阅读说明：本技术 一种防火保温复合挤塑板的制备方法 (Preparation method of fireproof heat-preservation composite extruded sheet ) 是由 马贵其 于 2019-10-10 设计创作，主要内容包括：本发明属于复合材料技术领域,具体涉及一种防火保温复合挤塑板的制备方法。本发明以天然鳞片石墨为原料,将载体聚酯、氧化铝纤维、纳米氧化亚铜加热熔化后浇于泡沫板表面后热压得到防火保温复合挤塑板,混合树脂在氯化锌和氯化铜的复合活化剂作用下水解降解、形成低聚物,产生较好的保温效果,在酸性条件下高浓度的锌、铜离子大量残余在芳构化有机物中,增强内部结构强度,降低导热系数。防火保温复合挤塑板为三层结构,中间层为泡沫板具有轻质保温的优点,阻燃性能也较好,表面的聚酯材料减小孔隙受外界应力的影响,天然鳞片石墨经过酸化电解后,起到一定的储能转换效果,使挤塑板应用于建筑外墙保温时冬暖夏凉,具有广阔的应用前景。(The invention belongs to the technical field of composite materials, and particularly relates to a preparation method of a fireproof heat-preservation composite extruded sheet. The invention takes natural crystalline flake graphite as raw material, heats and melts carrier polyester, alumina fiber and nano cuprous oxide, then pours the molten carrier polyester, alumina fiber and nano cuprous oxide on the surface of foam board, then carries out hot pressing to obtain the fireproof heat-preservation composite extruded sheet, the mixed resin is degraded under the action of the composite activating agent of zinc chloride and copper chloride to form oligomer, thereby producing better heat preservation effect, a great amount of high-concentration zinc and copper ions are remained in aromatized organic matter under acidic condition, the internal structural strength is enhanced, and the heat conductivity coefficient is reduced. The fireproof heat-insulation composite extruded sheet is of a three-layer structure, the foam sheet is arranged in the middle layer, the fireproof heat-insulation composite extruded sheet has the advantages of light weight and heat insulation, the flame retardant property is good, the influence of external stress on pores is reduced by the polyester material on the surface, and the natural crystalline flake graphite plays a certain energy storage conversion effect after being subjected to acidification and electrolysis, so that the extruded sheet is warm in winter and cool in summer when being applied to the heat insulation of the outer wall of a building, and has a wide application prospect.)

1. A preparation method of a fireproof heat-preservation composite extruded sheet is characterized by comprising the following specific preparation steps:

(1) putting the mixed resin into an oven with the set temperature of 100-120 ℃, preheating and drying for 40-50 min to obtain a raw material to be extruded, injecting the raw material into a double-screw device, stirring for 10-15 min, heating to 150-180 ℃, conveying the extruded raw material into an extruding machine after extrusion to obtain an extruded sheet blank, and then soaking the extruded sheet blank in a zinc-copper activator for 40-45 min to obtain an activated sheet blank;

(2) taking the activated plate blank out of the zinc-copper activator, putting the activated plate blank into a tubular furnace, heating, preserving heat, pre-burning for 15-20 min, then carrying out temperature programming at the speed of 5-7 ℃/min, introducing nitrogen into the tubular furnace from the beginning of heating, controlling the gas flow to be 80-100 mL/min, heating, preserving heat, and carbonizing for 40-50 min to obtain a foam plate;

(3) mixing carrier polyester, alumina fiber and nano cuprous oxide, heating to 180-200 ℃, pouring onto the surface of a foam plate, cooling to 70-80 ℃, performing calendering molding by using a press to form a polyester surface layer, controlling the thickness of the polyester surface layer to be 4-5 mm, and cooling to room temperature to obtain a fireproof heat-preservation composite extruded sheet;

the carrier polyester comprises the following specific preparation steps:

mixing polystyrene and vinyl acetate resin to obtain mixed resin, pouring the mixed resin into a three-neck flask filled with styrene, heating the three-neck flask to 80-90 ℃, starting a stirrer, stirring and dispersing at a rotating speed of 300-350 r/min, preserving heat, stirring and reacting for 4-5 hours, discharging, and naturally cooling to room temperature to obtain carrier polyester;

the preparation method of the graphite acid solution comprises the following specific steps:

taking 30-35 g of natural crystalline flake graphite, placing the natural crystalline flake graphite into a mesh bag, placing a titanium metal plate as an anode in the mesh bag, placing the mesh bag into a beaker, placing a titanium metal plate as a cathode in the beaker, adding 200-300 mL of electrolyte into the beaker, controlling the temperature of the electrolyte in the beaker to be 20-22 ℃, starting a power supply, and electrolyzing for 40-45 min to obtain the graphite acid solution.

