane coated zirconium dioxide porous polymer prepared in example 2;
FIG. 5 is a solid silicon nuclear magnetic spectrum of the vinyl-containing silsesquioxane coated zirconia polymer prepared in example 3;
FIG. 6 is a solid silicon nuclear magnetic spectrum of the carboxyl-containing silsesquioxane coated zirconium dioxide porous polymer prepared in example 3;
FIG. 7 is a graph showing the pore size distribution of a carboxyl-group-containing silsesquioxane-coated zirconium dioxide porous polymer prepared in example 3;
FIG. 8 is a graph showing the pore size distribution of a carboxyl-group-containing silsesquioxane-coated zirconium dioxide porous polymer prepared in example 4;
FIG. 9 is a graph showing the isothermal nitrogen adsorption desorption curve, the adsorption curve and the curve forming loop of the carboxyl-containing silsesquioxane coated zirconium dioxide porous polymer prepared in example 4;
FIG. 10 is a scanning electron micrograph and a corresponding energy spectrum of a carboxyl-containing silsesquioxane coated zirconium dioxide porous polymer prepared in example 4;
FIG. 11 is a thermogravimetric plot of the carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer prepared in example 4;
FIG. 12 is an SEM photograph of a carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer prepared in example 4;
fig. 13 is a graph showing heat release rate curves of an epoxy resin containing carboxyl-group-containing silsesquioxane-coated zirconium dioxide porous polymer prepared in example 4 and a pure epoxy resin.
Detailed Description
The invention provides a preparation method of carboxyl-containing silsesquioxane coated zirconium dioxide porous polymer, which comprises the following steps:
mixing polyvinyl cage-type silsesquioxane, nano zirconium dioxide, a pore-foaming agent, a first free radical initiator and a first organic solvent, and carrying out polymerization reaction to obtain a vinyl-containing silsesquioxane-coated zirconium dioxide polymer;
and mixing the vinyl-containing silsesquioxane coated zirconium dioxide polymer, a mercapto acid compound, a second free radical initiator and a second organic solvent, and carrying out click reaction to obtain the carboxyl-containing silsesquioxane coated zirconium dioxide porous polymer.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
The invention mixes polyvinyl cage-type silsesquioxane, nano zirconium dioxide, a pore-foaming agent, a first free radical initiator and a first organic solvent for polymerization reaction to obtain the vinyl silsesquioxane-containing coated zirconium dioxide polymer.
In the present invention, the multivinyl cage silsesquioxane is preferably an octavinyl cage silsesquioxane, a decavinyl cage silsesquioxane or a dodecavinyl cage silsesquioxane.
The particle size of the nano zirconium dioxide is not limited in any way, and can be in a nano level, which is well known to those skilled in the art.
In the present invention, the porogen is preferably polyethylene glycol, and more preferably polyethylene glycol 200 or polyethylene glycol 400.
In the present invention, the first radical initiator is preferably azobisisobutyl and/or azobisisoheptonitrile.
In the invention, the first organic solvent is preferably one or more of tetrahydrofuran, dichloromethane, acetone and trichloromethane; when the first organic solvent is more than two of the above specific choices, the present invention does not have any special limitation on the ratio of the specific substances, and the specific substances can be mixed according to any ratio.
In the invention, the dosage ratio of the polyvinyl cage-type silsesquioxane to the pore-forming agent to the nano zirconium dioxide to the first radical initiator is 1g (20-30) mL: 1g (0.01-0.02) g, more preferably 1g, 25 mL: 1g: 0.015 g.
In the present invention, the volume ratio of the total mass of the polyvinyl cage-type silsesquioxane, nano zirconia, and first radical initiator to the first organic solvent is preferably 1g: (30-40) mL, more preferably 1g: (33-36) mL, most preferably 1g: 35 mL.
In the invention, the mixing is preferably carried out by mixing the polyvinyl cage-type silsesquioxane, the nano zirconium dioxide, the pore-forming agent and the first organic solvent and then adding the first free radical initiator.
