阅读说明：本技术 一种建筑用纳米防火材料及其制备方法 (Nano fireproof material for building and preparation method thereof ) 是由 孙刚 于 2019-08-30 设计创作，主要内容包括：本发明涉及一种建筑用纳米防火材料及其制备方法,该建筑用纳米防火材料包括如下重量份的原料：纳米材料10-15份；氧化石墨烯-碳纳米管分散液10-15份；粘土20-25份；高钙粉煤灰22-35份；硅藻土18-26份；蛭石15-25份；发泡剂3-7份；聚乙烯醇4-10份；羟基锡酸锌5-12份；水35-50份。本发明的建筑用纳米防火材料,通过氧化石墨烯与碳纳米管形成分散液与纳米材料形成三维框架结构,与组分中的其它材料配合作用时,能够提高各原料之间的相容性、分散性,有效降低团聚现象的发生,最终增加防火材料的韧性、强度和阻燃性能。(The invention relates to a nano fireproof material for buildings and a preparation method thereof, wherein the nano fireproof material for buildings comprises the following raw materials in parts by weight: 10-15 parts of a nano material; 10-15 parts of graphene oxide-carbon nanotube dispersion liquid; 20-25 parts of clay; 22-35 parts of high-calcium fly ash; 18-26 parts of diatomite; 15-25 parts of vermiculite; 3-7 parts of a foaming agent; 4-10 parts of polyvinyl alcohol; 5-12 parts of zinc hydroxystannate; 35-50 parts of water. According to the nano fireproof material for the building, the graphene oxide and the carbon nano tube form the dispersion liquid to form the three-dimensional frame structure with the nano material, and when the nano fireproof material is matched with other materials in the components, the compatibility and the dispersity among the raw materials can be improved, the occurrence of the agglomeration phenomenon is effectively reduced, and finally the toughness, the strength and the flame retardant property of the fireproof material are improved.)

1. The nanometer fireproof material for the building is characterized by comprising the following raw materials in parts by weight: 10-15 parts of a nano material; 10-15 parts of graphene oxide-carbon nanotube dispersion liquid; 20-25 parts of clay; 22-35 parts of high-calcium fly ash; 18-26 parts of diatomite; 15-25 parts of vermiculite; 3-7 parts of a foaming agent; 4-10 parts of polyvinyl alcohol; 5-12 parts of zinc hydroxystannate; 35-50 parts of water.

2. The nano fireproof material for buildings according to claim 1, wherein the nano material comprises the following raw materials in parts by weight: 20-35 parts of nano cellulose; 8-16 parts of nano silicon carbide; 10-15 parts of nano silicon dioxide; 20-30 parts of nano titanium dioxide; 5-10 parts of nano magnesium oxide.

3. The nano fireproof building material of claim 1, wherein the nano cellulose is at least one of cellulose nano fiber, microcrystalline cellulose and bacterial nano cellulose.

4. The nano fireproof material for building of claim 1, wherein the preparation method of the graphene oxide-carbon nanotube dispersion comprises the following steps:

1) preparing graphene oxide from graphene by using a Hummers method;

2) ultrasonically dispersing graphene oxide in water for 30-40min to form a graphene oxide dispersion liquid;

3) adding a carbon nano tube into the graphene oxide dispersion liquid, and continuing to perform ultrasonic oscillation for 1-2 hours to obtain the graphene oxide-carbon nano tube dispersion liquid.

5. The nano fireproof material for buildings according to claim 4, wherein the mass ratio of graphene oxide to carbon nanotubes in the graphene oxide-carbon nanotube dispersion liquid is (1-2): (2-3).

6. The nano fireproof material for building of claim 5, wherein the carbon nanotubes comprise one or more of surface carboxyl modified carbon nanotubes, surface amino modified carbon nanotubes or surface hydroxyl modified carbon nanotubes.

7. The nano fire-proof material for construction as claimed in claim 1, wherein the foaming agent comprises one or more of petroleum ether, trichlorofluoromethane, dichlorodifluoromethane and dichlorotetrafluoromethane.

