Flame-retardant heat-insulating curtain wall material and preparation method thereof

Abstract

The invention discloses a flame-retardant heat-insulating curtain wall material and a preparation method thereof, and belongs to the technical field of preparation of special functional materials.The preparation method comprises the following steps that 1, a base foaming material is prepared; the substrate foaming material comprises zirconium silicon subcrystal nanofibers; (2) preparation of a surface modification solution, which is a polyurethane coating using a reaction product of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, paraformaldehyde and tris (hydroxymethyl) aminomethane as a curing agent and magnesium ammonium phosphate as a filler; and (3) surface treatment: immersing the substrate foaming material in the surface modification solution, taking out the substrate foaming material, drying the substrate foaming material, and then carrying out heat treatment, on the basis of an existing foaming material, the flame-retardant and heat-insulating properties of the foaming material are improved through nano-fiber embedding and surface modification.

Description

Technical Field

[0001] The invention relates to the technical field of special functional material preparation, and in particular to a flame retardant heat insulating curtain wall material and a preparation method thereof. Background Art

[0002] Curtain wall is a type of outer wall of a building. It is usually non-load-bearing and looks like a hanging curtain, so it is also called a hanging curtain or suspended curtain. The characteristics of curtain wall include good decorative effect, light weight, and fast installation. It is an ideal type of lightweight and assembled exterior wall. It is widely used in modern large and high-rise buildings.

[0003] As the concept of energy-saving economy becomes more and more popular, the thermal insulation performance of buildings has become the focus of people's attention. As the exterior decorative surface of buildings, building curtain walls can play multiple roles such as thermal insulation, decoration and beauty. However, in the past few decades, due to material and technical limitations, the thermal insulation and flame retardant properties of building exterior walls are not ideal. Therefore, optimization research on the thermal insulation and flame retardant properties of building curtain walls has become an inevitable trend.

[0004] At present, rock wool board, polyurethane foam board, phenolic resin foam board, polystyrene foam board have been widely used in the field of building curtain wall insulation. However, rock wool board insulation material has a large water absorption rate, the insulation layer is easy to crack, and it cannot meet the requirements of building energy saving; polyurethane foam board, phenolic foam board and polystyrene foam board have the problem of low flame retardancy or thermal insulation performance. Summary of the invention

[0005] In view of the above problems, the present invention provides a flame retardant heat insulating curtain wall material and a preparation method thereof.

[0006] The purpose of the present invention is achieved by the following technical solutions:

[0007] A method for preparing a flame retardant heat insulating curtain wall material comprises the following steps:

[0008] (1) Preparation of base foaming material

[0009] The base foaming material includes zirconium silicon nanofibers, and the preparation method of the zirconium silicon nanofibers is:

[0010] Weighing zirconium polyacetylacetonate, yttrium nitrate hexahydrate and triethoxysilane and dispersing them in a solvent, stirring and mixing until the solution is clear and transparent, adding polyoxyethylene ether at 40-60° C., stirring and mixing again to obtain a spinning solution, and sequentially performing electrospinning and high-temperature sintering to obtain the zirconium silicon nanofibers;

[0011] (2) Preparation of surface modification solution

[0012] Weigh 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, paraformaldehyde, and tris(hydroxymethyl)aminomethane and dissolve them in chloroform solvent, heat to 40-60° C., keep warm, reflux, stir and react for 6-12 hours, cool to room temperature after the reaction is completed, separate the precipitate, wash and dry in sequence to obtain an intermediate product; mix the intermediate product with terminal blocked diisocyanate and disperse them in a solvent, add carboxymethyl cellulose and magnesium ammonium phosphate and disperse them again to obtain the surface modification solution;

[0013] (3) Surface treatment

[0014] The base foaming material is immersed in the surface modification solution, taken out, dried, and then heat-treated to obtain the surface modification material.

[0015] In some preferred embodiments, the base foaming material is polyurethane, polyimide, phenolic resin or polystyrene.

[0016] In some preferred embodiments, the mass ratio of the zirconium polyacetylacetonate to the yttrium nitrate hexahydrate and the triethoxysilane in step (1) is (14.5-17):1:(5.7-9).

[0017] In some preferred embodiments, the solvent in step (1) is one or more of methanol, ethanol, and deionized water.

[0018] In some preferred embodiments, the weight average molecular weight of the polyoxyethylene ether in step (1) is 100,000-1,000,000, and the amount added to the mixed system is 0.1-0.4 wt%.

