A heat-insulating and heat-preserving material for passive houses and a preparation method thereof

Abstract

The present invention relates to the field of heat insulation materials, and specifically to a heat insulation material for passive houses and a preparation method thereof. Prepared from the following raw materials by weight: 40-60 parts of cellulose grafted polystyrene, 20-30 parts of styrene-butadiene-styrene block copolymer, 15-25 parts of POSS-SiO2 composite aerogel, 20-30 parts of light calcium carbonate, 1-3 parts of silane coupling agent, 0.5-1 part of monoglyceride stearate, 1-3 parts of flame retardant, and 3-5 parts of AC blowing agent. The heat insulation material prepared by the present invention has good mechanical properties, low thermal conductivity, excellent heat insulation performance, and also has a certain fireproof and flame retardant performance, and has a wide application prospect as a building decoration material for passive houses.

Description

Technical Field

[0001] The present invention relates to the field of heat insulation materials, and specifically to a heat insulation material for passive houses and a preparation method thereof. Background Art

[0002] A passive house is an integrated product of various technical products, and is a house that makes full use of renewable energy so that the total sum of all consumed primary energy does not exceed 120 kWh / (square meter·year). Such a low energy consumption standard is achieved through highly heat-insulating and sound-insulating, tightly sealed building exterior walls and renewable energy.

[0003] Polystyrene foam material, as a commonly used thermal insulation material for passive houses, has good sound insulation, heat insulation and thermal insulation performance. However, the polystyrene foam material has limited strength, poor load-bearing capacity, is easy to crack, has a short service life, needs to be frequently replaced and maintained, and is difficult to meet the performance requirements of high-quality passive houses.

[0004] Chinese Patent CN112028597A discloses a preparation method and product of a thermal insulation board for passive houses. The invention first prepares zirconium and hafnium, as well as nano-silica fiber and nano-aluminum oxide fiber-reinforced modified alumina-silica aerogel, and then modifies the aerogel with a silane coupling agent to improve the hydrophobicity and lipophilicity of the aerogel, and then coats polystyrene, and obtains a thermal insulation board through pre-expansion, curing, mold forming, and foaming. The prepared thermal insulation board has excellent flexural strength and low thermal conductivity, and is an ideal material for passive houses. However, its maximum flexural strength is only 4 MPa, and its mechanical properties are poor. Summary of the Invention

[0005] Object of the Invention: Aiming at the above technical problems, the present invention provides a heat insulation material for passive houses and a preparation method thereof.

[0006] The technical solution adopted is as follows:

[0007] A heat insulation material for passive houses is prepared from the following raw materials in parts by weight:

[0008] 40-60 parts of cellulose grafted polystyrene, 20-30 parts of styrene-butadiene-styrene block copolymer, 15-25 parts of POSS-SiO2 composite aerogel, 20-30 parts of light calcium carbonate, 1-3 parts of silane coupling agent, 0.5-1 part of monoglyceride stearate, 1-3 parts of flame retardant, 3-5 parts of AC foaming agent.

[0009] Further, it is prepared from the following raw materials in parts by weight:

[0010] 60 parts of cellulose grafted polystyrene, 25 parts of styrene-butadiene-styrene block copolymer, 20 parts of POSS-SiO2 composite aerogel, 25 parts of light calcium carbonate, 2 parts of silane coupling agent, 0.8 part of monoglyceride stearate, 1 part of flame retardant, 3 parts of AC blowing agent.

[0011] Furthermore, the preparation method of the cellulose grafted polystyrene is as follows:

[0012] Add microcrystalline cellulose into imidazole-based ionic liquid, heat up to 70 - 85 °C and stir for 1 - 3 h, cool down to 0 - 5 °C, add bromoisobutyryl bromide and pyridine, react at 40 - 50 °C for 12 - 18 h, pour the reaction solution into ice water, separate the precipitated solid, vacuum dry to constant weight to obtain an intermediate. Under nitrogen protection, add the intermediate into 1,4-dioxane, stir to dissolve, then add styrene, pentamethyldiethylenetriamine and copper bromide, seal and heat up to 75 - 85 °C to react for 3 - 5 h. After restoring to room temperature, add tetrahydrofuran into the reaction solution, stir for 30 - 50 min, then add absolute ethanol, separate the precipitated solid, and vacuum dry to constant weight.