8. A method for preparing the nano fireproof material for building as claimed in any one of claims 1 to 7, comprising the following steps:

1) uniformly mixing the nano material and the graphene oxide-carbon nanotube dispersion liquid to obtain a nano mixture;

2) ball-milling clay, high-calcium fly ash, diatomite, vermiculite and zinc hydroxystannate into powder by adopting a ball-milling technology to obtain ball-milled powder;

3) and adding a foaming agent, polyvinyl alcohol and water into the nano mixture and the ball milled powder, and uniformly stirring to obtain the nano fireproof material.

Technical Field

The invention belongs to the technical field of fireproof materials, and particularly relates to a nano fireproof material for a building and a preparation method thereof.

Background

The use of a large amount of electronic appliances in modern life and the use of too many flammable materials in decoration materials are easy to trigger fire, thereby bringing potential safety hazards and even disasters to the life of people.

The existing fireproof plates, fireproof doors, fireproof glass and fireproof coatings generally achieve the effects of reducing fire load and reducing the fire spreading speed by coating or adding materials with flame-retardant or flame-retardant characteristics on the surfaces, but the existing fireproof materials have the problems of low fire resistance level, thick and heavy materials, harmful gas generation in fire or poor aging resistance and the like.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a nano fireproof material for buildings and a preparation method thereof. The technical problem to be solved by the invention is realized by the following technical scheme:

a nano fireproof material for buildings comprises the following raw materials in parts by weight: 10-15 parts of a nano material; 10-15 parts of graphene oxide-carbon nanotube dispersion liquid; 20-25 parts of clay; 22-35 parts of high-calcium fly ash; 18-26 parts of diatomite; 15-25 parts of vermiculite; 3-7 parts of a foaming agent; 4-10 parts of polyvinyl alcohol; 5-12 parts of zinc hydroxystannate; 35-50 parts of water.

Preferably, the nano material comprises the following raw materials in parts by weight: 20-35 parts of nano cellulose; 8-16 parts of nano silicon carbide; 10-15 parts of nano silicon dioxide; 20-30 parts of nano titanium dioxide; 5-10 parts of nano magnesium oxide.

Preferably, the nanocellulose is at least one of cellulose nanofibres, microcrystalline cellulose and bacterial nanocellulose.

Preferably, the preparation method of the graphene oxide-carbon nanotube dispersion liquid comprises the following steps:

1) preparing graphene oxide from graphene by using a Hummers method;

2) ultrasonically dispersing graphene oxide in water for 30-40min to form a graphene oxide dispersion liquid;

3) adding a carbon nano tube into the graphene oxide dispersion liquid, and continuing to perform ultrasonic oscillation for 1-2 hours to obtain the graphene oxide-carbon nano tube dispersion liquid.

Preferably, the mass ratio of the graphene oxide to the carbon nanotubes in the graphene oxide-carbon nanotube dispersion liquid is (1-2): (2-3).

Preferably, the carbon nanotube includes one or more of a surface carboxyl modified carbon nanotube, a surface amino modified carbon nanotube or a surface hydroxyl modified carbon nanotube.

Preferably, the blowing agent comprises one or more of petroleum ether, trichlorofluoromethane, dichlorodifluoromethane and dichlorotetrafluoromethane.

The preparation method of the building nano fireproof material comprises the following steps:

1) uniformly mixing the nano material and the graphene oxide-carbon nanotube dispersion liquid to obtain a nano mixture;

2) ball-milling clay, high-calcium fly ash, diatomite, vermiculite and zinc hydroxystannate into powder by adopting a ball-milling technology to obtain ball-milled powder;

3) and adding a foaming agent, polyvinyl alcohol and water into the nano mixture and the ball milled powder, and uniformly stirring to obtain the nano fireproof material.

Compared with the prior art, the invention has the beneficial effects that:

1. according to the nano fireproof material for the building, the graphene oxide and the carbon nano tube form a dispersion liquid, the graphene oxide not only retains the original pi conjugated structure of the graphene, but also has a large number of oxygen-containing functional groups, so that the graphene oxide has good dispersibility; the carbon nano tube has excellent performances of heat, electricity, mechanics, hydrogen storage, catalysis and the like due to the unique structure, but has poor dispersibility; the dispersion liquid formed by the graphene oxide and the carbon nano tube can form a three-dimensional frame structure with the nano material, and when the dispersion liquid is matched with other materials in the components, the compatibility and the dispersibility among all raw materials can be improved, the occurrence of agglomeration phenomenon is effectively reduced, and finally the toughness, the strength, the flame retardance and the combustion resistance of the fireproof material are improved.