[0019] In some preferred embodiments, the high temperature sintering in step (1) is performed at a temperature of 900-1100° C., a sintering time of 0.5-2 h, and a heating rate of 2-5° C. / min.

[0020] In some preferred embodiments, the mass ratio of the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the paraformaldehyde and the tris(hydroxymethyl)aminomethane in step (2) is 10:(2.1-2.6):(2.8-3.5).

[0021] In some preferred embodiments, the terminal blocked isocyanate in step (2) is an aliphatic compound or an aromatic compound having two terminal isocyanate groups blocked by a blocking agent; the blocking agent is caprolactam, phenol or dimethylpyrazole.

[0022] In some preferred embodiments, the mass ratio of the intermediate product in step (2) to the end-group blocked diisocyanate, the carboxymethyl cellulose, and the magnesium ammonium phosphate is 10:(3.8-5.2):(0.1-1):(2.5-4.6).

[0023] In some preferred embodiments, the heat treatment temperature in step (3) is 130-200° C., and the heat treatment holding time is 1-2 h.

[0024] Another object of the present invention is to provide a flame retardant heat insulating curtain wall material, wherein the flame retardant heat insulating curtain wall material is prepared by the aforementioned preparation method.

[0025] The beneficial effects of the present invention are:

[0026] In view of the problem that the flame retardant and heat-insulating properties of existing foam boards are not high, the present invention improves the flame retardant and heat-insulating properties of existing foaming materials by embedding nanofibers and modifying the surface. Specifically, the zirconium silicon nanofibers of the present invention have excellent thermomechanical stability and ultra-low thermal conductivity, which can improve the heat-insulating and mechanical properties of the foaming materials and reduce the mechanical property loss caused by the doping of inorganic materials. The present invention also uses tris(hydroxymethyl)aminomethane as a raw material and a curing agent, and improves its flame retardant properties by introducing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and magnesium ammonium phosphate. The present invention covers a uniform layer of magnesium ammonium phosphate coating based on flame-retardant polyurethane on the surface of the channel through surface treatment, thereby obtaining a lightweight and high-strength composite material resistant to flame erosion and having excellent heat-insulating properties. DETAILED DESCRIPTION

[0027] The present invention is further described in conjunction with the following examples.

[0028] Example 1

[0029] A flame retardant heat insulating curtain wall material, the preparation method of which comprises the following steps:

[0030] (1) Preparation of base foaming material

[0031] The base foaming material is polyurethane. Referring to the preparation process of polyurethane foaming material in the prior art, the prepared isocyanate and polyether polyol are stirred and mixed, a catalyst, a foaming agent and zirconium silicon nanofibers are added, and the polyurethane liquid after the mixed reaction is injected and filled in a mold, and the base foaming material is obtained after curing, wherein the preparation method of the subcrystalline zirconium silicon nanofiber is:

[0032] Weighing zirconium polyacetylacetonate, yttrium nitrate hexahydrate and triethoxysilane and dispersing them in a solvent, stirring and mixing until the solution is clear and transparent, adding polyoxyethylene ether at 60° C., stirring and mixing again to obtain a spinning solution, and sequentially performing electrospinning and high-temperature sintering to obtain the zirconium silicon nanofibers;

[0033] The solvent is a mixed solution of ethanol and deionized water (v / v=2:1); the weight average molecular weight Mw of the polyoxyethylene ether is 500,000, and the amount added in the mixed system is 0.2wt%; the mass ratio of the polyacetylacetonate zirconium to the hexahydrated yttrium nitrate, the triethoxysilane, and the solvent is 15:1:6.9:10; the high temperature sintering temperature is 1000°C, the sintering time is 60min, and the heating rate is 2°C / min;

[0034] (2) Preparation of surface modification solution

[0035] Weigh 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, paraformaldehyde, and tris(hydroxymethyl)aminomethane and dissolve them in chloroform solvent, heat to 60° C. and keep reflux stirring for reaction for 10 hours, cool to room temperature after the reaction is completed, separate the precipitate, wash and dry in sequence to obtain an intermediate product; mix the intermediate product with terminal blocked diisocyanate and disperse them in a solvent, add carboxymethyl cellulose and magnesium ammonium phosphate and disperse them again to obtain the surface modification solution;

[0036] The terminal blocked isocyanate is a diisocyanate having two terminal groups blocked by dimethylpyrazole, the mass ratio of the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the polyformaldehyde, the tris(hydroxymethyl)aminomethane, and the chloroform solvent is 10:2.2:3.1:100; the mass ratio of the intermediate product to the terminal blocked diisocyanate, the carboxymethyl cellulose, and the magnesium ammonium phosphate is 10:4.2:0.4:3;

[0037] (3) Surface treatment

[0038] The base foaming material is immersed in the surface modification solution, taken out, dried, and then heat-treated to obtain the obtained material; wherein the heat treatment temperature is 175° C. and the heat treatment holding time is 1 hour.