[0013] Furthermore, the imidazole-based ionic liquid is any one or more of 1-carboxymethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride.

[0014] Furthermore, the preparation method of the POSS-SiO2 composite aerogel is as follows:

[0015] Add POSS into ethanol, then add dilute hydrochloric acid solution, stir for 10 - 15 min, dissolve tetraethyl orthosilicate in ethanol and add it into the reaction solution, stir at room temperature for 8 - 15 h, then stand for aging for 8 - 15 h, exchange with ethanol and acetone three times in sequence, and vacuum dry to constant weight.

[0016] Furthermore, the POSS is tris(dimethylethoxysilyloxy)-POSS.

[0017] Furthermore, the flame retardant is pentaerythritol phosphate and methyl octabromide ether.

[0018] Furthermore, the mass ratio of pentaerythritol phosphate to methyl octabromide ether is 1 - 5:1.

[0019] The present invention also provides a preparation method of a heat-insulating and heat-preserving material for a passive house:

[0020] Cellulose grafted polystyrene, styrene-butadiene-styrene block copolymer, POSS-SiO2 composite aerogel light calcium carbonate, silane coupling agent, stearic acid monoglyceride, flame retardant, AC foaming agent are added to a high-speed mixer and mixed for 10-30 minutes, and the mixture is added to a twin-screw extruder and heated to a molten state. After the carbon dioxide gas is heated and pressurized by a supercritical fluid injection device to reach a supercritical state, it is injected into the barrel of the twin-screw extruder and fully mixed with the melt in the twin-screw extruder to form a homogeneous melt, which is then transported into a melt pump, the pressure is released at the die head, and the mixture is added to a mold. After foaming, it is cooled and formed.

[0021] Furthermore, the temperature of the heating zone I-heating zone II of the twin-screw extruder is 150-155°C, the temperature of the heating zone III-heating zone IV is 155-165°C, and the temperature of the heating zone V-heating zone VI is 165-175°C.

[0022] Beneficial effects of the present invention:

[0023] The invention provides a thermal insulation material for passive houses. Polystyrene has good processability, dimensional stability and electrical insulation. Cellulose is a renewable material with good thermal insulation performance. The cellulose grafted polystyrene obtained by grafting cellulose with styrene has good heat resistance and mechanical properties. Styrene-butadiene-styrene block copolymer is a block copolymer of styrene and butadiene. The S block is similar to the structure of polystyrene and the two have good compatibility. After being added, the mechanical strength of the thermal insulation material can be improved. Polyhedral oligomeric silsesquioxane (POSS) can be used as a platform for combining organic and inorganic hybrid materials at the molecular level and can be used as a cornerstone for building a three-dimensional network structure. POSS-SiO2 composite aerogel overcomes the defects of common aerogel such as high brittleness and low mechanical strength, improves the network structure of aerogel and enhances the mechanical and surface properties of aerogel. Its rich pore structure also improves the thermal insulation performance of the material. The addition of silane coupling agent can play a coupling and bonding role, enhance the bonding performance between matrix materials, and realize the composite state of "you have me and I have you", so that the thermal insulation material has a uniform structure and higher mechanical strength. The thermal insulation material prepared by the present invention has good mechanical properties, low thermal conductivity, excellent thermal insulation performance, and certain fire retardant properties. It has broad application prospects as a building decoration material for passive houses. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a photo of the thermal insulation material prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0025] For those without specific conditions indicated in the examples, they are carried out under conventional conditions or the conditions recommended by the manufacturer. For the reagents or instruments without the manufacturer indicated, they are all conventional products that can be obtained through commercial purchase.

