A building energy-saving thermal insulation material and its preparation process
By adding safe and non-toxic flame retardant additives and surface-treated sepiolite fibers and aluminum silicate fibers to the polystyrene foam, the fire hazard and toxic gas generation problems of polystyrene foam are solved, and the problem of fire hazard and toxic gas generation is achieved. Highly efficient flame retardant and thermal insulation.
Patent Information
- Application Number
- CN202211315573.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-10-26
- Publication Date
- 2024-12-17
- Estimated Expiration
- 2042-10-26
AI Technical Summary
The existing polystyrene foam materials have problems with fire hazards and toxic gases in flame retardant modification, and the inorganic flame retardant is added large and has poor compatibility, which causes harm to the environment and human health.
Using a safe and non-toxic flame retardant additive DOPO derivative, melt blending with polystyrene, chemical bonding is formed to improve flame retardant performance, and sepiolite fibers and aluminum silicate fibers are treated with silane coupling agents. , improve the interface compatibility and heat insulation effect between the insulation filler and the substrate.
The safety, stable flame retardant performance and excellent thermal insulation effect of polystyrene foam materials are achieved, avoiding the easy migration and oozing defects of traditional flame retardants, and improving the longevity and stability of the material.
Smart Images
Figure BDA0003908642480000031 
Figure BDA0003908642480000032 
Figure BDA0003908642480000071
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of building materials, and in particular, relates to a building energy-saving and heat-insulating material and a preparation process thereof. Background Art
[0002] With the promotion and development of building energy conservation, thermal insulation materials and products are receiving more and more attention. There are many kinds of building materials, which can be roughly divided into: inorganic materials, which include metal materials (including ferrous metal materials and non-ferrous metal materials) and non-metallic materials (such as natural stone, burnt earth products, cement, concrete and silicate products, etc.). Organic materials, which include plant materials, synthetic polymer materials (including plastics, coatings, adhesives) and asphalt materials. Composite materials, which include asphalt concrete, polymer concrete, etc., are generally composed of inorganic non-metallic materials and organic materials. Among synthetic polymer materials, the most widely used is polystyrene foam material. Polystyrene foam has good thermal insulation properties and good processing properties, but it has potential fire hazards.
[0003] In the prior art, the flame retardant modification of EPS is mainly achieved by adding flame retardants. Additive flame retardants can be divided into two categories according to their chemical composition: organic flame retardants and inorganic flame retardants. Inorganic flame retardants such as magnesium hydroxide, aluminum hydroxide, antimony trioxide, etc. have the advantages of low smoke, low toxicity, halogen-free, good stability and low price, but have the disadvantages of large addition amount, poor compatibility with materials, and reduced material performance, which are subject to certain restrictions. Organic flame retardants are mainly halogen flame retardants, such as decabromodiphenyl ether, decabromodiphenyl ether, etc. Although this series of flame retardants has the advantages of good compatibility with materials, small addition amount, high cost performance, and little impact on material performance, a large amount of toxic gases such as hydrogen halides will be produced during flame retardancy, which will cause harm to humans and their environment. Summary of the invention
[0004] The purpose of the present invention is to overcome the defects of the prior art and provide a building energy-saving and thermal insulation material and a preparation process thereof.
[0005] The purpose of the present invention can be achieved through the following technical solutions:
[0006] A building energy-saving and heat-insulating material, comprising the following raw materials in parts by weight: 50 parts of polystyrene, 15-20 parts of heat-insulating filler, 4-6 parts of polyolefin elastomer, 2-3 parts of flame retardant additive, and 4-5 parts of azodicarbonamide (foaming agent);
[0007] The preparation process of the thermal insulation material comprises the following steps:
[0008] The raw materials were mixed in a high-speed mixer for 10 minutes according to the ratio, and then granulated by a twin-screw extruder. The temperatures of the six heating zones were set to 150-155°C, 150-155°C, 155-160°C, 155-160°C, 160-165°C, and 160-165°C in sequence. After granulation, a single-screw extruder was used for foaming extrusion. The temperatures of the feeding section and the compression section were 150-155°C, the temperature of the homogenizing section was 165-175°C, and the temperature of the die was 140-145°C to obtain a thermal insulation material.
