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WO2024216430A1 - Method for preparing aerogel modified gypsum - Google Patents

Method for preparing aerogel modified gypsum Download PDF

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Publication number
WO2024216430A1
WO2024216430A1 PCT/CN2023/088650 CN2023088650W WO2024216430A1 WO 2024216430 A1 WO2024216430 A1 WO 2024216430A1 CN 2023088650 W CN2023088650 W CN 2023088650W WO 2024216430 A1 WO2024216430 A1 WO 2024216430A1
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WO
WIPO (PCT)
Prior art keywords
aerogel
gypsum
parts
mass
preparation
Prior art date
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PCT/CN2023/088650
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French (fr)
Chinese (zh)
Inventor
白元宇
王渝徽
刘超
朱力伟
解洪兴
何新
Original Assignee
中科润资(重庆)气凝胶技术研究院有限公司
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Priority to PCT/CN2023/088650 priority Critical patent/WO2024216430A1/en
Publication of WO2024216430A1 publication Critical patent/WO2024216430A1/en

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  • the invention belongs to the technical field of building thermal insulation and relates to a method for preparing aerogel modified gypsum.
  • Gypsum is a widely used building insulation material, and optimizing its thermal insulation performance meets the current needs of green and sustainable development.
  • Aerogel is a lightweight solid material with a three-dimensional network structure, nano-scale skeleton and pores. It has the advantages of large specific surface area, high porosity, low density, and extremely low thermal conductivity, and can improve the performance of traditional thermal insulation materials.
  • the main methods currently used include increasing the stirring time, changing the mixing ratio, etc., but most of the existing methods can only improve the mixing of aerogel powder particles in gypsum slurry, and cannot effectively achieve uniform mixing.
  • the present invention provides the following technical solutions:
  • a method for preparing aerogel-modified gypsum comprises: mixing aerogel with raw materials and auxiliary materials of gypsum under vacuum stirring conditions, and then adding an air entraining agent under normal pressure conditions to mix uniformly to obtain the aerogel-modified gypsum.
  • the conditions for vacuum stirring specifically include: stirring under an absolute pressure of less than 1 KPa; the stirring time is no more than 5 minutes; and the stirring temperature is 8°C to 10°C.
  • the aerogel is added into the raw materials of gypsum.
  • the raw material of the gypsum is selected from plaster of Paris.
  • the mass ratio of aerogel to gypsum is (0-30):100 and the content of the aerogel is not zero.
  • the particle size of the aerogel is 1 nm-50 nm.
  • the aerogel is selected from hydrophilically modified aerogels and/or hydrophobic aerogels.
  • the aerogel includes hydrophilic modified aerogel and hydrophobic aerogel, wherein the mass ratio of hydrophilic modified aerogel to hydrophobic aerogel is 100:(0-100) and the content of the hydrophobic aerogel is not zero.
  • the mass ratio of the hydrophilic modified aerogel to the hydrophobic aerogel is 100:(20-50).
  • the hydrophilically modified aerogel is a hydrophilically modified aerogel particle.
  • the contact angle between the hydrophilic modified aerogel and water is less than 90°.
  • the contact angle between the hydrophobic aerogel and water is greater than 90°.
  • the auxiliary material includes water, and at least one of the following substances: vitrified microspheres, a reinforcing agent, a dispersant, reinforcing fibers, and a retarder.
  • the auxiliary material is added in an amount of 0.1 to 200 parts by mass per 100 parts by mass of the gypsum raw material.
  • the water is 100 to 120 parts by mass per 100 parts by mass of the raw material of gypsum.
  • the dispersant is in an amount of 0.01 to 5 parts by mass per 100 parts by mass of the gypsum raw material.
  • the dispersant is selected from polyoxyethylene dioleate, tetraethylene glycol monostearate, tetraethylene glycol monooleate, polyoxypropylene mannitol dioleate, polyoxyethylene sorbitol lanolin oleic acid derivatives, polyoxyethylene sorbitol lanolin derivatives, polyoxypropylene stearate, polyoxyethylene Ethylene (5EO) lanolin ether, sorbitan laurate, polyoxyethylene fatty acid, polyoxyethylene oxypropylene oleate, triethylhexyl phosphoric acid, sodium lauryl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide, guar gum, fatty acid polyethylene glycol esters.
  • the amount of the vitrified microspheres is 5 to 40 parts by mass per 100 parts by mass of the gypsum raw material.
  • the reinforcing fibers are selected from inorganic fibers and organic fibers.
  • the reinforcing fibers are short fibers, specifically fibers with a length of 3 mm to 60 mm.
  • the reinforcing fiber is present in an amount of 0.5-5 parts by mass per 100 parts by mass of the gypsum raw material.
  • the retarder is selected from organic acids and soluble salts thereof, alkaline phosphates, proteins and other retarders.
  • the retarder is 0.01-0.5 parts by mass per 100 parts by mass of the gypsum raw material.
  • the raw materials, auxiliary materials and aerogel of gypsum are premixed to obtain a uniform premix.
  • the temperature during premixing is controlled at 8°C to 10°C.
  • the mass ratio of the air entraining agent to the gypsum raw material is 0.1 to 1:100.
  • the present invention proposes a method for preparing aerogel-modified gypsum, wherein vacuum stirring is first performed, and then an air entraining agent is added and stirred under normal pressure, which effectively overcomes the problem of reduced air entraining agent effect caused by the introduction of vacuum stirring in the prior art.
  • the method of the present invention can fully exert the function of the air entraining agent while achieving a better mixing effect, and prepares a gypsum with significantly improved thermal insulation effect and strength.
  • the present invention further introduces hydrophilic modified aerogel, which is easier to mix with gypsum slurry.
  • the hydrophilic modified aerogel has better thermal insulation performance.
  • the present invention Ming also proposed a solution of mixing hydrophilic modified aerogel with hydrophobic aerogel, which can maintain the strength without reducing the thermal insulation performance. That is, the mixed aerogel has better thermal insulation performance and the strength of gypsum does not decrease much. After adding hydrophobic aerogel as an additive, the dispersibility of gypsum slurry can also be improved.
  • FIG1 is a schematic diagram of a preparation process of an aerogel thermal insulation gypsum according to the present invention.
  • FIG. 2 is a schematic diagram of the preparation process of another aerogel thermal insulation gypsum of the present invention.
  • the present invention provides a method for preparing aerogel-modified gypsum, which comprises: mixing aerogel with raw materials and auxiliary materials of gypsum under vacuum stirring conditions, and then adding an air entraining agent under normal pressure conditions to mix evenly to obtain the aerogel-modified gypsum.
  • vacuum stirring is first performed, and then the air entraining agent is added and stirred under normal pressure conditions, so as to achieve a better mixing effect and fully exert the function of the air entraining agent, and prepare a gypsum with significantly improved thermal insulation effect and strength.
  • the conditions for vacuum stirring specifically include: stirring under an absolute pressure of less than 1 KPa; the stirring time is no more than 5 minutes; and the stirring temperature is 8°C to 10°C.
  • the aerogel is added to the raw material of gypsum.
  • the aerogel can be added in multiple times to shorten the vacuum stirring time.
  • the number of additions can be selected according to actual conditions, for example, adding in 2-10 times.
  • the raw material of the gypsum is selected from gypsum powder (e.g., semi-hydrated gypsum powder).
  • gypsum powder e.g., semi-hydrated gypsum powder
  • the purity of the gypsum powder is at least greater than 90%, such as 95% or 98%.
  • the gypsum powder has a relatively high fineness, such as 100-120 mesh.
  • the mass ratio of aerogel to gypsum is (0-30):100 and the content of aerogel is not 0, for example, 5:100, 10:100, 15:100, 20:100, 25:100, 30:100.
  • the particle size of the aerogel is 1 nm-50 nm, preferably 20 nm-50 nm, for example, 1 nm, 10 nm, 20 nm, 30 nm, 40 nm or 50 nm.
  • the aerogel is selected from hydrophilically modified aerogels and/or hydrophobic aerogels.
  • hydrophilic modified aerogel when added, it is easier to mix with gypsum slurry. In addition, compared with untreated hydrophobic aerogel, the thermal insulation performance of hydrophilic modified aerogel is better.