[0026] Example 1:

[0027] A heat-insulating and heat-preserving material for passive houses is prepared from the following raw materials in parts by weight:

[0028] 60 parts of cellulose grafted polystyrene, 25 parts of styrene-butadiene-styrene block copolymer, 20 parts of POSS-SiO2 composite aerogel, 25 parts of light calcium carbonate, 2 parts of silane coupling agent KH-550, 0.8 part of monoglyceride stearate, 0.5 part of pentaerythritol phosphate, 0.5 part of methyl octabromether, and 3 parts of AC blowing agent.

[0029] Among them, the preparation method of cellulose grafted polystyrene is as follows:

[0030] Add 100 g of microcrystalline cellulose to 800 g of 1-allyl-3-methylimidazolium chloride, heat up to 80 °C and stir for 2 h, then cool down to 0 °C, add 250 mL of bromoisobutyryl bromide and 100 mL of pyridine, react at 50 °C for 15 h, pour the reaction solution into ice water, separate the precipitated solid, and vacuum dry at 60 °C to constant weight to obtain the intermediate. Under nitrogen protection, add 100 g of the intermediate to 800 mL of 1,4-dioxane, stir to dissolve, then add 208 g of styrene, 17.3 g of pentamethyldiethylenetriamine, and 44.6 g of copper bromide, close and heat up to 80 °C to react for 5 h. After restoring to room temperature, add 400 mL of tetrahydrofuran to the reaction solution, stir for 50 min, then add 1200 mL of absolute ethanol, separate the precipitated solid, and vacuum dry at 60 °C to constant weight.

[0031] The preparation method of POSS-SiO2 composite aerogel is as follows:

[0032] Add 108 g of tris(dimethylethenylsiloxy)-POSS to 710 mL of ethanol, and then add 8.6 mL

[0033] of 0.1 mol / L dilute hydrochloric acid solution, stir for 15 min, then dissolve 46 g of tetraethyl orthosilicate in 710 mL of ethanol, add it to the reaction solution, stir at room temperature for 12 h, then stand and age for 12 h, exchange with ethanol and acetone three times in sequence, and vacuum dry at 60 °C to constant weight.

[0034] The preparation method of the above heat-insulating and heat-preserving material for passive houses:

[0035] Graft cellulose onto polystyrene, styrene-butadiene-styrene block copolymer, POSS-SiO2 composite aerogel, light calcium carbonate, silane coupling agent KH-550, monoglyceryl stearate, flame retardant, and AC blowing agent are added to a high-speed mixer and mixed for 10 - 30 min. The mixture is then added to a twin-screw extruder and heated to a molten state. The temperature of heating zone I - heating zone II of the twin-screw extruder is 150 - 155 °C, the temperature of heating zone III - heating zone IV is 155 - 165 °C, and the temperature of heating zone V - heating zone VI is 165 - 175 °C. After the carbon dioxide gas is heated and pressurized to the supercritical state through a supercritical fluid injection device, it is injected into the barrel of the twin-screw extruder and fully mixed with the melt in the twin-screw extruder to form a homogeneous melt. Subsequently, it is transported into a melt pump, depressurized at the die head, added to a mold, foamed at 115 °C for 10 min, and then cooled and shaped.

[0036] Example 2:

[0037] A heat-insulating and heat-preserving material for a passive house is prepared from the following raw materials in parts by weight:

[0038] 60 parts of graft cellulose onto polystyrene, 30 parts of styrene-butadiene-styrene block copolymer, 25 parts of POSS-SiO2 composite aerogel, 30 parts of light calcium carbonate, 3 parts of silane coupling agent KH-550, 1 part of monoglyceryl stearate, 0.5 part of pentaerythritol phosphate, 0.5 part of methyl octabromide ether, and 5 parts of AC blowing agent.

[0039] Among them, the preparation methods of graft cellulose onto polystyrene and POSS-SiO2 composite aerogel are the same as those in Example 1.