[0009] Furthermore, the thermal insulation filler is sepiolite fiber and aluminum silicate fiber, the mass ratio of the two is 1:1, and both are surface treated with silane coupling agent KH550 to improve the interface compatibility with the polymer matrix and promote dispersion; sepiolite fiber and aluminum silicate fiber both have excellent thermal insulation properties, are evenly distributed in polystyrene foam, and can effectively improve the thermal insulation effect.
[0010] Furthermore, the polyolefin elastomer is an ethylene-octene block copolymer, which can play a toughening effect and improve the impact resistance of the polystyrene foam.
[0011] Furthermore, the flame retardant additive is prepared by the following steps:
[0012] S1. Add DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), fumaric acid and DMF (N,N-dimethylformamide) into a three-necked flask equipped with a mechanical stirring device and a reflux condenser, and continuously introduce nitrogen protection. First, heat to 90°C for 1 hour, then heat to 130°C for 6 hours. After the reaction is completed and the product cools to room temperature, pour distilled water into the product, transfer it to an ice-water bath to precipitate the solid, and then filter under reduced pressure to obtain a filter cake. After washing the filter cake with petroleum ether for 3-4 times, dry it in a vacuum oven at 80°C for 12 hours to obtain an intermediate product. The ratio of DOPO, fumaric acid, DMF and distilled water is 0.1 mol:0.1 mol:150 mL:300 mL.
[0013] The active PH bond in DOPO reacts with the unsaturated carbon-carbon double bond in fumaric acid to obtain an intermediate product. The reaction process is as follows:
[0014]
[0015] S2. Under N2 protection, the intermediate product, triethylamine (acid binding agent) and dichloromethane are added to a three-necked flask, and then p-aminostyrene and DIC (N, N-diisopropylcarbodiimide) are added, and nitrogen protection is continuously introduced. The reaction is stirred at room temperature for 3 hours. After the reaction is completed, the solvent dichloromethane is removed by reduced pressure distillation, and then deionized water is added to the product, and the pH value of the mixed solution is adjusted to 8.0 with potassium carbonate. The mixture is extracted with ethyl acetate, the organic layer is taken and washed with a saturated NaCl solution, dried over anhydrous magnesium sulfate, and the solvent is removed by reduced pressure rotary distillation to obtain a flame retardant additive; the ratio of the amount of the intermediate product, p-aminostyrene, triethylamine, DIC, dichloromethane and deionized water is 0.11 mol: 0.1 mol: 10.1 g: 12.6 g: 250 mL: 400 mL;
[0016] The -COOH on the intermediate product molecule undergoes a condensation reaction with the -NH2 on the p-aminostyrene. By controlling the molar ratio of the two to be close to 1:1 (the intermediate product is slightly excessive), only the -COOH at one end of the intermediate product participates in the reaction process to obtain a flame retardant additive. The reaction process is as follows:
[0017]
[0018] The flame retardant additive obtained is a DOPO derivative, which is a safe and non-toxic flame retardant ingredient. Therefore, the flame retardant additive has a flame retardant effect. Adding it to polystyrene foam can improve its flame retardant properties. In addition, the flame retardant additive molecules contain carbon-carbon double bond groups. During the melt blending process with polystyrene, it can participate in the repolymerization process and interact with the matrix in a chemically bonded manner. Compared with the addition of small molecule flame retardants alone, this method has the advantages of improving the defects of easy migration and exudation of flame retardants and improving the durability and stability of the flame retardant effect. It should be further explained that the flame retardant additive molecules also contain -COOH groups. During the melt blending process, it can react chemically with the KH550 molecular chain (-NH2 thereon) grafted on the surface of the thermal insulation filler, thereby increasing the interaction between the thermal insulation filler and the matrix, thereby further improving the thermal insulation effect.