  • the aerogel includes hydrophilic modified aerogel and hydrophobic aerogel, wherein the mass ratio of hydrophilic modified aerogel to hydrophobic aerogel is 100:(0-100) and the content of the hydrophobic aerogel is not zero.
  • the mass ratio of the hydrophilic modified aerogel to the hydrophobic aerogel is 100:(20-50), for example, 100:5, 100:10, 100:20, 100:30, 100:40, 100:60, 100:70, 100:80, 100:90.
  • the mass ratio of the hydrophobic aerogel to the hydrophilic modified aerogel is within the above range, the thermal insulation performance of the thermal insulation gypsum can be guaranteed and the mechanical strength of the thermal insulation gypsum can be maintained.
  • the hydrophilically modified aerogel is a hydrophilically modified aerogel particle.
  • the contact angle between the hydrophilic modified aerogel and water is less than 90°.
  • the surface of the hydrophilic modified aerogel contains hydrophilic groups, and the hydrophilic groups are selected from groups known in the art, such as hydroxyl groups (-OH).
  • the contact angle between the hydrophobic aerogel and water is greater than 90°.
  • the surface of the hydrophobic aerogel contains hydrophobic groups, and the hydrophobic groups are selected from groups known in the art, such as alkoxy groups (-OR, R represents an alkyl group).
  • the auxiliary material includes water and at least one of the following substances: glass
  • the auxiliary materials include water, vitrified microspheres, a reinforcing agent, a dispersant, a reinforcing fiber and a retarder.
  • the auxiliary material is added in an amount of 0.1 to 200 parts by mass per 100 parts by mass of the gypsum raw material.
  • the amount of water is 100 to 120 parts by mass, for example, 105 parts by mass, 110 parts by mass, 115 parts by mass, or 120 parts by mass, per 100 parts by mass of the gypsum raw material.
  • the dispersant can improve the fluidity of the product during molding and processing; it does not affect the performance of the product, and is non-toxic and reasonably priced.
  • the dispersant is 0.01-5 parts by mass, for example, 0.1 parts by mass, 0.5 parts by mass, 1 parts by mass, 2 parts by mass, 3 parts by mass, or 4 parts by mass, per 100 parts by mass of the gypsum raw material.
  • the dispersant is selected from polyoxyethylene dioleate, tetraethylene glycol monostearate, tetraethylene glycol monooleate, polyoxypropylene mannitol dioleate, polyoxyethylene sorbitol lanolin oleic acid derivatives, polyoxyethylene sorbitol lanolin derivatives, polyoxypropylene stearate, polyoxyethylene (5EO) lanolin ether, sorbitan laurate, polyoxyethylene fatty acid, polyoxyethylene oxypropylene oleate, triethylhexyl phosphoric acid, sodium lauryl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide, gur gum, fatty acid polyethylene glycol esters, preferably polyoxypropylene stearate and polyoxyethylene dioleate.
  • the amount of the vitrified microspheres is 5 to 40 parts by weight, for example, 10 parts by weight, 20 parts by weight, 30 parts by weight, or 40 parts by weight, per 100 parts by weight of the gypsum raw material.
  • the vitrified microspheres may be selected from materials known in the art, and are not specifically limited in the present invention.
  • the reinforcing fiber is selected from inorganic fibers and organic fibers, such as polyester fibers, glass fibers, basalt fibers, etc.
  • the reinforcing fiber should be short fibers, specifically fibers with a length of 3 mm to 60 mm, such as 10 mm, 20 mm, 30 mm, 40 mm, 50 mm.
  • the reinforcing fiber is 0.5-5 parts by weight, for example, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, or 0.9 parts by weight, per 100 parts by weight of the gypsum raw material.
  • the reinforcing fibers are used as skeleton filling materials to increase the strength of the aerogel-modified gypsum.
  • the retarder is selected from organic acids and soluble salts thereof, alkaline phosphates and proteins.
  • the retarder is selected from citric acid, sodium citrate, tartaric acid, potassium tartrate, acrylic acid and sodium acrylate, sodium hexametaphosphate, sodium polyphosphate, borax, sodium borate, sodium tripolyphosphate, sodium gluconate, preferably citric acid, tartaric acid, sodium gluconate.
  • the retarder can prolong the stirring time, increase the paste-water ratio, and improve the strength of the finished product.
  • the retarder is 0.01-0.5 parts by mass, for example, 0.05 parts by mass, 0.1 parts by mass, 0.2 parts by mass, 0.3 parts by mass, or 0.4 parts by mass, per 100 parts by mass of the gypsum raw material.
  • the raw materials, auxiliary materials and aerogel of gypsum can also be premixed to obtain a uniform premix.
  • the temperature during premixing is controlled at 8°C to 10°C, the purpose of which is to reduce the dissolution rate of hemihydrate gypsum in water, prolong the dissolution time of the raw materials of gypsum in water and the crystal nucleus formation time, that is, to slow down the reaction rate of the raw materials of gypsum and water.
  • the mass ratio of the air entraining agent to the gypsum raw material is 0.1 to 1:100, for example, 0.1:100 or 0.5:100.
  • the inventors have found that adding the air entraining agent and stirring evenly can improve the fluidity and cohesiveness of the mixture.
  • the air entraining agent can be selected from air entraining agents known in the art, for example, selected from rosin resin air entraining agents, alkylbenzene sulfonate air entraining agents, and fatty alcohol sulfonate air entraining agents.
  • the air entraining agent can be selected from at least one of sodium dodecyl sulfate, sodium rosin acid, triterpenoid saponin, and sodium ⁇ -olefin sulfonate.
  • the vacuum stirring and stirring are respectively carried out in a high-speed stirring device.
  • the high-speed stirring device can be a high-speed magnetic stirrer, a self-falling stirrer or a forced stirrer.
  • hardening and curing can be further performed.
  • the curing can be performed by methods known in the art.
  • the maintenance includes: first natural maintenance, then enhanced maintenance.
  • the natural curing refers to curing at 0-40°C for 12-36 hours.
  • the enhanced curing refers to: the ambient temperature is 30-50°C (preferably 40°C); the humidity is not more than 90% (preferably 10%, 20%, 50%, 70%, 80%); the curing time is 48h-72h.
  • the present invention also provides aerogel modified gypsum obtained by the preparation method.
  • the thermal conductivity of the aerogel-modified gypsum is not higher than 0.25w/(m.k), for example, 0.2w/(m.k), 0.1w/(m.k), 0.07w/(m.k), or 0.05w/(m.k).
  • the compressive strength of the aerogel-modified gypsum is 1 to 10 MPa, for example, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, or 9 MPa.
  • Plaster of Paris powder commercially available gypsum powder (calcium sulfate hemihydrate) may be used, and the content (purity) of CaSO 4 ⁇ 0.5H 2 O is greater than 90%, preferably greater than 98%.
  • the reinforcing fiber includes at least one of glass fiber, polypropylene fiber and polyester fiber.
  • the reinforcing fiber can improve the anti-cracking performance of the thermal insulation gypsum and increase the tensile strength.
  • Vitrified microspheres particle size is 100 ⁇ m ⁇ 300 ⁇ m.
  • Hydrophobic aerogel Zhongke Runzi Technology Co., Ltd., brand RZF500 or RZF1000.
  • Dispersant polyoxyethylene oleate, Polyshun Chemical.
  • Hydrophilic modification method 1 Take the above hydrophobic aerogel (Zhongke Runzi Technology Co., Ltd., brand RZF500 or RZF1000), treat it at high temperature of 200-350°C for 1-10 minutes to obtain a hydrophilic Modified aerogel.
  • Hydrophilic modification method 2 Take the above hydrophobic aerogel (Zhongke Runzi Technology Co., Ltd., brand RZF500 or RZF1000), impregnate it with ethanol and dry it to obtain a hydrophilic modified aerogel; it can be naturally dried or heated and dried.
  • the conditions for heating and drying are: high temperature 90-110°C, treatment for 1-10 minutes.
  • the performance of the hydrophilic modified aerogel prepared in Preparation Example 2 is basically equivalent to that in Preparation Example 1, and both hydrophilic modification methods can achieve the hydrophilic modification effect.