2. According to the preparation method, the clay, the high-calcium fly ash, the diatomite, the vermiculite and the zinc hydroxystannate are ball-milled into powder by adopting a ball milling technology, and the powder and the nano mixture are more easily and uniformly dispersed in the foaming agent, the polyvinyl alcohol and the water, so that the dispersibility among the raw materials is improved, and the better flame-retardant and fireproof performance is achieved.

Detailed Description

The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.

Example one

The nano fireproof material for the building comprises the following raw materials in parts by weight: 12 parts of a nano material; 12 parts of graphene oxide-carbon nanotube dispersion liquid; 22 parts of clay; 28 parts of high-calcium fly ash; 24 parts of diatomite; 20 parts of vermiculite; 5 parts of a foaming agent; 7 parts of polyvinyl alcohol; 8 parts of zinc hydroxystannate; and 45 parts of water.

In this embodiment, the nano material may be nano titanium dioxide, nano silicon dioxide, nano cellulose, and the like, and the preferably adopted nano material includes the following raw materials in parts by weight: 26 parts of nano-cellulose; 12 parts of nano silicon carbide; 12 parts of nano silicon dioxide; 25 parts of nano titanium dioxide; and 8 parts of nano magnesium oxide. The nano-cellulose is at least one of cellulose nano-fiber, microcrystalline cellulose and bacterial nano-cellulose. Microcrystalline cellulose was selected for this example.

The preparation method of the graphene oxide-carbon nanotube dispersion liquid may include the steps of:

1) preparing graphene oxide from graphene by using a Hummers method;

2) ultrasonically dispersing graphene oxide in water for 35min to form a graphene oxide dispersion liquid;

3) adding carbon nano tubes into the graphene oxide dispersion liquid, and continuing to perform ultrasonic oscillation for 1.5 hours to obtain the graphene oxide-carbon nano tube dispersion liquid.

The mass ratio of the graphene oxide to the carbon nanotubes in the graphene oxide-carbon nanotube dispersion liquid is preferably 1: 2. the carbon nano tube comprises one or more of a surface carboxyl modified carbon nano tube, a surface amino modified carbon nano tube or a surface hydroxyl modified carbon nano tube. In this embodiment, the carbon nanotube is modified by carboxyl group.

The foaming agent comprises one or more of petroleum ether, trichlorofluoromethane, dichlorodifluoromethane and dichlorotetrafluoromethane. In this example, petroleum ether was used as the blowing agent.

The preparation method of the nano fireproof material for the building comprises the following steps:

1) uniformly mixing 12 parts of a nano material and 12 parts of graphene oxide-carbon nanotube dispersion liquid to obtain a nano mixture;

2) ball-milling 22 parts of clay, 28 parts of high-calcium fly ash, 24 parts of diatomite, 20 parts of vermiculite and 8 parts of zinc hydroxystannate into powder by adopting a ball-milling technology to obtain ball-milled powder;

3) and adding 5 parts of foaming agent, 7 parts of polyvinyl alcohol and 45 parts of water into the nano mixture and the ball milled powder, and uniformly stirring to obtain the nano fireproof material.

Example two

The nano fireproof material for the building comprises the following raw materials in parts by weight: 10 parts of a nano material; 10 parts of graphene oxide-carbon nanotube dispersion liquid; 20 parts of clay; 22 parts of high-calcium fly ash; 18 parts of diatomite; 15 parts of vermiculite; 3 parts of a foaming agent; 4 parts of polyvinyl alcohol; 5 parts of zinc hydroxystannate; 35 parts of water.

In this embodiment, the nano material may be nano titanium dioxide, nano silicon dioxide, nano cellulose, and the like, and the preferably adopted nano material includes the following raw materials in parts by weight: 20 parts of nano-cellulose; 8 parts of nano silicon carbide; 10 parts of nano silicon dioxide; 20 parts of nano titanium dioxide; and 5 parts of nano magnesium oxide. The nano-cellulose is at least one of cellulose nano-fiber, microcrystalline cellulose and bacterial nano-cellulose. In this example, cellulose nanofibers were selected.