[0019] Beneficial effects of the present invention:
[0020] The thermal insulation material of the present invention is polystyrene foam, which itself has a rich pore structure, so that it has excellent thermal insulation and heat preservation performance; by adding thermal insulation fillers-sepiolite fiber and aluminum silicate fiber into the foam raw material, both of which have excellent thermal insulation properties and are evenly distributed in the polystyrene foam, the thermal insulation effect can be effectively improved; in addition, by adding a flame retardant additive into the raw material, the flame retardant additive can not only give the polystyrene foam safe and stable flame retardant performance, but also can produce a chemical reaction with the thermal insulation filler, improve the force between the thermal insulation filler and the matrix, thereby further improving the thermal insulation effect; finally, a material with both thermal insulation and flame retardant effects is obtained, which has extremely high application value in the field of construction. DETAILED DESCRIPTION
[0021] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0022] Example 1
[0023] Preparation of flame retardant additives:
[0024] S1. Add 0.1 mol of DOPO, 0.1 mol of fumaric acid and 150 mL of DMF to a three-necked flask equipped with a mechanical stirring device and a reflux condenser, and continuously introduce nitrogen protection. First, heat to 90°C for 1 hour, then heat to 130°C for 6 hours. After the reaction is completed and the product cools to room temperature, pour 300 mL of distilled water into the product, transfer to an ice-water bath to precipitate solids, and then filter under reduced pressure to obtain a filter cake. After washing the filter cake with petroleum ether for 3 times, dry it in a vacuum oven at 80°C for 12 hours to obtain an intermediate product.
[0025] S2. Under N2 protection, 0.11 mol of the intermediate product, 10.1 g of triethylamine and 250 mL of dichloromethane were added to a three-necked flask, and then 0.1 mol of p-aminostyrene and 12.6 g of DIC were added, and nitrogen was continuously introduced for protection. The reaction was stirred at room temperature for 3 h. After the reaction was completed, the solvent dichloromethane was removed by vacuum distillation, and then 400 mL of deionized water was added to the product, and the pH value of the mixed solution was adjusted to 8.0 with potassium carbonate. The mixture was extracted with ethyl acetate, the organic layer was taken and washed with saturated NaCl solution, dried over anhydrous magnesium sulfate, and the solvent was removed by vacuum rotary distillation to obtain a flame retardant additive.
[0026] Example 2
[0027] Preparation of flame retardant additives:
[0028] S1. Add 0.2 mol of DOPO, 0.2 mol of fumaric acid and 300 mL of DMF to a three-necked flask equipped with a mechanical stirring device and a reflux condenser, and continuously introduce nitrogen protection. First, heat to 90°C for 1 hour, then heat to 130°C for reaction for 6 hours. After the reaction is completed and the product cools to room temperature, pour 600 mL of distilled water into the product, transfer to an ice-water bath to precipitate solids, then filter under reduced pressure to obtain a filter cake, wash the filter cake with petroleum ether 4 times, and dry it in a vacuum oven at 80°C for 12 hours to obtain an intermediate product.
[0029] S2. Under N2 protection, 0.22 mol of the intermediate product, 20.2 g of triethylamine and 500 mL of dichloromethane were added to a three-necked flask, and then 0.2 mol of p-aminostyrene and 25.2 g of DIC were added, and nitrogen was continuously introduced for protection. The reaction was stirred at room temperature for 3 h. After the reaction was completed, the solvent dichloromethane was removed by vacuum distillation, and then 800 mL of deionized water was added to the product, and the pH value of the mixed solution was adjusted to 8.0 with potassium carbonate. The mixture was extracted with ethyl acetate, the organic layer was taken and washed with saturated NaCl solution, dried over anhydrous magnesium sulfate, and the solvent was removed by vacuum rotary distillation to obtain a flame retardant additive.