  • A. Preparation of mixed aerogel mixing hydrophilic modified aerogel and hydrophobic modified aerogel in proportion to obtain aerogel; wherein the mixed aerogel comprises the hydrophilic modified aerogel of Preparation Example 1 and commercially available hydrophobic aerogel, and the mass ratio of the two is 1:1;
  • step A The aerogel obtained in step A is pre-mixed with gypsum powder, water, auxiliary materials and aerogel, and then stirred in a mixer to obtain gypsum slurry;
  • the specific preparation method is as follows (the following parts are all parts by mass):
  • auxiliary materials include: 0.2 parts of retarder citric acid, 1 part of dispersant, 10 parts of vitrified microspheres, and 1 part of reinforcing fiber glass fiber;
  • Vacuum stirring add 100-120 parts of water to the dry powder mixture of step 2), the water temperature is 8-10°C, and evacuate to an absolute pressure of less than 1KPa, and perform vacuum stirring under vacuum condition for 2 minutes to obtain slurry A;
  • the preparation method of the thermal insulation gypsum of this embodiment is basically the same as that of Embodiment 1, except that in step 2), the mixed aerogel is 5 parts, of which the hydrophilic modified aerogel is added in an amount of 3.33 parts, that is, the mass ratio of the hydrophilic modified aerogel to the hydrophobic aerogel is 2:1.
  • the preparation method of the thermal insulation gypsum of this embodiment is basically the same as that of Embodiment 1, except that in step 2), the mixed aerogel is 10 parts, of which 5 parts are added in the amount of hydrophilic modified aerogel, and the mass ratio of hydrophilic modified aerogel to hydrophobic aerogel is 1:1.
  • the preparation method of the thermal insulation gypsum of this embodiment is basically the same as that of Embodiment 2, except that in step 2), the mixed aerogel is 10 parts, of which the added amount of hydrophilic modified aerogel is 6.67 parts, and the mass ratio of hydrophilic modified aerogel to hydrophobic aerogel is 2:1.
  • the preparation method of the thermal insulation gypsum of this embodiment is basically the same as that of Embodiment 1, except that in step 2), the mixed aerogel is 20 parts, of which the hydrophilic modified aerogel is added in an amount of 10 parts, and the mass ratio of the hydrophilic modified aerogel to the hydrophobic aerogel is 1:1.
  • the preparation method of the thermal insulation gypsum of this embodiment is basically the same as that of Embodiment 3, except that in step 2), the mixed aerogel is 20 parts, of which the added amount of hydrophilic modified aerogel is 13.33 parts, and the mass ratio of hydrophilic modified aerogel to hydrophobic aerogel is 2:1.
  • the preparation method of the thermal insulation gypsum of this embodiment is basically the same as that of Embodiment 1, except that in step 2), the mixed aerogel is 15 parts, of which the hydrophilic modified aerogel is added in an amount of 7.5 parts, and the mass ratio of the hydrophilic modified aerogel to the hydrophobic aerogel is 1:1.
  • the preparation method of the thermal insulation gypsum of this embodiment is basically the same as that of Embodiment 4, except that in step 2), the mixed aerogel is 15 parts, of which the hydrophilic modified aerogel is added in an amount of 10 parts, and the mass ratio of the hydrophilic modified aerogel to the hydrophobic aerogel is 2:1.
  • the preparation method of the thermal insulation gypsum of this embodiment is basically the same as that of Embodiment 1, except that in step 2), the mixed aerogel is 25 parts, of which the hydrophilic modified aerogel is added in an amount of 12.5 parts, and the mass ratio of the hydrophilic modified aerogel to the hydrophobic aerogel is 1:1.
  • the preparation method of the thermal insulation gypsum of this embodiment is basically the same as that of Embodiment 5, except that in step 2), the mixed aerogel is 25 parts, of which the hydrophilic modified aerogel is added in an amount of 16.7 parts, and the mass ratio of the hydrophilic modified aerogel to the hydrophobic aerogel is 2:1.
  • the preparation method of the thermal insulation gypsum of this embodiment is basically the same as that of Example 1, except that only the hydrophilic modified aerogel of Preparation Example 1 is used in step A;
  • step B step 2) uses the hydrophilic modified aerogel of Preparation Example 1.
  • the preparation method of the thermal insulation gypsum of this embodiment is basically the same as that of Embodiment 1, except that only commercially available hydrophobic aerogel is used in step A;
  • step B step 2) uses commercially available hydrophobic aerogel.
  • This comparative example is basically the same as Example 2, except that:
  • step 3 0.2 parts of an air entraining agent, sodium dodecyl sulfate, was also added, and no vacuum operation was performed. The mixture was directly stirred at normal pressure for 5 minutes to obtain slurry B.
  • This comparative example is basically the same as Example 2-1, except that:
  • step 3 0.2 parts of an air entraining agent, sodium dodecyl sulfate, was also added, and no vacuum operation was performed. The mixture was directly stirred at normal pressure for 5 minutes to obtain slurry B.
  • This comparative example is basically the same as Example 2, except that in step 2), only hydrophilic modified aerogel is used, and the addition amount thereof is 10 parts.
  • step 3 0.2 parts of an air entraining agent, sodium dodecyl sulfate, was also added, and no vacuum operation was performed. The mixture was directly stirred at normal pressure for 5 minutes to obtain slurry B.
  • This comparative example is basically the same as Example 2, except that in step 2), only hydrophobic aerogel is used, and the addition amount thereof is 10 parts.
  • step 3 0.2 parts of an air entraining agent, sodium dodecyl sulfate, was also added, and no vacuum operation was performed. The mixture was directly stirred at normal pressure for 5 minutes to obtain slurry B.

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Abstract

Disclosed is a method for preparing aerogel modified gypsum. The preparation method of the present invention comprises: mixing aerogel with gypsum raw materials and auxiliary materials while vacuum stirring, then adding an air entraining agent under normal-pressure conditions, and uniformly mixing to obtain an aerogel modified gypsum. By first performing vacuum stirring and then adding the air entraining agent and stirring under normal pressure, the present invention effectively overcomes the problem in the prior art whereby the the effect of the air entraining agent is reduced due to introduction during vacuum stirring. The method of the present invention achieves a better mixing effect while maximizing the function of the air entraining agent, and prepares a gypsum having significantly improved thermal insulation and strength.

Description

一种气凝胶改性石膏的制备方法A method for preparing aerogel modified gypsum 技术领域Technical Field
本发明属于建筑保温隔热技术领域，涉及一种气凝胶改性石膏的制备方法。The invention belongs to the technical field of building thermal insulation and relates to a method for preparing aerogel modified gypsum.
背景技术Background Art
随着人们对绿色节能的环保建筑的需求持续提高，而建筑保温材料属于建筑节能的主要研究方向之一。石膏是作为一种广泛应用的建筑保温材料，优化其隔热性能符合当前绿色可持续发展的需求。As people's demand for green and energy-saving environmentally friendly buildings continues to increase, building insulation materials are one of the main research directions for building energy conservation. Gypsum is a widely used building insulation material, and optimizing its thermal insulation performance meets the current needs of green and sustainable development.
气凝胶是一种具有三维网状结构，骨架和孔洞均为纳米级的轻质固态材料。具有比表面积大、孔隙率高、密度小、导热系数极低等优势，可提升传统保温材料的性能。Aerogel is a lightweight solid material with a three-dimensional network structure, nano-scale skeleton and pores. It has the advantages of large specific surface area, high porosity, low density, and extremely low thermal conductivity, and can improve the performance of traditional thermal insulation materials.
一些现有技术尝试将气凝胶加入石膏中，以提高石膏的隔热保温性能，但是气凝胶粉极轻，在混合过程中会悬浮在石膏浆料上方，不易混合。亟需开发一种方法以实现气凝胶的有效添加，以期获得一种隔热和强度性能俱佳的改性石膏。Some existing technologies attempt to add aerogel to gypsum to improve the thermal insulation performance of gypsum, but aerogel powder is extremely light and will float above the gypsum slurry during the mixing process, making it difficult to mix. It is urgent to develop a method to achieve effective addition of aerogel in order to obtain a modified gypsum with excellent thermal insulation and strength properties.
为解决气凝胶粉与石膏不易混合的问题，目前主要运用的方法包括增加搅拌时长、改变混合比例等，但现有方法大多只能改善气凝胶粉粒在石膏浆料中的混合情况，无法有效实现混合均匀。To solve the problem that aerogel powder and gypsum are difficult to mix, the main methods currently used include increasing the stirring time, changing the mixing ratio, etc., but most of the existing methods can only improve the mixing of aerogel powder particles in gypsum slurry, and cannot effectively achieve uniform mixing.