[0040] The preparation method of the above heat-insulating and heat-preserving material for a passive house:

[0041] Graft cellulose onto polystyrene, styrene-butadiene-styrene block copolymer, POSS-SiO2 composite aerogel, light calcium carbonate, silane coupling agent KH-550, monoglyceryl stearate, flame retardant, and AC blowing agent are added to a high-speed mixer and mixed for 10 - 30 min. The mixture is then added to a twin-screw extruder and heated to a molten state. The temperature of heating zone I - heating zone II of the twin-screw extruder is 150 - 155 °C, the temperature of heating zone III - heating zone IV is 155 - 165 °C, and the temperature of heating zone V - heating zone VI is 165 - 175 °C. After the carbon dioxide gas is heated and pressurized to the supercritical state through a supercritical fluid injection device, it is injected into the barrel of the twin-screw extruder and fully mixed with the melt in the twin-screw extruder to form a homogeneous melt. Subsequently, it is transported into a melt pump, depressurized at the die head, added to a mold, foamed at 115 °C for 10 min, and then cooled and shaped.

[0042] Example 3:

[0043] A thermal insulation material for a passive house is prepared from the following raw materials in parts by weight:

[0044] 40 parts of cellulose grafted polystyrene, 20 parts of styrene-butadiene-styrene block copolymer, 15 parts of POSS-SiO2 composite aerogel, 20 parts of light calcium carbonate, 1 part of silane coupling agent KH-550, 0.5 parts of stearic acid monoglyceride, 0.5 parts of pentaerythritol phosphate, 0.5 parts of methyl octabromoether, and 3 parts of AC foaming agent.

[0045] Wherein, the preparation method of cellulose grafted polystyrene and POSS-SiO2 composite aerogel is the same as that in Example 1.

[0046] Preparation method of the above passive house thermal insulation material:

[0047] Cellulose grafted polystyrene, styrene-butadiene-styrene block copolymer, POSS-SiO2 composite aerogel light calcium carbonate, silane coupling agent KH-550, stearic acid monoglyceride, flame retardant, AC foaming agent are added to a high-speed mixer and mixed for 10-30 minutes. The mixture is added to a twin-screw extruder and heated to a molten state. The temperature of the heating zone I-heating zone II of the twin-screw extruder is 150-155°C, the temperature of the heating zone III-heating zone IV is 155-165°C, and the temperature of the heating zone V-heating zone VI is 165-175°C. After the carbon dioxide gas is heated and pressurized to reach a supercritical state through a supercritical fluid injection device, it is injected into the barrel of the twin-screw extruder and fully mixed with the melt in the twin-screw extruder to form a homogeneous melt. The melt is then transported into a melt pump, the pressure is released at the die head, and the melt is added to a mold. After foaming at 115°C for 10 minutes, it is cooled and formed.

[0048] Embodiment 4:

[0049] A thermal insulation material for a passive house is prepared from the following raw materials in parts by weight:

[0050] 60 parts of cellulose grafted polystyrene, 20 parts of styrene-butadiene-styrene block copolymer, 25 parts of POSS-SiO2 composite aerogel, 20 parts of light calcium carbonate, 3 parts of silane coupling agent KH-550, 0.5 parts of stearic acid monoglyceride, 0.5 parts of pentaerythritol phosphate, 0.5 parts of methyl octabromoether, and 5 parts of AC foaming agent.

[0051] Wherein, the preparation method of cellulose grafted polystyrene and POSS-SiO2 composite aerogel is the same as that in Example 1.

[0052] Preparation method of the above passive house thermal insulation material:

[0053] Graft cellulose onto polystyrene, styrene-butadiene-styrene block copolymer, POSS-SiO2 composite aerogel, light calcium carbonate, silane coupling agent KH-550, monoglyceride stearate, flame retardant, and AC blowing agent were added to a high-speed mixer and mixed for 10 - 30 min. The mixture was then added to a twin-screw extruder and heated to a molten state. The temperature of heating zone I - heating zone II of the twin-screw extruder was 150 - 155 °C, the temperature of heating zone III - heating zone IV was 155 - 165 °C, and the temperature of heating zone V - heating zone VI was 165 - 175 °C. After the carbon dioxide gas was heated and pressurized to reach the supercritical state through a supercritical fluid injection device, it was injected into the barrel of the twin-screw extruder and fully mixed with the melt in the twin-screw extruder to form a homogeneous melt. Subsequently, it was transported into a melt pump, depressurized at the die head, added to a mold, foamed at 115 °C for 10 min, and then cooled and shaped.