2. The preparation method of the fireproof heat-preservation composite extruded sheet according to claim 1, characterized by comprising the following steps: the preparation method of the fireproof heat-preservation composite extruded sheet comprises the step (1) of mixing the resin obtained in the step (1) with a graphite acid solution, asphalt and epoxy resin according to a mass ratio of 1: 4: 5.

3. The preparation method of the fireproof heat-preservation composite extruded sheet according to claim 2, characterized by comprising the following steps: the fireproof heat-preservation composite extruded sheet is prepared by compounding a zinc-copper activator in the step (1) according to the equal volume ratio of a zinc chloride solution with the concentration of 3.0-4.0 mol/L and a copper chloride solution with the concentration of 0.3-0.5 mol/L.

4. The preparation method of the fireproof heat-preservation composite extruded sheet according to claim 1, characterized by comprising the following steps: the specific preparation steps (2) of the fireproof heat-preservation composite extruded sheet are that the heat-preservation pre-sintering temperature and the heat-preservation carbonization temperature are preferably 100-120 ℃ and 250-280 ℃ respectively.

5. The preparation method of the fireproof heat-preservation composite extruded sheet according to claim 1, characterized by comprising the following steps: the fireproof heat-preservation composite extruded sheet is prepared by mixing the carrier polyester, the alumina fiber and the nano cuprous oxide at a mixing mass ratio of 20: 4: 1 in the step (3).

6. The preparation method of the fireproof heat-preservation composite extruded sheet according to claim 1, characterized by comprising the following steps: and (3) specifically preparing the fireproof heat-preservation composite extruded sheet, wherein the calendering pressure is controlled to be 0.8-1.0 MPa during calendering molding.

7. The preparation method of the fireproof heat-preservation composite extruded sheet according to claim 1, characterized by comprising the following steps: the raw materials of the components in the specific preparation step of the carrier polyester comprise, by weight, 60-70 parts of polystyrene, 30-40 parts of vinyl acetate resin and 60-70 parts of styrene.

8. The preparation method of the fireproof heat-preservation composite extruded sheet according to claim 1, characterized by comprising the following steps: the electrolyte in the specific preparation step of the graphite acid liquid is obtained by mixing 75% of perchloric acid solution and 95% of glacial acetic acid solution according to the volume ratio of 4: 1.

9. The preparation method of the fireproof heat-preservation composite extruded sheet according to claim 1, characterized by comprising the following steps: the current intensity is controlled to be 0.3-0.5A in the electrolysis process in the specific preparation step of the graphitic acid liquid.

Technical Field

The invention belongs to the technical field of composite materials, and particularly relates to a preparation method of a fireproof heat-preservation composite extruded sheet.

Background

With the development of economy and society, energy conservation and environmental protection have become common knowledge, and reducing energy consumption has become a goal of human co-efforts. In order to save energy more effectively, energy-saving buildings are an important subject, and the improvement of the heat-insulating performance of buildings can have a remarkable effect on energy consumption caused by air conditioning, so that the demand of buildings for high-performance heat-insulating materials is increased.

The heat insulation and preservation materials can be roughly divided into two categories, one is an organic high polymer material, the other is an inorganic material, the organic high polymer material such as an extruded polystyrene heat insulation board is increasingly and widely applied to the building material industry as the heat insulation and preservation board due to light weight, good heat insulation performance and good comprehensive performance, and the inorganic heat insulation material has the characteristics of good economy, high compression modulus and good flame retardance, but the inorganic heat insulation material has the defects of heavy weight, large water absorption rate, brittleness and easiness in crushing. Therefore, the heat-insulating building material board obtained by combining the organic material and the inorganic material has a problem of thickness, and cannot reflect the light property of the organic polymer material, so that it is inconvenient to actually use the heat-insulating building material board in buildings.