发明内容Summary of the invention
为解决上述技术问题，本发明提供如下技术方案：In order to solve the above technical problems, the present invention provides the following technical solutions:
一种气凝胶改性石膏的制备方法，所述制备方法包括：将气凝胶与石膏的原料、辅料在真空搅拌的条件下混合后，再在常压条件下加入引气剂混合均匀，得到所述气凝胶改性石膏。A method for preparing aerogel-modified gypsum comprises: mixing aerogel with raw materials and auxiliary materials of gypsum under vacuum stirring conditions, and then adding an air entraining agent under normal pressure conditions to mix uniformly to obtain the aerogel-modified gypsum.
根据本发明的实施方案，真空搅拌的条件具体包括：在绝对压强小于1KPa的条件下，进行搅拌；搅拌时间为不大于5min；搅拌温度为8℃～10℃。 According to an embodiment of the present invention, the conditions for vacuum stirring specifically include: stirring under an absolute pressure of less than 1 KPa; the stirring time is no more than 5 minutes; and the stirring temperature is 8°C to 10°C.
根据本发明的实施方案，气凝胶的添加方式是将所述气凝胶加入石膏的原料中。According to an embodiment of the present invention, the aerogel is added into the raw materials of gypsum.
根据本发明的实施方案，所述石膏的原料选自熟石膏粉。According to an embodiment of the present invention, the raw material of the gypsum is selected from plaster of Paris.
根据本发明的实施方案，所述气凝胶改性石膏中，气凝胶与石膏的质量比为(0～30):100且所述气凝胶的含量不为0。According to an embodiment of the present invention, in the aerogel-modified gypsum, the mass ratio of aerogel to gypsum is (0-30):100 and the content of the aerogel is not zero.
根据本发明的实施方案，所述气凝胶改性石膏中，气凝胶的粒径为1nm-50nm。According to an embodiment of the present invention, in the aerogel-modified gypsum, the particle size of the aerogel is 1 nm-50 nm.
根据本发明的实施方案，气凝胶选自亲水改性气凝胶和/或疏水气凝胶。According to an embodiment of the present invention, the aerogel is selected from hydrophilically modified aerogels and/or hydrophobic aerogels.
根据本发明的优选方案，所述气凝胶包括亲水改性气凝胶和疏水气凝胶，其中，亲水改性气凝胶与疏水气凝胶的质量比为100:(0～100)且所述疏水气凝胶的含量不为0。According to a preferred embodiment of the present invention, the aerogel includes hydrophilic modified aerogel and hydrophobic aerogel, wherein the mass ratio of hydrophilic modified aerogel to hydrophobic aerogel is 100:(0-100) and the content of the hydrophobic aerogel is not zero.
优选地，所述亲水改性气凝胶与疏水气凝胶的质量比为100:(20～50)。Preferably, the mass ratio of the hydrophilic modified aerogel to the hydrophobic aerogel is 100:(20-50).
根据本发明的实施方案，所述亲水改性气凝胶是一种亲水改性气凝胶颗粒。According to an embodiment of the present invention, the hydrophilically modified aerogel is a hydrophilically modified aerogel particle.
根据本发明的实施方案，所述亲水改性气凝胶与水的接触角小于90°。According to an embodiment of the present invention, the contact angle between the hydrophilic modified aerogel and water is less than 90°.
根据本发明的实施方案，所述疏水气凝胶与水的接触角大于90°。According to an embodiment of the present invention, the contact angle between the hydrophobic aerogel and water is greater than 90°.
根据本发明的实施方案，所述辅料包括水，和下述物质中的至少一种：玻化微珠、增强剂、分散剂、增强纤维和缓凝剂。According to an embodiment of the present invention, the auxiliary material includes water, and at least one of the following substances: vitrified microspheres, a reinforcing agent, a dispersant, reinforcing fibers, and a retarder.
根据本发明的实施方案，以每100质量份石膏的原料计，所述辅料的添加量为0.1～200质量份。According to an embodiment of the present invention, the auxiliary material is added in an amount of 0.1 to 200 parts by mass per 100 parts by mass of the gypsum raw material.
根据本发明的实施方案，以每100质量份石膏的原料计，水为100～120质量份。According to an embodiment of the present invention, the water is 100 to 120 parts by mass per 100 parts by mass of the raw material of gypsum.
根据本发明的实施方案，以每100质量份石膏的原料计，所述分散剂为0.01-5质量份。According to an embodiment of the present invention, the dispersant is in an amount of 0.01 to 5 parts by mass per 100 parts by mass of the gypsum raw material.
根据本发明的实施方案，所述分散剂选自聚氧乙烯二油酸酯、四乙二醇单硬脂酸酯、四乙二醇单油酸酯、聚氧丙烯甘露醇二油酸酯、聚氧乙烯山梨醇羊毛脂油酸衍生物、聚氧乙烯山梨醇羊毛脂衍生物、聚氧丙烯硬脂酸酯、聚氧乙 烯(5EO)羊毛醇醚、失水山梨醇月桂酸酯、聚氧乙烯脂肪酸、聚氧乙烯氧丙烯油酸酯、三乙基己基磷酸、十二烷基硫酸钠、甲基戊醇、纤维素衍生物、聚丙烯酰胺、古尔胶、脂肪酸聚乙二醇酯。According to an embodiment of the present invention, the dispersant is selected from polyoxyethylene dioleate, tetraethylene glycol monostearate, tetraethylene glycol monooleate, polyoxypropylene mannitol dioleate, polyoxyethylene sorbitol lanolin oleic acid derivatives, polyoxyethylene sorbitol lanolin derivatives, polyoxypropylene stearate, polyoxyethylene Ethylene (5EO) lanolin ether, sorbitan laurate, polyoxyethylene fatty acid, polyoxyethylene oxypropylene oleate, triethylhexyl phosphoric acid, sodium lauryl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide, guar gum, fatty acid polyethylene glycol esters.
根据本发明的实施方案，以每100质量份石膏的原料计，所述玻化微珠为5～40质量份。According to an embodiment of the present invention, the amount of the vitrified microspheres is 5 to 40 parts by mass per 100 parts by mass of the gypsum raw material.
根据本发明的实施方案，所述增强纤维选自无机纤维和有机纤维。优选地，所述增强纤维应为短纤维，具体为纤维的长度为3mm-60mm。According to an embodiment of the present invention, the reinforcing fibers are selected from inorganic fibers and organic fibers. Preferably, the reinforcing fibers are short fibers, specifically fibers with a length of 3 mm to 60 mm.
根据本发明的实施方案，以每100质量份石膏的原料计，所述增强纤维为0.5-5质量份。According to an embodiment of the present invention, the reinforcing fiber is present in an amount of 0.5-5 parts by mass per 100 parts by mass of the gypsum raw material.
根据本发明的实施方案，所述缓凝剂选自有机酸及其可溶盐、碱性磷酸盐以及蛋白质类等缓凝剂。According to an embodiment of the present invention, the retarder is selected from organic acids and soluble salts thereof, alkaline phosphates, proteins and other retarders.
根据本发明的实施方案，以每100质量份石膏的原料计，所述缓凝剂为0.01-0.5质量份。According to an embodiment of the present invention, the retarder is 0.01-0.5 parts by mass per 100 parts by mass of the gypsum raw material.
根据本发明的实施方案，在所述真空搅拌前，石膏的原料、辅料和气凝胶还进行预混合以得到均匀预混料。优选地，预混合时温度控制在8℃～10℃。According to an embodiment of the present invention, before the vacuum stirring, the raw materials, auxiliary materials and aerogel of gypsum are premixed to obtain a uniform premix. Preferably, the temperature during premixing is controlled at 8°C to 10°C.
根据本发明的实施方案，所述引气剂与所述石膏的原料的质量比为0.1～1：100。According to an embodiment of the present invention, the mass ratio of the air entraining agent to the gypsum raw material is 0.1 to 1:100.