In the invention, the polymerization reaction temperature is preferably 42-82 ℃, more preferably 52-72 ℃, and most preferably 58-68 ℃; the time is preferably 12 to 36 hours, and more preferably 18 to 30 hours. In the present invention, the polymerization reaction is preferably carried out under stirring conditions, and the stirring conditions in the present invention are not particularly limited, and may be carried out under conditions well known to those skilled in the art.
In the present invention, in the above process, the addition reaction of the polyvinyl cage silsesquioxane is initiated to coat the nano zirconium dioxide in the solvent.
After the polymerization reaction is finished, the invention also preferably comprises filtering and drying which are carried out in sequence; the filtration is not particularly limited in the present invention and may be carried out by a process known to those skilled in the art. In the present invention, the drying is preferably performed by drying the white solid obtained by the filtration; the drying temperature is preferably 80 ℃ and the drying time is preferably 6 h.
After the vinyl-containing silsesquioxane-coated zirconium dioxide polymer is obtained, the vinyl-containing silsesquioxane-coated zirconium dioxide polymer, a mercapto acid compound, a second free radical initiator and a second organic solvent are mixed for click reaction to obtain the carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer.
In the present invention, the mercapto acid compound is preferably thioglycolic acid or mercaptopropionic acid. In the present invention, the second organic solvent is preferably chloroform. In the present invention, the second radical initiator is preferably azobisisobutyl and/or azobisisoheptonitrile.
In the invention, the mass ratio of the vinyl-containing silsesquioxane-coated zirconium dioxide polymer to the second radical initiator to the mercapto acid compound is 1: (0.01-0.03): (3-4), more preferably 1: (0.012-0.016): (3.3 to 3.8), most preferably 1: (0.013-0.015): (3.5-3.6).
In the present invention, the volume ratio of the total mass of the vinyl-containing silsesquioxane-coated zirconium dioxide polymer and mercapto acid compound to the second organic solvent is preferably 1g: (10-20) mL, more preferably 1g: (14-16) mL.
In the present invention, the mixing is preferably performed by mixing the vinyl-containing silsesquioxane-coated zirconium dioxide polymer, the mercapto acid compound, and the second organic solvent, and then adding the second radical initiator.
In the invention, the temperature of the click reaction is preferably 50-70 ℃, more preferably 53-62 ℃, and most preferably 58-60 ℃; the time is preferably 6 to 12 hours, and more preferably 8 to 10 hours. In the present invention, the click reaction is preferably performed under stirring conditions, and the stirring conditions in the present invention are not particularly limited, and may be performed under conditions well known to those skilled in the art.
In the invention, the click reaction is the nucleophilic addition of the mercapto group on the mercapto compound and the vinyl group on the POSS molecule.
After the click reaction is completed, the method also preferably comprises filtering, washing and drying which are sequentially carried out. The filtration is not particularly limited in the present invention and may be carried out by a process known to those skilled in the art. In the invention, the detergent used for washing is preferably chloroform; the washing process of the present invention is not particularly limited, and may be carried out by a process known to those skilled in the art. In the invention, the drying temperature is preferably 60-80 ℃, more preferably 65-75 ℃, and most preferably 68-72 ℃; the time is preferably 7-9 h, and more preferably 8 h.
The invention also provides a carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer prepared by the preparation method in the technical scheme, which comprises zirconium dioxide and a carboxyl-containing silsesquioxane polymer;
the structural unit in the carboxyl-containing silsesquioxane polymer has a structure shown as a formula I:
Figure GDA0003216747680000061
wherein n is 1 or 2;
the zirconium dioxide is encapsulated in the network of the carboxyl-containing silsesquioxane polymer.
In the invention, the mass ratio of the zirconium dioxide to the carboxyl-containing silsesquioxane is preferably (1-1.5): 1, more preferably (1.2 to 1.3): 1.
the invention also provides application of the carboxyl-containing silsesquioxane coated zirconium dioxide porous polymer in the technical scheme in the flame retardant field. In the present invention, the application is preferably as an epoxy resin flame retardant. The method of the present invention is not particularly limited, and the method may be performed by a method known to those skilled in the art.
The carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer provided by the present invention, the preparation method and the application thereof are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing 0.316g of octavinyl polyhedral oligomeric silsesquioxane, 0.316g of nano zirconium dioxide, 15.8mL of polyethylene glycol 200 and 22.5mL of tetrahydrofuran, adding 0.00954g of azobisisobutyronitrile, carrying out polymerization reaction for 24h at 62 ℃ under the stirring condition, filtering, and drying at 80 ℃ for 6h to obtain a vinyl silsesquioxane-containing coated zirconium dioxide polymer;
mixing 1g of the vinyl-containing silsesquioxane-coated zirconium dioxide polymer, 3.5g of mercaptopropionic acid and 67.5mL of trichloromethane, adding 0.068g of azobisisobutyronitrile, carrying out click reaction for 8h at 60 ℃ under stirring, filtering, washing with trichloromethane for 3 times, and drying the obtained filter cake at 70 ℃ for 8h to obtain the carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer (the mass ratio of the zirconium dioxide to the carboxyl-containing silsesquioxane is 1.2:1, the pore diameter is 3.01nm, and the specific surface area is 432.7 m)2/g)；
The vinyl-containing silsesquioxane-coated zirconium dioxide polymer is subjected to infrared spectroscopy, and the test result is shown in figure 1, and as can be seen from figure 1, the vinyl-containing silsesquioxane-coated zirconium dioxide polymer is 2900cm-1The peak is the vibration peak of saturated C-H, 1604cm-1、1400cm-1And 1240cm-1The peak is a vibration peak of C ═ C, and is 1081cm-1The peak at (A) is a stretching vibration peak of Si-O-Si, which proves that the polymer contains the vinyl silsesquioxane;
the carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer is subjected to infrared spectroscopy, and the test result is shown in fig. 2, and as can be seen from fig. 2, the carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer is 1700cm-1The peak is a stretching vibration peak of C ═ O; at 2900cm-1The central broad peak is the stretching vibration peak of-OH in carboxyl, 1080cm-1The peak is the stretching vibration peak of Si-O-Si.
Example 2
Mixing 0.316g of octavinyl polyhedral oligomeric silsesquioxane, 0.316g of nano zirconium dioxide, 15.8mL of polyethylene glycol 200 and 25mL of tetrahydrofuran, adding 0.0497g of azodiisoheptane, carrying out polymerization reaction for 24h at 62 ℃ under the condition of stirring, filtering, and drying at 80 ℃ for 6h to obtain a vinyl-containing silsesquioxane-coated zirconium dioxide polymer;
1g of the vinyl-containing silsesquioxaneMixing the siloxane-coated zirconium dioxide polymer, 3.5g of mercaptopropionic acid and 67.5mL of trichloromethane, adding 0.068g of azobisisobutyronitrile, carrying out click reaction for 8h at 60 ℃ under the condition of stirring, filtering, washing 3 times by using the trichloromethane, drying the obtained filter cake for 8h at 70 ℃ to obtain the carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer (the mass ratio of the zirconium dioxide to the carboxyl-containing silsesquioxane is 1.2:1, the pore diameter is 2.94nm, and the specific surface area is 481.1m2/g)；
FIG. 3 is a magnetic nuclear magnetic spectrum of the solid silicon containing the vinyl silsesquioxane coated zirconium dioxide polymer, as shown in FIG. 3, wherein-78.3 ppm corresponds to the silicon atoms bonded to the unsaturated carbon chains and-63.1 ppm corresponds to the silicon atoms bonded to the saturated carbon chains, indicating that the vinyl silsesquioxane was successfully polymerized and vinyl groups remained;
FIG. 4 is a solid silicon nuclear magnetic spectrum of the carboxyl-containing silsesquioxane coated zirconium dioxide porous polymer, and compared with FIG. 3, the peak at-78.3 ppm disappears, which shows that the carbon-carbon double bonds have all reacted, and the silicon atoms corresponding to the saturated carbon chains at-63.3 ppm shows that the remaining vinyl groups have all reacted with mercapto acids.