[0030] Example 3
[0031] Preparation of thermal insulation filler:
[0032] The silane coupling agent KH-550 and ethanol are fully mixed in a mass ratio of 1:4 to obtain a coupling agent solution; sepiolite fiber and aluminum silicate fiber are mixed in a mass ratio of 1:1, and then mixed with the coupling agent solution in a solid-liquid ratio of 1g:10mL, and the mixture is mixed at high speed in a high-speed mixer at a mixing temperature of 80°C and a mixing time of 20min. After filtering, the solid material is dried in a blast dryer at 105°C for 4h to obtain a thermal insulation filler.
[0033] Example 4
[0034] A building energy-saving and heat-insulating material, comprising the following raw materials in parts by weight: 50 parts of polystyrene, 15 parts of the heat-insulating filler prepared in Example 3, 4 parts of ethylene-octene block copolymer, 2 parts of the flame retardant additive prepared in Example 1, and 4 parts of azodicarbonamide (foaming agent);
[0035] The preparation process of the thermal insulation material comprises the following steps:
[0036] According to the ratio, each raw material was mixed with a high-speed mixer for 10 minutes, and then granulated with a twin-screw extruder. The temperatures of the six heating zones were set to 150°C, 150°C, 155°C, 155°C, 160°C, and 160°C respectively. After granulation, a single-screw extruder was used for foaming extrusion. The temperatures of the feeding section and the compression section were 150°C, the temperature of the homogenizing section was 165°C, and the temperature of the die was 140°C to obtain the thermal insulation material.
[0037] Example 5
[0038] A building energy-saving and heat-insulating material, comprising the following raw materials in parts by weight: 50 parts of polystyrene, 17.5 parts of the heat-insulating filler prepared in Example 3, 5 parts of ethylene-octene block copolymer, 2.5 parts of the flame retardant additive prepared in Example 2, and 4.5 parts of azodicarbonamide (foaming agent);
[0039] The preparation process of the thermal insulation material comprises the following steps:
[0040] According to the ratio, each raw material was mixed with a high-speed mixer for 10 minutes, and then granulated with a twin-screw extruder. The temperatures of the six heating zones were set to 153°C, 153°C, 158°C, 158°C, 163°C, and 163°C respectively. After granulation, a single-screw extruder was used for foaming extrusion. The temperatures of the feeding section and the compression section were 153°C, the temperature of the homogenizing section was 170°C, and the temperature of the die was 143°C to obtain the thermal insulation material.
[0041] Example 6
[0042] A building energy-saving and heat-insulating material, comprising the following raw materials in parts by weight: 50 parts of polystyrene, 20 parts of the heat-insulating filler prepared in Example 3, 6 parts of ethylene-octene block copolymer, 3 parts of the flame retardant additive prepared in Example 1, and 5 parts of azodicarbonamide (foaming agent);
[0043] The preparation process of the thermal insulation material comprises the following steps:
[0044] According to the ratio, each raw material was mixed with a high-speed mixer for 10 minutes, and then granulated with a twin-screw extruder. The temperatures of the six heating zones were set to 155°C, 155°C, 160°C, 160°C, 165°C, and 165°C respectively. After granulation, a single-screw extruder was used for foaming extrusion. The temperatures of the feeding section and the compression section were 155°C, the temperature of the homogenizing section was 175°C, and the temperature of the die was 145°C to obtain the thermal insulation material.
[0045] Comparative Example
[0046] The difference from Example 4 is that no flame retardant additive is added to the raw materials, and the other raw materials and preparation process remain unchanged.