[0054] Example 5:

[0055] A heat-insulating and heat-preserving material for a passive house is prepared from the following raw materials in parts by weight:

[0056] 40 parts of graft cellulose onto polystyrene, 30 parts of styrene-butadiene-styrene block copolymer, 15 parts of POSS-SiO2 composite aerogel, 30 parts of light calcium carbonate, 1 part of silane coupling agent KH-550, 1 part of monoglyceride stearate, 0.5 part of pentaerythritol phosphate, 0.5 part of methyl octabromide ether, and 3 parts of AC blowing agent.

[0057] Among them, the preparation methods of graft cellulose onto polystyrene and POSS-SiO2 composite aerogel are the same as those in Example 1.

[0058] The preparation method of the above heat-insulating and heat-preserving material for a passive house:

[0059] Graft cellulose onto polystyrene, styrene-butadiene-styrene block copolymer, POSS-SiO2 composite aerogel, light calcium carbonate, silane coupling agent KH-550, monoglyceride stearate, flame retardant, and AC blowing agent were added to a high-speed mixer and mixed for 10 - 30 min. The mixture was then added to a twin-screw extruder and heated to a molten state. The temperature of heating zone I - heating zone II of the twin-screw extruder was 150 - 155 °C, the temperature of heating zone III - heating zone IV was 155 - 165 °C, and the temperature of heating zone V - heating zone VI was 165 - 175 °C. After the carbon dioxide gas was heated and pressurized to reach the supercritical state through a supercritical fluid injection device, it was injected into the barrel of the twin-screw extruder and fully mixed with the melt in the twin-screw extruder to form a homogeneous melt. Subsequently, it was transported into a melt pump, depressurized at the die head, added to a mold, foamed at 115 °C for 10 min, and then cooled and shaped.

[0060] Comparative Example 1:

[0061] It is basically the same as Example 1, except that polystyrene is used to replace cellulose-grafted polystyrene.

[0062] Comparative Example 2:

[0063] It is basically the same as Example 1, except that styrene-butadiene-styrene block copolymer is not added.

[0064] Comparative Example 3:

[0065] It is basically the same as Example 1, except that POSS-SiO2 composite aerogel is not added.

[0066] Comparative Example 4:

[0067] It is basically the same as Example 1, except that commercially available SiO2 aerogel (Dongguan Chuangyi New Material Technology Co., Ltd.) is used to replace POSS-SiO2 composite aerogel.

[0068] Comparative Example 5:

[0069] It is basically the same as Example 1, except that silane coupling agent KH-550 is not added.

[0070] Performance Test:

[0071] The heat insulation and heat preservation materials prepared in Examples 1-5 and Comparative Examples 1-5 of the present invention were used as specimens for performance testing;

[0072] Density: Tested according to GB / T6343-2009, unit g / cm 3 ;

[0073] Tensile property test: Tested according to GB / T1040.1-2018, tensile rate 20mm / min, unit MPa;

[0074] Flexural property test: Tested according to GB / T 9341—2008, unit MPa;

[0075] Impact property test: Tested according to GB / T 1843—2008, unit KJ / m -2 ;

[0076] Flammability property test: LOI was tested according to GB / T2408-2008, unit %;

[0077] Thermal conductivity test: Tested according to GB / T10294-2008, unit W / (m·K);

[0078] Heat release rate (HRR) was tested according to ASTM D3801, unit kW / m 2 ;

[0079] The test results are shown in Table 1 below:

[0080] Table 1:

[0081]

[0082] As can be seen from Table 1 above, the heat-insulating and heat-preserving material prepared by the present invention has good mechanical properties, low thermal conductivity, excellent heat-insulating and heat-preserving performance, and also has certain fireproof and flame-retardant properties, and has a wide application prospect as a building decoration material for passive houses.