The preparation method of the graphene oxide-carbon nanotube dispersion liquid may include the steps of:

1) preparing graphene oxide from graphene by using a Hummers method;

2) ultrasonically dispersing graphene oxide in water for 30min to form a graphene oxide dispersion liquid;

3) adding carbon nano tubes into the graphene oxide dispersion liquid, and continuing to perform ultrasonic oscillation for 1 hour to obtain the graphene oxide-carbon nano tube dispersion liquid.

The mass ratio of the graphene oxide to the carbon nanotubes in the graphene oxide-carbon nanotube dispersion liquid is preferably 2: 3. the carbon nano tube comprises one or more of a surface carboxyl modified carbon nano tube, a surface amino modified carbon nano tube or a surface hydroxyl modified carbon nano tube. In this embodiment, the carbon nanotube modified by amino group on the surface and the carbon nanotube modified by hydroxyl group on the surface are selected.

The foaming agent comprises one or more of petroleum ether, trichlorofluoromethane, dichlorodifluoromethane and dichlorotetrafluoromethane. Trichlorofluoromethane was selected as the blowing agent in this example.

The preparation method of the nano fireproof material for the building comprises the following steps:

1) uniformly mixing 10 parts of nano material and 10 parts of graphene oxide-carbon nanotube dispersion liquid to obtain a nano mixture;

2) ball-milling 20 parts of clay, 22 parts of high-calcium fly ash, 18 parts of diatomite, 15 parts of vermiculite and 5 parts of zinc hydroxystannate into powder by adopting a ball-milling technology to obtain ball-milled powder;

3) and adding 3 parts of foaming agent, 4 parts of polyvinyl alcohol and 35 parts of water into the nano mixture and the ball milled powder, and uniformly stirring to obtain the nano fireproof material.

EXAMPLE III

The nano fireproof material for the building comprises the following raw materials in parts by weight: 15 parts of a nano material; 15 parts of graphene oxide-carbon nanotube dispersion liquid; 25 parts of clay; 35 parts of high-calcium fly ash; 26 parts of diatomite; 25 parts of vermiculite; 7 parts of a foaming agent; 10 parts of polyvinyl alcohol; 12 parts of zinc hydroxystannate; 50 parts of water.

In this embodiment, the nano material may be nano titanium dioxide, nano silicon dioxide, nano cellulose, and the like, and the preferably adopted nano material includes the following raw materials in parts by weight: 35 parts of nano-cellulose; 16 parts of nano silicon carbide; 15 parts of nano silicon dioxide; 30 parts of nano titanium dioxide; 10 parts of nano magnesium oxide. The nano-cellulose is at least one of cellulose nano-fiber, microcrystalline cellulose and bacterial nano-cellulose. Microcrystalline cellulose and bacterial nanocellulose were selected for use in this example.

The preparation method of the graphene oxide-carbon nanotube dispersion liquid may include the steps of:

1) preparing graphene oxide from graphene by using a Hummers method;

2) ultrasonically dispersing graphene oxide in water for 40min to form a graphene oxide dispersion liquid;

3) adding carbon nano tubes into the graphene oxide dispersion liquid, and continuing ultrasonic oscillation for 2 hours to obtain the graphene oxide-carbon nano tube dispersion liquid.

The mass ratio of graphene oxide to carbon nanotubes in the graphene oxide-carbon nanotube dispersion liquid is preferably (1-2): (2-3). The carbon nano tube comprises one or more of a surface carboxyl modified carbon nano tube, a surface amino modified carbon nano tube or a surface hydroxyl modified carbon nano tube. In this embodiment, the carbon nanotube with amino group modified surface is selected.

The foaming agent comprises one or more of petroleum ether, trichlorofluoromethane, dichlorodifluoromethane and dichlorotetrafluoromethane. In this example, a mixture of dichlorodifluoromethane and dichlorotetrafluoromethane was used as the blowing agent.