有益效果Beneficial Effects
1、本发明提出了一种气凝胶改性石膏的制备方法，本发明中先进行真空搅拌，然后加入引气剂在常压条件下进行搅拌，有效克服了现有技术中因真空搅拌的引入而导致的引气剂效果降低的问题。本发明的方法在达到较好的混合效果的同时还能完全发挥引气剂的功能，制备得到了一种兼具显著提高的保温效果和强度的石膏。1. The present invention proposes a method for preparing aerogel-modified gypsum, wherein vacuum stirring is first performed, and then an air entraining agent is added and stirred under normal pressure, which effectively overcomes the problem of reduced air entraining agent effect caused by the introduction of vacuum stirring in the prior art. The method of the present invention can fully exert the function of the air entraining agent while achieving a better mixing effect, and prepares a gypsum with significantly improved thermal insulation effect and strength.
2、本发明进一步引入了亲水改性气凝胶，其更容易与石膏浆料混合，另外，相比于未处理的疏水气凝胶，亲水改性气凝胶的保温性能更优。2. The present invention further introduces hydrophilic modified aerogel, which is easier to mix with gypsum slurry. In addition, compared with untreated hydrophobic aerogel, the hydrophilic modified aerogel has better thermal insulation performance.
3、为了解决石膏中加入亲水改性气凝胶会带来石膏强度降低的问题，本发 明还提出了亲水改性气凝胶与疏水气凝胶混合使用的方案，在保持保温性能的前提下，保持强度不降低，即混合添加的气凝胶，既拥有较好的保温性能提升，石膏的强度下降不多；且加入疏水气凝胶作为添加料后，还可以提高石膏浆料的分散性。3. In order to solve the problem that adding hydrophilic modified aerogel to gypsum will reduce the strength of gypsum, the present invention Ming also proposed a solution of mixing hydrophilic modified aerogel with hydrophobic aerogel, which can maintain the strength without reducing the thermal insulation performance. That is, the mixed aerogel has better thermal insulation performance and the strength of gypsum does not decrease much. After adding hydrophobic aerogel as an additive, the dispersibility of gypsum slurry can also be improved.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本发明的一种气凝胶保温石膏的制备流程示意图。FIG1 is a schematic diagram of a preparation process of an aerogel thermal insulation gypsum according to the present invention.
图2为本发明的另一种气凝胶保温石膏的制备流程示意图。FIG. 2 is a schematic diagram of the preparation process of another aerogel thermal insulation gypsum of the present invention.
具体实施方式DETAILED DESCRIPTION
如前所述，本发明提供了一种气凝胶改性石膏的制备方法，所述制备方法包括：将气凝胶与石膏的原料、辅料在真空搅拌的条件下混合后，再在常压条件下加入引气剂混合均匀，得到所述气凝胶改性石膏。As mentioned above, the present invention provides a method for preparing aerogel-modified gypsum, which comprises: mixing aerogel with raw materials and auxiliary materials of gypsum under vacuum stirring conditions, and then adding an air entraining agent under normal pressure conditions to mix evenly to obtain the aerogel-modified gypsum.
发明人发现，虽然真空搅拌可以降低气凝胶飞溅的问题，但真空搅拌导致引气剂效果降低的问题。因此，本发明中先进行真空搅拌，然后在常压条件下加入引气剂并进行搅拌，从而达到较好的混合效果的同时还能完全发挥引气剂的功能，制备得到了一种兼具显著提高的保温效果和强度的石膏。The inventors found that although vacuum stirring can reduce the problem of aerogel splashing, vacuum stirring leads to a problem of reduced effect of air entraining agent. Therefore, in the present invention, vacuum stirring is first performed, and then the air entraining agent is added and stirred under normal pressure conditions, so as to achieve a better mixing effect and fully exert the function of the air entraining agent, and prepare a gypsum with significantly improved thermal insulation effect and strength.
根据本发明的实施方案，真空搅拌的条件具体包括：在绝对压强小于1KPa的条件下，进行搅拌；搅拌时间为不大于5min；搅拌温度为8℃～10℃。According to an embodiment of the present invention, the conditions for vacuum stirring specifically include: stirring under an absolute pressure of less than 1 KPa; the stirring time is no more than 5 minutes; and the stirring temperature is 8°C to 10°C.
根据本发明的实施方案，气凝胶的添加方式是将所述气凝胶加入石膏的原料中。优选地，所述气凝胶可以分多次加入，从而缩短真空搅拌的时间。加入次数可根据实际情况选择，例如分2-10次加入。According to an embodiment of the present invention, the aerogel is added to the raw material of gypsum. Preferably, the aerogel can be added in multiple times to shorten the vacuum stirring time. The number of additions can be selected according to actual conditions, for example, adding in 2-10 times.
根据本发明的实施方案，所述石膏的原料选自熟石膏粉(例如为半水石膏粉)。优选地，所述熟石膏粉的纯度至少大于90％，例如为95％或98％。优选地，所述熟石膏粉具有较高细度，例如100～120目为宜。According to an embodiment of the present invention, the raw material of the gypsum is selected from gypsum powder (e.g., semi-hydrated gypsum powder). Preferably, the purity of the gypsum powder is at least greater than 90%, such as 95% or 98%. Preferably, the gypsum powder has a relatively high fineness, such as 100-120 mesh.
根据本发明的实施方案，所述气凝胶改性石膏中，气凝胶与石膏的质量比为(0～30):100且所述气凝胶的含量不为0，例如为5:100、10:100、15:100、20:100、25:100、30:100。 According to an embodiment of the present invention, in the aerogel-modified gypsum, the mass ratio of aerogel to gypsum is (0-30):100 and the content of aerogel is not 0, for example, 5:100, 10:100, 15:100, 20:100, 25:100, 30:100.
根据本发明的实施方案，所述气凝胶改性石膏中，气凝胶的粒径为1nm-50nm，优选为20nm-50nm，例如为1nm、10nm、20nm、30nm、40mm或50nm。According to an embodiment of the present invention, in the aerogel-modified gypsum, the particle size of the aerogel is 1 nm-50 nm, preferably 20 nm-50 nm, for example, 1 nm, 10 nm, 20 nm, 30 nm, 40 nm or 50 nm.
根据本发明的实施方案，气凝胶选自亲水改性气凝胶和/或疏水气凝胶。According to an embodiment of the present invention, the aerogel is selected from hydrophilically modified aerogels and/or hydrophobic aerogels.
研究发现，当加入亲水改性气凝胶时，更容易与石膏浆料混合，另外，相比于未处理的疏水气凝胶，亲水改性气凝胶的保温性能更优。The study found that when hydrophilic modified aerogel is added, it is easier to mix with gypsum slurry. In addition, compared with untreated hydrophobic aerogel, the thermal insulation performance of hydrophilic modified aerogel is better.
根据本发明的优选方案，所述气凝胶包括亲水改性气凝胶和疏水气凝胶，其中，亲水改性气凝胶与疏水气凝胶的质量比为100:(0～100)且所述疏水气凝胶的含量不为0。According to a preferred embodiment of the present invention, the aerogel includes hydrophilic modified aerogel and hydrophobic aerogel, wherein the mass ratio of hydrophilic modified aerogel to hydrophobic aerogel is 100:(0-100) and the content of the hydrophobic aerogel is not zero.
研究发现，若石膏中仅加入亲水改性气凝胶，会带来石膏强度降低的问题，而若在添加亲水改性气凝胶的同时还引入疏水气凝胶，则可以在保持保温性能的前提下，保持强度不降低，即混合添加的气凝胶，既拥有较好的保温性能提升，石膏的强度下降不多；且加入疏水型粉体作为添加料后，还可以提高石膏浆料的分散性。The study found that if only hydrophilic modified aerogel is added to gypsum, the strength of the gypsum will be reduced. However, if hydrophobic aerogel is introduced at the same time as the hydrophilic modified aerogel, the strength can be maintained without reducing while maintaining the thermal insulation performance. That is, the mixed aerogel has better thermal insulation performance and the strength of the gypsum does not decrease much. After adding hydrophobic powder as an additive, the dispersibility of the gypsum slurry can also be improved.