A modified extruded sheet and its preparation method, the composition of the modified extruded sheet comprises polystyrene granule, graphite, hexabromocyclododecane, ethanol and foaming agent, wherein graphite accounts for 5% -8% of the total weight of the polystyrene granule, hexabromocyclododecane accounts for 5% -8% of the total weight of the polystyrene granule, ethanol accounts for 5% -8% of the total weight of the polystyrene granule, and foaming agent accounts for 10% of the total weight of the polystyrene granule; the method comprises the steps of firstly putting polystyrene particles, graphite, hexabromocyclododecane and an auxiliary agent into a mixing bin, uniformly stirring to form a first mixture, then injecting the first mixture into a heated double-screw device, simultaneously adding a foaming agent and ethanol, heating and stirring to form a second mixture, and finally adding the second mixture into a plastic extruding machine to extrude to form the modified extruded sheet. The modified extruded sheet prepared by the composition and the method has the problem that the heat preservation effect cannot meet the requirement of a specific occasion to a certain extent.

The technology is advanced, the era is developed, and the society is continuously advanced along with the continuous forward development of the economic society of China; along with the continuous deepening of the urbanization process of China, a large number of people enter cities; china is in continuous construction all the time, especially after reform is opened; the problems of energy conservation, heat preservation and environmental protection in the building field are more and more aroused attention of people.

The industrialization process of China is continuously promoted, fossil fuels are continuously used, the emission of greenhouse gases is continuously increased, and the degree of acid rain is continuously increased; acid rain has great influence on industries such as industry, agriculture, forestry, animal husbandry, fishery and the like; similarly, acid rain can corrode buildings, ancient buildings, cultural relics and the like, modern buildings are affected to different degrees, and extruded sheets used in the buildings can be affected by the acid rain.

In recent years, the extruded sheet has the advantages of high strength, excellent heat insulation effect, low coefficient rate and the like, is widely popularized and applied in the market of building exterior wall heat insulation, and is deeply favored by users. However, the fireproof performance of the extruded sheet is poor, and the extruded sheet is easy to generate fire when meeting open fire in engineering application, poses certain threat to personnel and property safety, and cannot reach the current fireproof standard, so that the research and development of the extruded sheet with higher fireproof performance are urgent.

The traditional extruded foam insulation board has higher heat conductivity coefficient and increased selected thickness; the fire-proof performance is poor, and the fire-proof requirement of flame-retardant B1 grade cannot be really met. The graphite type extruded sheet (CXPS) takes graphite polystyrene synthetic resin as a main raw material, is added with inorganic flame retardants such as magnesium oxide, aluminum oxide and other auxiliary materials, is heated and mixed by a special process, is injected with a CO2 catalyst, and is continuously extruded and molded to obtain the foam insulation board, which is called CXPS for short.

At present, extruded sheets exist: general heat preservation effect, general security, general fire behavior etc.

Therefore, the invention of the excellent extruded sheet has positive significance in the technical field of composite materials.

Disclosure of Invention

The invention mainly solves the technical problem and provides a preparation method of a fireproof heat-preservation composite extruded sheet aiming at the defects that the heat-preservation effect of the existing extruded sheet is general, the fireproof performance of the existing organic polymer extruded sheet is poor, and the safety is lower when the organic polymer extruded sheet is applied to a building external wall heat-preservation material.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

a preparation method of a fireproof heat-preservation composite extruded sheet is characterized by comprising the following specific preparation steps:

(1) putting the mixed resin into an oven with the set temperature of 100-120 ℃, preheating and drying for 40-50 min to obtain a raw material to be extruded, injecting the raw material into a double-screw device, stirring for 10-15 min, heating to 150-180 ℃, conveying the extruded raw material into an extruding machine after extrusion to obtain an extruded sheet blank, and then soaking the extruded sheet blank in a zinc-copper activator for 40-45 min to obtain an activated sheet blank;

(2) taking the activated plate blank out of the zinc-copper activator, putting the activated plate blank into a tubular furnace, heating, preserving heat, pre-burning for 15-20 min, then carrying out temperature programming at the speed of 5-7 ℃/min, introducing nitrogen into the tubular furnace from the beginning of heating, controlling the gas flow to be 80-100 mL/min, heating, preserving heat, and carbonizing for 40-50 min to obtain a foam plate;