The preparation method of the nano fireproof material for the building comprises the following steps:

1) uniformly mixing 15 parts of the nano material and 15 parts of the graphene oxide-carbon nanotube dispersion liquid to obtain a nano mixture;

2) ball-milling 25 parts of clay, 35 parts of high-calcium fly ash, 26 parts of diatomite, 25 parts of vermiculite and 12 parts of zinc hydroxystannate into powder by adopting a ball-milling technology to obtain ball-milled powder;

3) and adding 7 parts of foaming agent, 10 parts of polyvinyl alcohol and 50 parts of water into the nano mixture and the ball milled powder, and uniformly stirring to obtain the nano fireproof material.

Comparative example 1

The difference between the comparative example and the first example is that the raw materials do not contain nano materials, and other components are the same; namely, the fireproof material of the comparative example comprises the following raw materials in parts by weight: 12 parts of graphene oxide-carbon nanotube dispersion liquid; 22 parts of clay; 28 parts of high-calcium fly ash; 24 parts of diatomite; 20 parts of vermiculite; 5 parts of a foaming agent; 7 parts of polyvinyl alcohol; 8 parts of zinc hydroxystannate; and 45 parts of water.

Comparative example No. two

The comparative example is different from the first example in that the raw materials do not contain the graphene oxide-carbon nanotube dispersion liquid, and other components are the same; namely, the fireproof material of the comparative example comprises the following raw materials in parts by weight: 12 parts of a nano material; 22 parts of clay; 28 parts of high-calcium fly ash; 24 parts of diatomite; 20 parts of vermiculite; 5 parts of a foaming agent; 7 parts of polyvinyl alcohol; 8 parts of zinc hydroxystannate; and 45 parts of water.

Comparative example No. three

The difference between the comparative example and the first example is that the raw materials contained in the comparative example are the same and have different contents; namely, the fireproof material of the comparative example comprises the following raw materials in parts by weight: 5 parts of a nano material; 5 parts of graphene oxide-carbon nanotube dispersion liquid; 10 parts of clay; 40 parts of high-calcium fly ash; 30 parts of diatomite; 30 parts of vermiculite; 1 part of foaming agent; 3 parts of polyvinyl alcohol; 2 parts of zinc hydroxystannate; 55 parts of water.

The fire-resistant performance of the fire-resistant material of each embodiment and each proportion of the invention is tested, and the test results are shown in the following table:

	fire resistance rating	Limiting oxygen index	Compressive strength (MPa)	Tensile strength (MPa)
					Example one	A1	32	6.8	4.5
Example two	A1	30	5.5	4.0
					EXAMPLE III	A1	31	6.0	4.2
Comparative example 1	B1	28	2.5	2.3
					Comparative example No. two	B1	28	2.0	2.1
Comparative example No. three	B1	27	2.3	2.0

It can be seen from the above table that the contents of the nanomaterial and the graphene oxide-carbon nanotube dispersion liquid in the components of the nano fireproof material for buildings and the mutual proportion of the raw materials have great influence on indexes such as the fire resistance and the mechanical property of the finally formed fireproof material product.

According to the nano fireproof material for the building, the graphene oxide not only retains the original pi conjugated structure of the graphene, but also has a large number of oxygen-containing functional groups through the dispersion liquid formed by the graphene oxide and the carbon nano tubes, so that the graphene oxide has good dispersibility; the carbon nano tube has excellent performances of heat, electricity, mechanics, hydrogen storage, catalysis and the like due to the unique structure, but has poor dispersibility; the dispersion liquid formed by the graphene oxide and the carbon nano tube can form a three-dimensional frame structure with the nano material, and when the dispersion liquid is matched with other materials in the components, the compatibility and the dispersibility among all raw materials can be improved, the occurrence of an agglomeration phenomenon is effectively reduced, and finally the toughness, the strength, the flame retardance and the combustion resistance of the fireproof material are improved. In addition, in the preparation method, the clay, the high-calcium fly ash, the diatomite, the vermiculite and the zinc hydroxystannate are ball-milled into powder by adopting a ball milling technology, and the powder and the nano mixture are more easily and uniformly dispersed in the foaming agent, the polyvinyl alcohol and the water, so that the dispersibility among the raw materials is improved, and the better flame-retardant and fireproof performance is achieved.

The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.