优选地，所述亲水改性气凝胶与疏水气凝胶的质量比为100:(20～50)，例如为100:5、100:10、100:20、100:30、100:40、100:60、100:70、100:80、100:90。研究发现，当疏水气凝胶与亲水改性气凝胶的质量比在上述范围内时，既可以保证所述保温石膏的保温性能，又可以维持所述保温石膏的机械强度。Preferably, the mass ratio of the hydrophilic modified aerogel to the hydrophobic aerogel is 100:(20-50), for example, 100:5, 100:10, 100:20, 100:30, 100:40, 100:60, 100:70, 100:80, 100:90. Studies have found that when the mass ratio of the hydrophobic aerogel to the hydrophilic modified aerogel is within the above range, the thermal insulation performance of the thermal insulation gypsum can be guaranteed and the mechanical strength of the thermal insulation gypsum can be maintained.
根据本发明的实施方案，所述亲水改性气凝胶是一种亲水改性气凝胶颗粒。According to an embodiment of the present invention, the hydrophilically modified aerogel is a hydrophilically modified aerogel particle.
根据本发明的实施方案，所述亲水改性气凝胶与水的接触角小于90°。优选地，所述亲水改性气凝胶的表面含有亲水基团，所述亲水基团选择本领域已知的基团，例如为羟基(-OH)。According to an embodiment of the present invention, the contact angle between the hydrophilic modified aerogel and water is less than 90°. Preferably, the surface of the hydrophilic modified aerogel contains hydrophilic groups, and the hydrophilic groups are selected from groups known in the art, such as hydroxyl groups (-OH).
根据本发明的实施方案，所述疏水气凝胶与水的接触角大于90°。优选地，所述疏水气凝胶的表面含有疏水基团，所述疏水基团选择本领域已知的基团，例如为烷氧基(-OR，R表示烷基)。According to an embodiment of the present invention, the contact angle between the hydrophobic aerogel and water is greater than 90°. Preferably, the surface of the hydrophobic aerogel contains hydrophobic groups, and the hydrophobic groups are selected from groups known in the art, such as alkoxy groups (-OR, R represents an alkyl group).
根据本发明的实施方案，所述辅料包括水，和下述物质中的至少一种：玻 化微珠、增强剂、分散剂、增强纤维和缓凝剂。示例性地，所述辅料包括水、玻化微珠、增强剂、分散剂、增强纤维和缓凝剂。According to an embodiment of the present invention, the auxiliary material includes water and at least one of the following substances: glass Exemplarily, the auxiliary materials include water, vitrified microspheres, a reinforcing agent, a dispersant, a reinforcing fiber and a retarder.
根据本发明的实施方案，以每100质量份石膏的原料计，所述辅料的添加量为0.1～200质量份。According to an embodiment of the present invention, the auxiliary material is added in an amount of 0.1 to 200 parts by mass per 100 parts by mass of the gypsum raw material.
根据本发明的实施方案，以每100质量份石膏的原料计，水为100～120质量份，例如为105重量份、110质量份、115质量份、120质量份。According to an embodiment of the present invention, the amount of water is 100 to 120 parts by mass, for example, 105 parts by mass, 110 parts by mass, 115 parts by mass, or 120 parts by mass, per 100 parts by mass of the gypsum raw material.
根据本发明的实施方案，所述分散剂可以提高产品成型加工时流动性；且不影响产品的性能，且无毒、价格适宜。According to the embodiment of the present invention, the dispersant can improve the fluidity of the product during molding and processing; it does not affect the performance of the product, and is non-toxic and reasonably priced.
根据本发明的实施方案，以每100质量份石膏的原料计，所述分散剂为0.01-5质量份，例如为0.1重量份、0.5质量份、1质量份、2质量份、3质量份、4质量份。According to an embodiment of the present invention, the dispersant is 0.01-5 parts by mass, for example, 0.1 parts by mass, 0.5 parts by mass, 1 parts by mass, 2 parts by mass, 3 parts by mass, or 4 parts by mass, per 100 parts by mass of the gypsum raw material.
根据本发明的实施方案，所述分散剂选自聚氧乙烯二油酸酯、四乙二醇单硬脂酸酯、四乙二醇单油酸酯、聚氧丙烯甘露醇二油酸酯、聚氧乙烯山梨醇羊毛脂油酸衍生物、聚氧乙烯山梨醇羊毛脂衍生物、聚氧丙烯硬脂酸酯、聚氧乙烯(5EO)羊毛醇醚、失水山梨醇月桂酸酯、聚氧乙烯脂肪酸、聚氧乙烯氧丙烯油酸酯、三乙基己基磷酸、十二烷基硫酸钠、甲基戊醇、纤维素衍生物、聚丙烯酰胺、古尔胶、脂肪酸聚乙二醇酯，优选为聚氧丙烯硬脂酸酯、聚氧乙烯二油酸酯。According to an embodiment of the present invention, the dispersant is selected from polyoxyethylene dioleate, tetraethylene glycol monostearate, tetraethylene glycol monooleate, polyoxypropylene mannitol dioleate, polyoxyethylene sorbitol lanolin oleic acid derivatives, polyoxyethylene sorbitol lanolin derivatives, polyoxypropylene stearate, polyoxyethylene (5EO) lanolin ether, sorbitan laurate, polyoxyethylene fatty acid, polyoxyethylene oxypropylene oleate, triethylhexyl phosphoric acid, sodium lauryl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide, gur gum, fatty acid polyethylene glycol esters, preferably polyoxypropylene stearate and polyoxyethylene dioleate.
根据本发明的实施方案，以每100质量份石膏的原料计，所述玻化微珠为5～40质量份，例如为10重量份、20重量份、30重量份、40重量份。According to an embodiment of the present invention, the amount of the vitrified microspheres is 5 to 40 parts by weight, for example, 10 parts by weight, 20 parts by weight, 30 parts by weight, or 40 parts by weight, per 100 parts by weight of the gypsum raw material.
根据本发明的实施方案，所述玻化微珠可选自本领域已知的材料，本发明中不做具体限定。According to an embodiment of the present invention, the vitrified microspheres may be selected from materials known in the art, and are not specifically limited in the present invention.
根据本发明的实施方案，所述增强纤维选自无机纤维和有机纤维，例如聚酯纤维、玻璃纤维、玄武岩纤维等。优选地，所述增强纤维应为短纤维，具体为纤维的长度为3mm-60mm，例如为10mm、20mm、30mm、40mm、50mm。According to an embodiment of the present invention, the reinforcing fiber is selected from inorganic fibers and organic fibers, such as polyester fibers, glass fibers, basalt fibers, etc. Preferably, the reinforcing fiber should be short fibers, specifically fibers with a length of 3 mm to 60 mm, such as 10 mm, 20 mm, 30 mm, 40 mm, 50 mm.
根据本发明的实施方案，以每100质量份石膏的原料计，所述增强纤维为0.5-5质量份，例如为0.6重量份、0.7质量份、0.8质量份、0.9质量份。本发明中， 将增强纤维作为骨架填充材料，以增加气凝胶改性石膏的强度。According to an embodiment of the present invention, the reinforcing fiber is 0.5-5 parts by weight, for example, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, or 0.9 parts by weight, per 100 parts by weight of the gypsum raw material. The reinforcing fibers are used as skeleton filling materials to increase the strength of the aerogel-modified gypsum.
根据本发明的实施方案，所述缓凝剂选自有机酸及其可溶盐、碱性磷酸盐以及蛋白质类等缓凝剂。示例性地，所述缓凝剂选自柠檬酸、柠檬酸钠、酒石酸、酒石酸钾、丙烯酸及丙烯酸钠，六偏磷酸钠、多聚磷酸钠、硼砂、硼酸钠、三聚磷酸钠、葡萄糖酸钠，优选为柠檬酸、酒石酸、葡萄糖酸钠。本发明中，缓凝剂可延长搅拌时间，提高膏水比例，提高成品的强度。According to an embodiment of the present invention, the retarder is selected from organic acids and soluble salts thereof, alkaline phosphates and proteins. Exemplarily, the retarder is selected from citric acid, sodium citrate, tartaric acid, potassium tartrate, acrylic acid and sodium acrylate, sodium hexametaphosphate, sodium polyphosphate, borax, sodium borate, sodium tripolyphosphate, sodium gluconate, preferably citric acid, tartaric acid, sodium gluconate. In the present invention, the retarder can prolong the stirring time, increase the paste-water ratio, and improve the strength of the finished product.