[0039] Example 2

[0040] A flame retardant heat insulating curtain wall material, the preparation method of which comprises the following steps:

[0041] (1) Preparation of base foaming material

[0042] The base foam material is polyurethane. Referring to the preparation process of polyurethane foam material in the prior art, the prepared isocyanate and polyether polyol are stirred and mixed, a catalyst and a foaming agent are added, and the polyurethane liquid after the mixed reaction is injected and filled in a mold, and the base foam material is obtained after curing;

[0043] (2) Preparation of surface modification solution

[0044] Weigh 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, paraformaldehyde, and tris(hydroxymethyl)aminomethane and dissolve them in chloroform solvent, heat to 60° C. and keep reflux stirring for reaction for 10 hours, cool to room temperature after the reaction is completed, separate the precipitate, wash and dry in sequence to obtain an intermediate product; mix the intermediate product with terminal blocked diisocyanate and disperse them in a solvent, add carboxymethyl cellulose and magnesium ammonium phosphate and disperse them again to obtain the surface modification solution;

[0045] The terminal blocked isocyanate is a diisocyanate having two terminal groups blocked by dimethylpyrazole, the mass ratio of the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the polyformaldehyde, the tris(hydroxymethyl)aminomethane, and the chloroform solvent is 10:2.2:3.1:100; the mass ratio of the intermediate product to the terminal blocked diisocyanate, the carboxymethyl cellulose, and the magnesium ammonium phosphate is 10:4.2:0.4:3;

[0046] (3) Surface treatment

[0047] The base foaming material is immersed in the surface modification solution, taken out, dried, and then heat-treated to obtain the obtained material; wherein the heat treatment temperature is 175° C. and the heat treatment holding time is 1 hour.

[0048] Example 3

[0049] A flame retardant heat insulating curtain wall material, the preparation method of which comprises the following steps:

[0050] (1) Preparation of base foaming material

[0051] The base foam material is polyurethane. Referring to the preparation process of polyurethane foam material in the prior art, the prepared isocyanate and polyether polyol are stirred and mixed, a catalyst, a foaming agent and zirconium silicon nanofibers are added, and the polyurethane liquid after the mixed reaction is injected and filled in the mold, and the base foam material is obtained after curing, wherein the preparation method of the subcrystalline zirconium silicon nanofiber is:

[0052] Weighing zirconium polyacetylacetonate, yttrium nitrate hexahydrate and triethoxysilane and dispersing them in a solvent, stirring and mixing until the solution is clear and transparent, adding polyoxyethylene ether at 60° C., stirring and mixing again to obtain a spinning solution, and sequentially performing electrospinning and high-temperature sintering to obtain the zirconium silicon nanofibers;

[0053] The solvent is a mixed solution of ethanol and deionized water (v / v=2:1); the weight average molecular weight Mw of the polyoxyethylene ether is 500,000, and the amount added in the mixed system is 0.2wt%; the mass ratio of the polyacetylacetonate zirconium to the hexahydrated yttrium nitrate, the triethoxysilane, and the solvent is 15:1:6.9:10; the high temperature sintering temperature is 1000°C, the sintering time is 60min, and the heating rate is 2°C / min;

[0054] (2) The base foam material is heat treated to obtain a product; wherein the heat treatment temperature is 175° C. and the heat treatment holding time is 1 hour.