(3) mixing carrier polyester, alumina fiber and nano cuprous oxide, heating to 180-200 ℃, pouring onto the surface of a foam plate, cooling to 70-80 ℃, performing calendering molding by using a press to form a polyester surface layer, controlling the thickness of the polyester surface layer to be 4-5 mm, and cooling to room temperature to obtain a fireproof heat-preservation composite extruded sheet;

the carrier polyester comprises the following specific preparation steps:

mixing polystyrene and vinyl acetate resin to obtain mixed resin, pouring the mixed resin into a three-neck flask filled with styrene, heating the three-neck flask to 80-90 ℃, starting a stirrer, stirring and dispersing at a rotating speed of 300-350 r/min, preserving heat, stirring and reacting for 4-5 hours, discharging, and naturally cooling to room temperature to obtain carrier polyester;

the preparation method of the graphite acid solution comprises the following specific steps:

taking 30-35 g of natural crystalline flake graphite, placing the natural crystalline flake graphite into a mesh bag, placing a titanium metal plate as an anode in the mesh bag, placing the mesh bag into a beaker, placing a titanium metal plate as a cathode in the beaker, adding 200-300 mL of electrolyte into the beaker, controlling the temperature of the electrolyte in the beaker to be 20-22 ℃, starting a power supply, and electrolyzing for 40-45 min to obtain the graphite acid solution.

The preparation method of the fireproof heat-preservation composite extruded sheet comprises the step (1) of mixing the resin obtained in the step (1) with a graphite acid solution, asphalt and epoxy resin according to a mass ratio of 1: 4: 5.

The fireproof heat-preservation composite extruded sheet is prepared by compounding a zinc-copper activator in the step (1) according to the equal volume ratio of a zinc chloride solution with the concentration of 3.0-4.0 mol/L and a copper chloride solution with the concentration of 0.3-0.5 mol/L.

The specific preparation steps (2) of the fireproof heat-preservation composite extruded sheet are that the heat-preservation pre-sintering temperature and the heat-preservation carbonization temperature are preferably 100-120 ℃ and 250-280 ℃ respectively.

The fireproof heat-preservation composite extruded sheet is prepared by mixing the carrier polyester, the alumina fiber and the nano cuprous oxide at a mixing mass ratio of 20: 4: 1 in the step (3).

And (3) specifically preparing the fireproof heat-preservation composite extruded sheet, wherein the calendering pressure is controlled to be 0.8-1.0 MPa during calendering molding.

The raw materials of the components in the specific preparation step of the carrier polyester comprise, by weight, 60-70 parts of polystyrene, 30-40 parts of vinyl acetate resin and 60-70 parts of styrene.

The electrolyte in the specific preparation step of the graphite acid liquid is obtained by mixing 75% of perchloric acid solution and 95% of glacial acetic acid solution according to the volume ratio of 4: 1.

The current intensity is controlled to be 0.3-0.5A in the electrolysis process in the specific preparation step of the graphitic acid liquid.

The invention has the beneficial effects that:

(1) the invention takes natural flake graphite as raw material, as anode in acid electrolyte, obtains graphite acid liquid by electrolysis, mixes graphite acid liquid, asphalt and epoxy resin to obtain mixed resin, puts the mixed resin into a mould after preheating and drying, pours the mixed resin melt into an activation slab after heating and raising temperature, puts the activation slab into a tubular furnace after dipping into a zinc-copper activator, heats and preserves heat and chars under the protection of nitrogen to obtain a foam board, pours the carrier polyester, alumina fiber and nano cuprous oxide into the surface of the foam board after heating and melting, then carries out hot pressing to obtain the fireproof heat preservation composite extruded sheet, the mixed resin is hydrolyzed and degraded under the action of the composite activator of zinc chloride and copper chloride to form oligomer, after dehydration by heating and charing reaction, can promote the condensation and aromatization of intermediate products to form a graphite-like microcrystal structure, and a porous system is generated, so that a good heat preservation effect is achieved, a large amount of high-concentration zinc and copper ions are remained in the aromatized organic matter under an acidic condition to form a complex and are adsorbed in the micropores of the graphite-like microcrystalline structure, and the copper and zinc ions can also enhance the internal structural strength of the formed porous foam plate and reduce the heat conductivity coefficient.