根据本发明的实施方案，以每100质量份石膏的原料计，所述缓凝剂为0.01-0.5质量份，例如为0.05质量份、0.1质量份、0.2质量份、0.3质量份、0.4质量份。According to an embodiment of the present invention, the retarder is 0.01-0.5 parts by mass, for example, 0.05 parts by mass, 0.1 parts by mass, 0.2 parts by mass, 0.3 parts by mass, or 0.4 parts by mass, per 100 parts by mass of the gypsum raw material.
根据本发明的实施方案，在所述真空搅拌前，石膏的原料、辅料和气凝胶还可以进行预混合以得到均匀预混料。优选地，预混合时温度控制在8℃～10℃，其目的是降低半水石膏在水中的溶解速率，延长石膏的原料在水中的溶解和晶核形成时间，即延缓石膏的原料与水的反应速度。According to an embodiment of the present invention, before the vacuum stirring, the raw materials, auxiliary materials and aerogel of gypsum can also be premixed to obtain a uniform premix. Preferably, the temperature during premixing is controlled at 8°C to 10°C, the purpose of which is to reduce the dissolution rate of hemihydrate gypsum in water, prolong the dissolution time of the raw materials of gypsum in water and the crystal nucleus formation time, that is, to slow down the reaction rate of the raw materials of gypsum and water.
根据本发明的实施方案，所述引气剂与所述石膏的原料的质量比为0.1～1：100，例如为0.1:100、0.5:100。发明人发现，加入引气剂后搅拌均匀，可以改善混合物的流动性、黏聚性。According to an embodiment of the present invention, the mass ratio of the air entraining agent to the gypsum raw material is 0.1 to 1:100, for example, 0.1:100 or 0.5:100. The inventors have found that adding the air entraining agent and stirring evenly can improve the fluidity and cohesiveness of the mixture.
根据本发明的实施方案，所述引气剂可选自本领域已知的引气剂，例如选自松香树脂类引气剂、烷基苯磺酸盐类引气剂、脂肪醇磺酸盐类引气剂。According to an embodiment of the present invention, the air entraining agent can be selected from air entraining agents known in the art, for example, selected from rosin resin air entraining agents, alkylbenzene sulfonate air entraining agents, and fatty alcohol sulfonate air entraining agents.
具体的，所述引气剂可以选自十二烷基硫酸钠、松香酸钠、三萜皂苷、α-烯基磺酸钠中的至少一种。Specifically, the air entraining agent can be selected from at least one of sodium dodecyl sulfate, sodium rosin acid, triterpenoid saponin, and sodium α-olefin sulfonate.
根据本发明的实施方案，所述真空搅拌和搅拌分别在高速搅拌设备中进行，具体的，所述高速搅拌设备可以是高速磁力搅拌机、自落式搅拌机或强制式搅拌机。According to an embodiment of the present invention, the vacuum stirring and stirring are respectively carried out in a high-speed stirring device. Specifically, the high-speed stirring device can be a high-speed magnetic stirrer, a self-falling stirrer or a forced stirrer.
根据本发明的实施方案，加入引气剂混合均匀后，还可进一步进行硬化和养护。优选地，所述养护可选用本领域已知的方法进行。According to an embodiment of the present invention, after the air entraining agent is added and mixed evenly, hardening and curing can be further performed. Preferably, the curing can be performed by methods known in the art.
示例性地，所述养护包括：先自然养护后，再进行加强养护。进一步地， 所述自然养护是指在0-40℃下养护12-36小时。进一步地，所述加强养护是指：环境温度为30-50℃(优选40℃)；湿度不大于90％(优选为10％、20％、50％、70％、80％)；养护时间48h-72h。Exemplarily, the maintenance includes: first natural maintenance, then enhanced maintenance. The natural curing refers to curing at 0-40°C for 12-36 hours. Furthermore, the enhanced curing refers to: the ambient temperature is 30-50°C (preferably 40°C); the humidity is not more than 90% (preferably 10%, 20%, 50%, 70%, 80%); the curing time is 48h-72h.
本发明还提供上述制备方法得到的气凝胶改性石膏。The present invention also provides aerogel modified gypsum obtained by the preparation method.
根据本发明的实施方案，所述气凝胶改性石膏的导热系数不高于0.25w/(m.k)，例如为0.2w/(m.k)、0.1w/(m.k)、0.07w/(m.k)、0.05w/(m.k)。According to an embodiment of the present invention, the thermal conductivity of the aerogel-modified gypsum is not higher than 0.25w/(m.k), for example, 0.2w/(m.k), 0.1w/(m.k), 0.07w/(m.k), or 0.05w/(m.k).
根据本发明的实施方案，所述气凝胶改性石膏的抗压强度为1～10MPa，例如为2MPa、3MPa、4MPa、5MPa、6MPa、7MPa、8MPa、9MPa。According to an embodiment of the present invention, the compressive strength of the aerogel-modified gypsum is 1 to 10 MPa, for example, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, or 9 MPa.
下文将结合具体实施例对本发明的技术方案做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included in the scope that the present invention is intended to protect.
除非另有说明，以下实施例中使用的原料和试剂均为市售商品，或者可以通过已知方法制备。Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.
下述实施例中使用的试剂如下：The reagents used in the following examples are as follows:
熟石膏粉：市售石膏粉(半水硫酸钙)即可，CaSO4·0.5H2O的含量(纯度)大于90％，98％以上优选。Plaster of Paris powder: commercially available gypsum powder (calcium sulfate hemihydrate) may be used, and the content (purity) of CaSO 4 ·0.5H 2 O is greater than 90%, preferably greater than 98%.
增强纤维包括：自玻璃纤维、聚丙烯纤维和聚酯纤维中的至少一种。增强纤维可以提高保温石膏的防开裂性能，增加抗拉强度。The reinforcing fiber includes at least one of glass fiber, polypropylene fiber and polyester fiber. The reinforcing fiber can improve the anti-cracking performance of the thermal insulation gypsum and increase the tensile strength.
玻化微珠：粒径大小为100μm～300μm。Vitrified microspheres: particle size is 100μm~300μm.
疏水气凝胶：中科润资科技股份有限公司，牌号RZF500或RZF1000。Hydrophobic aerogel: Zhongke Runzi Technology Co., Ltd., brand RZF500 or RZF1000.
分散剂：聚氧乙烯油酸酯，聚舜化工。Dispersant: polyoxyethylene oleate, Polyshun Chemical.
制备例1Preparation Example 1
制备亲水改性气凝胶：Preparation of hydrophilic modified aerogel:
亲水改性方法1：取上述疏水气凝胶(中科润资科技股份有限公司，牌号RZF500或RZF1000)，在高温200～350℃条件下，处理1～10分钟，得到亲水 改性气凝胶。Hydrophilic modification method 1: Take the above hydrophobic aerogel (Zhongke Runzi Technology Co., Ltd., brand RZF500 or RZF1000), treat it at high temperature of 200-350℃ for 1-10 minutes to obtain a hydrophilic Modified aerogel.
制备例2Preparation Example 2
制备亲水改性气凝胶：Preparation of hydrophilic modified aerogel:
亲水改性方法2：取上述疏水气凝胶(中科润资科技股份有限公司，牌号RZF500或RZF1000)，使用乙醇浸渍后并干燥，得到亲水改性气凝胶；可以是自然干燥或者加热烘干。加热烘干的条件是：在高温90～110℃，处理1～10分钟。Hydrophilic modification method 2: Take the above hydrophobic aerogel (Zhongke Runzi Technology Co., Ltd., brand RZF500 or RZF1000), impregnate it with ethanol and dry it to obtain a hydrophilic modified aerogel; it can be naturally dried or heated and dried. The conditions for heating and drying are: high temperature 90-110°C, treatment for 1-10 minutes.
制备例2制备得到的亲水改性气凝胶的性能与制备例1基本相当，两种亲水改性方法均可以达到亲水改性的效果。The performance of the hydrophilic modified aerogel prepared in Preparation Example 2 is basically equivalent to that in Preparation Example 1, and both hydrophilic modification methods can achieve the hydrophilic modification effect.