[0055] Example 4

[0056] A flame retardant heat insulating curtain wall material, the preparation method of which comprises the following steps:

[0057] (1) Preparation of base foaming material

[0058] The base foaming material is polyurethane. Referring to the preparation process of polyurethane foaming material in the prior art, the prepared isocyanate and polyether polyol are stirred and mixed, a catalyst, a foaming agent and zirconium silicon nanofibers are added, and the polyurethane liquid after the mixed reaction is injected and filled in a mold, and the base foaming material is obtained after curing, wherein the preparation method of the subcrystalline zirconium silicon nanofiber is:

[0059] Weighing yttrium nitrate hexahydrate and triethoxysilane and dispersing them in a solvent, stirring and mixing until the solution is clear and transparent, adding polyoxyethylene ether at 60° C., stirring and mixing again to obtain a spinning solution, and then sequentially performing electrospinning and high-temperature sintering to obtain the zirconium silicon nanofibers;

[0060] The solvent is a mixed solution of ethanol and deionized water (v / v=2:1); the weight average molecular weight Mw of the polyoxyethylene ether is 500,000, and the amount added in the mixed system is 0.2wt%; the mass ratio of the yttrium nitrate hexahydrate to the triethoxysilane and the solvent is 1:6.9:10; the high temperature sintering temperature is 1000°C, the sintering time is 60min, and the heating rate is 2°C / min;

[0061] (2) Preparation of surface modification solution

[0062] Weigh 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, paraformaldehyde, and tris(hydroxymethyl)aminomethane and dissolve them in chloroform solvent, heat to 60° C. and keep reflux stirring for reaction for 10 hours, cool to room temperature after the reaction is completed, separate the precipitate, wash and dry in sequence to obtain an intermediate product; mix the intermediate product with terminal blocked diisocyanate and disperse them in a solvent, add carboxymethyl cellulose and magnesium ammonium phosphate and disperse them again to obtain the surface modification solution;

[0063] The terminal blocked isocyanate is a diisocyanate having two terminal groups blocked by dimethylpyrazole, the mass ratio of the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the polyformaldehyde, the tris(hydroxymethyl)aminomethane, and the chloroform solvent is 10:2.2:3.1:100; the mass ratio of the intermediate product to the terminal blocked diisocyanate, the carboxymethyl cellulose, and the magnesium ammonium phosphate is 10:4.2:0.4:3;

[0064] (3) Surface treatment

[0065] The base foaming material is immersed in the surface modification solution, taken out, dried, and then heat-treated to obtain the obtained material; wherein the heat treatment temperature is 175° C. and the heat treatment holding time is 1 hour.

[0066] Example 5

[0067] A flame retardant heat insulating curtain wall material, the preparation method of which comprises the following steps:

[0068] (1) Preparation of base foaming material

[0069] The base foaming material is polyurethane. Referring to the preparation process of polyurethane foaming material in the prior art, the prepared isocyanate and polyether polyol are stirred and mixed, a catalyst, a foaming agent and zirconium silicon nanofibers are added, and the polyurethane liquid after the mixed reaction is injected and filled in a mold, and the base foaming material is obtained after curing, wherein the preparation method of the subcrystalline zirconium silicon nanofiber is:

[0070] Weighing zirconium polyacetylacetonate and triethoxysilane and dispersing them in a solvent, stirring and mixing until the solution is clear and transparent, adding polyoxyethylene ether at 60° C., stirring and mixing again to obtain a spinning solution, and sequentially subjecting the zirconium silicon nanofibers to electrospinning and high-temperature sintering;

[0071] The solvent is a mixed solution of ethanol and deionized water (v / v=2:1); the weight average molecular weight Mw of the polyoxyethylene ether is 500,000, and the amount added in the mixed system is 0.2wt%; the mass ratio of the polyacetylacetonate zirconium to the triethoxysilane and the solvent is 15:6.9:10; the high temperature sintering temperature is 1000°C, the sintering time is 60min, and the heating rate is 2°C / min;

[0072] (2) Preparation of surface modification solution

[0073] Weigh 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, paraformaldehyde, and tris(hydroxymethyl)aminomethane and dissolve them in chloroform solvent, heat to 60° C. and keep reflux stirring for reaction for 10 hours, cool to room temperature after the reaction is completed, separate the precipitate, wash and dry in sequence to obtain an intermediate product; mix the intermediate product with terminal blocked diisocyanate and disperse them in a solvent, add carboxymethyl cellulose and magnesium ammonium phosphate and disperse them again to obtain the surface modification solution;

[0074] The terminal blocked isocyanate is a diisocyanate having two terminal groups blocked by dimethylpyrazole, the mass ratio of the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the polyformaldehyde, the tris(hydroxymethyl)aminomethane, and the chloroform solvent is 10:2.2:3.1:100; the mass ratio of the intermediate product to the terminal blocked diisocyanate, the carboxymethyl cellulose, and the magnesium ammonium phosphate is 10:4.2:0.4:3;

[0075] (3) Surface treatment

[0076] The base foaming material is immersed in the surface modification solution, taken out, dried, and then heat-treated to obtain the obtained material; wherein the heat treatment temperature is 175° C. and the heat treatment holding time is 1 hour.