The fireproof heat-preservation composite extruded sheet has a three-layer structure, the middle layer is a foam sheet, the middle layer is coated with a polyester layer, the thickness of middle foam carbon is larger, the fireproof heat-preservation composite extruded sheet has the advantages of light heat preservation, the flame retardant property is better than that of a common organic polymer extruded sheet, the foam sheet is substantially a foam carbon material, in the preparation process of the foam carbon, the graphite acid liquid has a promoting effect on the carbonization of mixed resin, the gases such as carbon monoxide and the like are generated to enable open pores to be more permeable, loose and porous foam carbon is generated to improve the pore forming rate, the graphite and a zinc-copper activating agent have a synergistic effect in the carbonization process, microcrystalline pores can be formed in the foam carbon, the strength of the pores is improved, the polyester material on the surface plays a buffering effect and reduces the influence of the pores by external stress, in addition, the thermal expansion coefficient of the natural flake graphite is increased after acidification and electrolysis, the prepared foam carbon is more fluffy, and part of the non-carbonized asphalt has a certain energy storage conversion effect in the plastic floor, so that the extruded sheet is warm in winter and cool in summer when being applied to the heat insulation of the outer wall of the building, and has wide application prospect.

Detailed Description

Mixing 60-70 parts of polystyrene and 30-40 parts of vinyl acetate resin according to parts by weight to obtain mixed resin, pouring the mixed resin into a three-neck flask filled with 60-70 parts of styrene, heating the three-neck flask to 80-90 ℃, starting a stirrer, stirring and dispersing at a rotating speed of 300-350 r/min, carrying out heat preservation stirring reaction for 4-5 hours, discharging, and naturally cooling to room temperature to obtain carrier polyester; weighing 30-35 g of natural crystalline flake graphite, placing the natural crystalline flake graphite into a mesh bag, placing a titanium metal plate as an anode in the mesh bag, placing the mesh bag into a beaker, placing a titanium metal plate as a cathode in the beaker, mixing 75% by mass of perchloric acid solution and 95% by mass of glacial acetic acid solution according to a volume ratio of 4: 1 to obtain electrolyte, adding 200-300 mL of the electrolyte into the beaker, controlling the temperature of the electrolyte in the beaker to be 20-22 ℃, starting a power supply, and electrolyzing for 40-45 min at a current intensity of 0.3-0.5A to obtain a graphite acid solution; mixing the graphite acid liquid, the asphalt and the epoxy resin according to a mass ratio of 1: 4: 5 to obtain mixed resin, putting the mixed resin into an oven with a set temperature of 100-120 ℃, preheating and drying for 40-50 min to obtain a raw material to be extruded, injecting the raw material into a double-screw device, stirring for 10-15 min, heating to 150-180 ℃, extruding, conveying into an extruding machine, extruding to obtain an extruded plate blank, soaking in a zinc-copper activating agent for 40-45 min to obtain an activated plate blank, and compounding the zinc-copper activating agent by using a zinc chloride solution with a concentration of 3.0-4.0 mol/L and a copper chloride solution with a concentration of 0.3-0.5 mol/L in an equal volume ratio;

taking the activated plate blank out of the zinc-copper activator, putting the activated plate blank into a tubular furnace, heating to 100-120 ℃, preserving heat and presintering for 15-20 min, then carrying out temperature program heating at the speed of 5-7 ℃/min, introducing nitrogen into the tubular furnace from the beginning of heating, controlling the gas flow to be 80-100 mL/min, heating to 250-280 ℃, preserving heat and carbonizing for 40-50 min, and obtaining a foam plate; mixing carrier polyester, alumina fiber and nano cuprous oxide according to a mass ratio of 20: 4: 1, heating to 180-200 ℃, pouring onto the surface of a foam plate, cooling to 70-80 ℃, performing calendering molding by using a press to form a polyester surface layer, controlling the thickness of the polyester surface layer to be 4-5 mm, and the calendering pressure to be 0.8-1.0 MPa, and cooling to room temperature to obtain the fireproof heat-preservation composite extruded sheet.