[0083] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A heat-insulating and heat-preserving material for a passive house, characterized in that, It is prepared from the following raw materials in parts by weight: 40 - 60 parts of cellulose grafted polystyrene, 20 - 30 parts of styrene-butadiene-styrene block copolymer, 15 - 25 parts of POSS-SiO2 composite aerogel, 20 - 30 parts of light calcium carbonate, 1 - 3 parts of silane coupling agent, 0.5 - 1 part of monoglyceride stearate, 1 - 3 parts of flame retardant, 3 - 5 parts of AC blowing agent; The preparation method of the cellulose grafted polystyrene is as follows: Add microcrystalline cellulose into imidazole-based ionic liquid, heat up to 70 - 85 °C and stir for 1 - 3 h, cool down to 0 - 5 °C, add bromoisobutyryl bromide and pyridine, react at 40 - 50 °C for 12 - 18 h, pour the reaction solution into ice water, separate the precipitated solid, vacuum dry to constant weight to obtain the intermediate. Under nitrogen protection, add the intermediate into 1,4-dioxane, stir to dissolve, then add styrene, pentamethyldiethylenetriamine and copper bromide, close and heat up to 75 - 85 °C and react for 3 - 5 h. After restoring to room temperature, add tetrahydrofuran into the reaction solution, stir for 30 - 50 min, then add absolute ethanol, separate the precipitated solid, and vacuum dry to constant weight; The preparation method of the POSS-SiO2 composite aerogel is as follows: Add POSS into ethanol, then add dilute hydrochloric acid solution, stir for 10 - 15 min, dissolve tetraethyl orthosilicate in ethanol, add it into the reaction solution, stir at room temperature for 8 - 15 h, then stand and age for 8 - 15 h, exchange with ethanol and acetone three times in sequence, and vacuum dry to constant weight; The POSS is tris(dimethylethenylsiloxy)-POSS.

2. The heat-insulating and heat-preserving material for passive houses according to claim 1, wherein It is prepared from the following raw materials in parts by weight: 60 parts of cellulose grafted polystyrene, 25 parts of styrene-butadiene-styrene block copolymer, 20 parts of POSS-SiO2 composite aerogel, 25 parts of light calcium carbonate, 2 parts of silane coupling agent, 0.8 part of monoglyceride stearate, 1 part of flame retardant, 3 parts of AC blowing agent.

3. The heat insulation and thermal insulation material for passive houses according to claim 1, characterized in that The imidazole-based ionic liquid is any one or more of 1-carboxymethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride.

4. The heat-insulating and heat-preserving material for passive houses according to claim 1, characterized in that The flame retardant is pentaerythritol phosphate and methyl octabromodiphenyl ether.

5. The heat-insulating and heat-preserving material for passive houses according to claim 4, wherein, The mass ratio of the pentaerythritol phosphate to the methyl octabromodiphenyl ether is 1 - 5:

1.

6. A method for preparing a heat-insulating and heat-preserving material for a passive house according to any one of claims 1-5, characterized in that, Add cellulose grafted polystyrene, styrene-butadiene-styrene block copolymer, POSS-SiO2 composite aerogel, light calcium carbonate, silane coupling agent, monoglyceride stearate, flame retardant, and AC blowing agent into a high-speed mixer and mix for 10 - 30 min. Add the mixture into a twin-screw extruder, heat to reach the molten state. After the carbon dioxide gas is heated and pressurized to reach the supercritical state through a supercritical fluid injection device, inject it into the barrel of the twin-screw extruder, fully mix with the melt in the twin-screw extruder to form a homogeneous melt, then transport it into a melt pump, depressurize at the die head of the extruder, add it into the mold, and cool and shape after foaming.

7. The preparation method of the heat-insulating and heat-preserving material for passive houses according to claim 6, characterized in that, The temperature of the heating zone I - heating zone II of the twin-screw extruder is 150 - 155 °C, the temperature of the heating zone III - heating zone IV is 155 - 165 °C, and the temperature of the heating zone V - heating zone VI is 165 - 175 °C.

Images