[0077] Comparison Example

[0078] A base foam material without the zirconium-silicon nanofibers described in Example 1 was used as a control, and its preparation method was the same as step (1) of Example 1.

[0079] Experimental example

[0080] The flame retardant and thermal insulation properties of the foamed materials prepared in Examples 1-5 and the control example were measured, wherein the thermal conductivity was measured in accordance with GB / T10294-2008; the oxygen index was measured in accordance with GB / T2406.2-2009; and the combustion grade was measured in accordance with GB8624-2012. The results are as follows:

[0081]

[0082] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A method for preparing a flame retardant and heat insulating curtain wall material, characterized in that: The following steps are involved: (1) Preparation of base foaming material The base foaming material includes zirconium silicon nanofibers, and the preparation method of the zirconium silicon nanofibers is: Weighing zirconium polyacetylacetonate, yttrium nitrate hexahydrate and triethoxysilane and dispersing them in a solvent, stirring and mixing until the solution is clear and transparent, adding polyoxyethylene ether at 40-60° C., stirring and mixing again to obtain a spinning solution, and sequentially performing electrospinning and high-temperature sintering to obtain the zirconium silicon nanofibers; (2) Preparation of surface modification solution Weigh 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, paraformaldehyde, and tris(hydroxymethyl)aminomethane and dissolve them in chloroform solvent, heat to 40-60° C., keep warm, reflux, stir and react for 6-12 hours, cool to room temperature after the reaction is completed, separate the precipitate, wash and dry in sequence to obtain an intermediate product; mix the intermediate product with terminal blocked diisocyanate and disperse them in a solvent, add carboxymethyl cellulose and magnesium ammonium phosphate and disperse them again to obtain the surface modification solution; (3) Surface treatment The base foaming material is immersed in the surface modification solution, taken out, dried, and then heat-treated to obtain the surface modification material.

2. The method for preparing a flame retardant and heat insulating curtain wall material according to claim 1, characterized in that: The base foaming material is polyurethane, polyimide, phenolic resin or polystyrene.

3. The method for preparing a flame retardant and heat insulating curtain wall material according to claim 1, characterized in that: In step (1), the mass ratio of the polyacetylacetonate zirconium to the yttrium nitrate hexahydrate and the triethoxysilane is (14.5-17):1:(5.7-9).

4. The method for preparing a flame retardant and heat insulating curtain wall material according to claim 1, characterized in that: The weight average molecular weight of the polyoxyethylene ether in step (1) is between 100,000 and 1,000,000, and its addition amount in the mixed system is 0.1-0.4 wt%.

5. The method for preparing a flame retardant and heat insulating curtain wall material according to claim 1, characterized in that: The high temperature sintering temperature in step (1) is 900-1100° C., the sintering time is 0.5-2 h, and the heating rate is 2-5° C. / min.

6. The method for preparing a flame retardant and heat insulating curtain wall material according to claim 1, characterized in that: In step (2), the mass ratio of the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the polyformaldehyde and the tris(hydroxymethyl)aminomethane is 10:(2.1-2.6):(2.8-3.5).

7. The method for preparing a flame retardant and heat insulating curtain wall material according to claim 1, characterized in that: The terminal blocked isocyanate in step (2) is an aliphatic compound or an aromatic compound having two terminal isocyanate groups blocked by a blocking agent; the blocking agent is caprolactam, phenol or dimethylpyrazole.

8. The method for preparing a flame retardant and heat insulating curtain wall material according to claim 1, characterized in that: The mass ratio of the intermediate product in step (2) to the end-group blocked diisocyanate, the carboxymethyl cellulose and the magnesium ammonium phosphate is 10:(3.8-5.2):(0.1-1):(2.5-4.6).

9. The method for preparing a flame retardant and heat insulating curtain wall material according to claim 1, characterized in that: The heat treatment temperature in step (3) is 130-200°C, and the heat treatment holding time is 1-2h.

10. A flame retardant heat insulating curtain wall material, characterized in that: The compound is prepared by the preparation method according to any one of claims 1 to 9.

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