Example 3
Mixing 0.316g of octavinyl polyhedral oligomeric silsesquioxane, 0.316g of nano zirconium dioxide, 15.8mL of polyethylene glycol 200 and 25mL of tetrahydrofuran, adding 0.0497g of azobisisoheptonitrile, carrying out polymerization reaction for 24h at 62 ℃ under the condition of stirring, filtering, and drying at 80 ℃ for 8h to obtain a vinyl silsesquioxane-containing coated zirconium dioxide polymer;
mixing 1g of the vinyl-containing silsesquioxane-coated zirconium dioxide polymer, 3.1g of thioglycolic acid and 67.5mL of trichloromethane, adding 0.068g of azobisisobutyronitrile, carrying out click reaction for 8h at 61 ℃ under stirring, filtering, washing with trichloromethane for 3 times, and drying the obtained filter cake at 75 ℃ for 9h to obtain the carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer (the mass ratio of the zirconium dioxide to the carboxyl-containing silsesquioxane is 1.2:1, the pore diameter is 4.66nm, and the specific surface area is 397.3m2/g)；
FIG. 5 is a solid magnetic silica nuclear spectrum of the vinyl-containing silsesquioxane-coated zirconium dioxide polymer consistent with the product of example 2 at-79.8 ppm for silicon atoms attached to unsaturated carbon chains and-64.9 ppm for silicon atoms attached to saturated carbon chains, indicating successful polymerization of the vinyl-containing silsesquioxane with vinyl groups remaining;
FIG. 6 is a solid silicon nuclear magnetic spectrum of the carboxyl-containing silsesquioxane coated zirconium dioxide porous polymer, compared with FIG. 5, wherein the peak at-79.8 ppm disappears, which indicates that the carbon-carbon double bonds have all reacted, and the peak at-64.9 ppm corresponds to the silicon atoms connected with the saturated carbon chains, which indicates that the remaining vinyl groups have all reacted with mercaptoacid;
fig. 7 is a pore size distribution diagram of the carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer, and it can be seen from fig. 7 that the pore size distribution of the carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer has a single peak at 4.66nm and is in a mesoporous range; the carboxyl-containing silsesquioxane coated zirconium dioxide porous polymer is explained to be in a mesoporous structure.
Example 4
Mixing 0.316g of octavinyl polyhedral oligomeric silsesquioxane, 0.316g of nano zirconium dioxide, 15.8mL of polyethylene glycol 200 and 25mL of tetrahydrofuran, adding 0.0497g of azobisisoheptonitrile, carrying out polymerization reaction for 24h at 62 ℃ under the condition of stirring, filtering, and drying at 80 ℃ for 8h to obtain a vinyl silsesquioxane-containing coated zirconium dioxide polymer;
mixing 1g of the vinyl-containing silsesquioxane-coated zirconium dioxide polymer, 3.5g of thioglycolic acid and 67.5mL of trichloromethane, adding 0.068g of azobisisobutyronitrile, carrying out click reaction for 10h at 60 ℃ under stirring, filtering, washing with trichloromethane for 3 times, and drying the obtained filter cake at 75 ℃ for 9h to obtain the carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer (the mass ratio of the zirconium dioxide to the carboxyl-containing silsesquioxane is 1.2:1, the pore diameter is 3.57nm, and the specific surface area is 491.7 m)2/g)；
Fig. 8 is a pore size distribution diagram of the carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer, and it can be seen from fig. 8 that the pore size distribution of the carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer has a single peak at 3.57nm and is in a mesoporous range; the carboxyl-containing silsesquioxane coated zirconium dioxide porous polymer is explained to be in a mesoporous structure;
fig. 9 is an isothermal nitrogen adsorption-desorption curve of the carboxyl-containing silsesquioxane coated zirconia porous polymer, the adsorption curve and the desorption curve forming a loop; as can be seen from fig. 9, the carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer has a porous structure;
fig. 10 is a scanning electron micrograph and a corresponding energy spectrum of the carboxyl-containing silsesquioxane coated zirconia porous polymer, and it can be seen from fig. 10 that silicon and zirconium are present in the carboxyl-containing silsesquioxane coated zirconia porous polymer at the same time, which indicates that the zirconia is successfully coated with carboxyl-containing silsesquioxane;
fig. 11 is a thermal weight loss curve of the carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer, and it can be seen from fig. 11 that the temperature at which 5% of weight loss occurs is 339.5 ℃, and the weight loss at 800 ℃ is 19.05%.