[0047] The following performance tests were performed on the thermal insulation materials obtained in Examples 4-6 and the comparative example:
[0048] Tensile strength test: Tested according to GB / T1040.1-2018, tensile rate 20mm / min;
[0049] Thermal conductivity test: Tested according to GB / T10294-2008;
[0050] Flame retardant performance test: LOI is tested according to GB / T2408-2008;
[0051] The measured results are shown in the following table:
[0052]
[0053] It can be seen from the data in the above table that the thermal insulation material obtained by the present invention has mechanical properties that meet the requirements, and has excellent thermal insulation and flame retardant properties; combined with the data of the comparative example, it can be seen that the addition of flame retardant additives can not only improve the flame retardant properties of the material, but also interact with the thermal insulation filler to improve the thermal insulation effect and mechanical properties to a certain extent.
[0054] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.
[0055] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.
Claims
1. A building energy-saving and thermal insulation material, characterized in that: The raw materials include the following parts by weight: 50 parts of polystyrene, 15-20 parts of thermal insulation filler, 4-6 parts of polyolefin elastomer, 2-3 parts of flame retardant additive, and 4-5 parts of azodicarbonamide; The thermal insulation filler is sepiolite fiber and aluminum silicate fiber, the mass ratio of the two is 1:1, and both are surface treated with silane coupling agent KH550; The flame retardant additive is prepared by the following steps: S1. Add DOPO, fumaric acid and DMF to a three-necked flask equipped with a mechanical stirring device and a reflux condenser, and continuously introduce nitrogen protection. First, heat to 90°C for 1 hour, then heat to 130°C for 6 hours. After the reaction is completed and the product cools to room temperature, pour distilled water into the product, transfer to an ice water bath to precipitate solids, and then filter under reduced pressure to obtain a filter cake. After washing the filter cake with petroleum ether for 3-4 times, dry it in a vacuum oven at 80°C for 12 hours to obtain an intermediate product. S2. Under N2 protection, the intermediate product, triethylamine and dichloromethane are added to a three-necked flask, and then p-aminostyrene and N,N-diisopropylcarbodiimide are added, and nitrogen is continuously introduced for protection. The reaction is stirred at room temperature for 3 hours. After the reaction is completed, the solvent dichloromethane is removed by vacuum distillation, and then deionized water is added to the product, and the pH value of the mixed solution is adjusted to 8.0 with potassium carbonate. The mixture is extracted with ethyl acetate, the organic layer is taken and washed with saturated NaCl solution, dried over anhydrous magnesium sulfate, and the solvent is removed by vacuum rotary evaporation to obtain a flame retardant additive.
2. A building energy-saving and heat-insulating material according to claim 1, characterized in that: In step S1, the ratio of DOPO, fumaric acid, DMF and distilled water is 0.1 mol: 0.1 mol: 150 mL: 300 mL.
3. A building energy-saving and heat-insulating material according to claim 1, characterized in that: In step S2, the ratio of the intermediate product, p-aminostyrene, triethylamine, N,N-diisopropylcarbodiimide, dichloromethane and deionized water is 0.11 mol: 0.1 mol: 10.1 g: 12.6 g: 250 mL: 400 mL.
4. A building energy-saving and heat-insulating material according to claim 1, characterized in that: The polyolefin elastomer is an ethylene-octene block copolymer.
5. The preparation process of a building energy-saving and heat-insulating material according to claim 1, characterized in that: The steps include: The raw materials were mixed for 10 minutes using a high-speed mixer according to the ratio, and then granulated using a twin-screw extruder. After the granulation was completed, a single-screw extruder was used for foaming and extrusion to obtain a thermal insulation material.
6. The preparation process of a building energy-saving and heat-insulating material according to claim 5, characterized in that: The temperatures of the six heating zones of the twin-screw extruder are set to 150-155°C, 150-155°C, 155-160°C, 155-160°C, 160-165°C, and 160-165°C respectively; the temperatures of the feeding section and compression section of the single-screw extruder are 150-155°C, the temperature of the homogenizing section is 165-175°C, and the die temperature is 140-145°C.