FIG. 12 is an SEM image of the carboxyl-group-containing silsesquioxane-coated zirconium dioxide porous polymer prepared in example 4, and it can be seen from FIG. 12 that the slit pores between the larger carboxyl-group-containing silsesquioxane particles disappear, indicating that example 4 successfully coats zirconium dioxide in the slit pores;
adding 0.45g of carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer prepared in example 4 into 22.73g of epoxy resin monomer, stirring at 140 ℃ for 1h, then adding 6.82g of 4, 4-diaminodiphenyl sulfone, continuing stirring for 30min and vacuumizing, then pouring the mixture into a mold, and transferring the mold to an oven at 180 ℃ for curing for 4h to obtain epoxy resin containing carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer; FIG. 13 is a heat release rate curve of the epoxy resin containing the carboxyl-group-containing silsesquioxane coated zirconium dioxide porous polymer and a pure epoxy resin, and it can be seen from FIG. 13 that the peak value of the heat release rate of the pure epoxy resin is 1206kW/m2The peak value of the heat release rate of the epoxy resin after doping the carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer prepared in example 4 was 818kW/m2The heat release rate of the epoxy resin is reduced by 33% compared with that of the pure epoxy resin, which shows that the carboxyl-containing silsesquioxane coated zirconium dioxide porous polymer can improve the flame retardance of the epoxy resin.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. The preparation method of the carboxyl-containing silsesquioxane coated zirconium dioxide porous polymer is characterized by comprising the following steps of:
mixing polyvinyl cage-type silsesquioxane, nano zirconium dioxide, a pore-foaming agent, a first free radical initiator and a first organic solvent, and carrying out polymerization reaction to obtain a vinyl-containing silsesquioxane-coated zirconium dioxide polymer;
mixing the vinyl-containing silsesquioxane coated zirconium dioxide polymer, a mercapto acid compound, a second free radical initiator and a second organic solvent, and carrying out click reaction to obtain the carboxyl-containing silsesquioxane coated zirconium dioxide porous polymer;
the dosage ratio of the polyvinyl cage-type silsesquioxane to the pore-foaming agent to the nano zirconium dioxide to the first free radical initiator is 1g (20-30) mL: 1g (0.01-0.02) g;
the mass ratio of the vinyl-containing silsesquioxane coated zirconium dioxide polymer to the second radical initiator to the mercapto acid compound is 1: (0.01-0.03): (3-4).
2. The method of claim 1, wherein said multivinyl cage silsesquioxane is an octavinyl cage silsesquioxane, a decavinyl cage silsesquioxane or a dodecavinyl cage silsesquioxane.
3. The method of claim 1, wherein the porogen is polyethylene glycol.
4. The method of claim 1, wherein the first free radical initiator and the second free radical initiator are independently azobisisobutyl and/or azobisisoheptonitrile.
5. The method according to claim 1, wherein the polymerization reaction is carried out at a temperature of 42 to 82 ℃ for 12 to 36 hours.
6. The method according to claim 1, wherein the mercapto acid compound is thioglycolic acid or mercaptopropionic acid.
7. The method according to claim 1 or 6, wherein the click reaction is carried out at a temperature of 50 to 70 ℃ for 6 to 12 hours.
8. The carboxyl-containing silsesquioxane-coated zirconium dioxide porous polymer prepared by the preparation method of any one of claims 1 to 7 is characterized by comprising zirconium dioxide and carboxyl-containing silsesquioxane polymer;
the structural unit in the carboxyl-containing silsesquioxane polymer has a structure shown as a formula I:
Figure FDA0003565806580000021
wherein n is 1 or 2;
the zirconium dioxide is encapsulated in the network of the carboxyl-containing silsesquioxane polymer.
9. Use of the carboxyl-containing silsesquioxane coated zirconia porous polymer of claim 8 in the field of flame retardancy.
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