实施例1Example 1
气凝胶改性石膏的制备方法如下：The preparation method of aerogel modified gypsum is as follows:
A、制备混合气凝胶：将亲水改性气凝胶和疏水改性气凝胶按比例混合得到气凝胶；其中，混合气凝胶包括制备例1的亲水改性气凝胶和市购的疏水气凝胶，两者的质量比为1:1；A. Preparation of mixed aerogel: mixing hydrophilic modified aerogel and hydrophobic modified aerogel in proportion to obtain aerogel; wherein the mixed aerogel comprises the hydrophilic modified aerogel of Preparation Example 1 and commercially available hydrophobic aerogel, and the mass ratio of the two is 1:1;
B、将步骤A得到的气凝胶与熟石膏粉、水、辅料和气凝胶预混合均匀后，在搅拌机中进行搅拌操作得到石膏浆料；具体的制备方法如下(以下份数均指质量份)：B. The aerogel obtained in step A is pre-mixed with gypsum powder, water, auxiliary materials and aerogel, and then stirred in a mixer to obtain gypsum slurry; the specific preparation method is as follows (the following parts are all parts by mass):
1)石膏粉预处理：取市售石膏粉过筛，经100～150目筛网过筛后，得到粒径为100～120目的石膏粉；1) Pretreatment of gypsum powder: sieve commercially available gypsum powder through a 100-150 mesh sieve to obtain gypsum powder with a particle size of 100-120 mesh;
2)干粉原料混合：将100份步骤1)的熟石膏粉与5份混合气凝胶(其中含亲水改性气凝胶2.5份)、辅料在2～8℃条件下混合均匀，得到干粉混料，其中辅料包括：0.2份缓凝剂柠檬酸、1份分散剂、10份玻化微珠、1份增强纤维玻璃纤维混合均匀；2) Mixing dry powder raw materials: 100 parts of the gypsum powder prepared in step 1) are mixed evenly with 5 parts of mixed aerogel (including 2.5 parts of hydrophilic modified aerogel) and auxiliary materials at 2-8° C. to obtain a dry powder mixture, wherein the auxiliary materials include: 0.2 parts of retarder citric acid, 1 part of dispersant, 10 parts of vitrified microspheres, and 1 part of reinforcing fiber glass fiber;
3)真空搅拌：向步骤2)的干粉混料中加入100-120份水，水温在8～10℃，并抽真空至绝对压强小于1KPa，维持真空情况下进行真空搅拌，搅拌时间2分钟，得到浆料A；3) Vacuum stirring: add 100-120 parts of water to the dry powder mixture of step 2), the water temperature is 8-10°C, and evacuate to an absolute pressure of less than 1KPa, and perform vacuum stirring under vacuum condition for 2 minutes to obtain slurry A;
4)常压搅拌：向步骤3)得到的浆料A中加入0.2份引气剂十二烷基硫酸 钠，并再次进行常压搅拌(即搅拌环境为常压)，搅拌时间3分钟，得到浆料B；4) Stirring at normal pressure: Add 0.2 parts of air entraining agent dodecyl sulfuric acid to the slurry A obtained in step 3) Sodium was added, and the mixture was stirred at normal pressure again (i.e., the stirring environment was at normal pressure) for 3 minutes to obtain slurry B;
C：将浆料B浇筑至模具或者涂抹至目标基体表面，并进行硬化与养护，具体包括：C: Pour slurry B into the mold or apply it to the surface of the target substrate, and harden and cure it, including:
1)自然养护：将浆料B浇筑在模具中或涂抹在基体上后置于常温环境下12-36小时；1) Natural curing: pour slurry B into a mold or apply it on the substrate and place it at room temperature for 12-36 hours;
2)加强养护：将自然养护后的含有浆料B的模具或涂抹浆料B的基体进行加强养护，加强养护的环境温度为40℃，湿度不大于70％，养护时间48h-72h，得到所述气凝胶改性石膏。2) Strengthening curing: Strengthening curing the mold containing slurry B or the substrate coated with slurry B after natural curing, the environment temperature of the strengthened curing is 40° C., the humidity is not more than 70%, and the curing time is 48h-72h to obtain the aerogel modified gypsum.
经测试可知，本实施例的保温石膏的抗压强度7.36Mpa，导热系数为0.160W/(m·K)，记录于表1中。The test shows that the compressive strength of the thermal insulation gypsum of this embodiment is 7.36 MPa, and the thermal conductivity is 0.160 W/(m·K), which are recorded in Table 1.
实施例1-1Example 1-1
本实施例的保温石膏的制备方法基本同实施例1，不同在于，步骤2)中，混合气凝胶为5份，其中，亲水改性气凝胶添加量3.33份，即亲水改性气凝胶和疏水气凝胶的质量比2:1。The preparation method of the thermal insulation gypsum of this embodiment is basically the same as that of Embodiment 1, except that in step 2), the mixed aerogel is 5 parts, of which the hydrophilic modified aerogel is added in an amount of 3.33 parts, that is, the mass ratio of the hydrophilic modified aerogel to the hydrophobic aerogel is 2:1.
经测试可知，本实施例的保温石膏的抗压强度7.40Mpa，导热系数为0.157W/(m·K)，记录于表1中。The test shows that the compressive strength of the thermal insulation gypsum of this embodiment is 7.40 MPa, and the thermal conductivity is 0.157 W/(m·K), which are recorded in Table 1.
实施例2Example 2
本实施例的保温石膏的制备方法基本同实施例1，不同在于，步骤2)中，混合气凝胶为10份，其中，亲水改性气凝胶添加量5份，亲水改性气凝胶和疏水气凝胶的质量比1:1。The preparation method of the thermal insulation gypsum of this embodiment is basically the same as that of Embodiment 1, except that in step 2), the mixed aerogel is 10 parts, of which 5 parts are added in the amount of hydrophilic modified aerogel, and the mass ratio of hydrophilic modified aerogel to hydrophobic aerogel is 1:1.
经测试可知，本实施例的保温石膏的抗压强度6.19Mpa，导热系数为0.111W/(m·K)，记录于表1中。The test shows that the compressive strength of the thermal insulation gypsum of this embodiment is 6.19 MPa, and the thermal conductivity is 0.111 W/(m·K), which are recorded in Table 1.
实施例2-1Example 2-1
本实施例的保温石膏的制备方法基本同实施例2，不同在于，步骤2)中，混合气凝胶为10份，其中，亲水改性气凝胶添加量6.67份，亲水改性气凝胶和疏水气凝胶的质量比2:1。 The preparation method of the thermal insulation gypsum of this embodiment is basically the same as that of Embodiment 2, except that in step 2), the mixed aerogel is 10 parts, of which the added amount of hydrophilic modified aerogel is 6.67 parts, and the mass ratio of hydrophilic modified aerogel to hydrophobic aerogel is 2:1.
经测试可知，本实施例的保温石膏的抗压强度5.97Mpa，导热系数为0.109W/(m·K)，记录于表1中。The test shows that the compressive strength of the thermal insulation gypsum of this embodiment is 5.97 MPa, and the thermal conductivity is 0.109 W/(m·K), which are recorded in Table 1.
实施例3Example 3
本实施例的保温石膏的制备方法基本同实施例1，不同在于，步骤2)中，混合气凝胶为20份，其中，亲水改性气凝胶添加量10份，亲水改性气凝胶和疏水气凝胶的质量比1:1。The preparation method of the thermal insulation gypsum of this embodiment is basically the same as that of Embodiment 1, except that in step 2), the mixed aerogel is 20 parts, of which the hydrophilic modified aerogel is added in an amount of 10 parts, and the mass ratio of the hydrophilic modified aerogel to the hydrophobic aerogel is 1:1.
经测试可知，本实施例的保温石膏的抗压强度2.76Mpa，导热系数为0.091W/(m·K)，记录于表1中。The test shows that the compressive strength of the thermal insulation gypsum of this embodiment is 2.76 MPa, and the thermal conductivity is 0.091 W/(m·K), which are recorded in Table 1.
实施例3-1Example 3-1
本实施例的保温石膏的制备方法基本同实施例3，不同在于，步骤2)中，混合气凝胶为20份，其中，亲水改性气凝胶添加量13.33份，亲水改性气凝胶和疏水气凝胶的质量比2:1。The preparation method of the thermal insulation gypsum of this embodiment is basically the same as that of Embodiment 3, except that in step 2), the mixed aerogel is 20 parts, of which the added amount of hydrophilic modified aerogel is 13.33 parts, and the mass ratio of hydrophilic modified aerogel to hydrophobic aerogel is 2:1.
经测试可知，本实施例的保温石膏的抗压强度2.45Mpa，导热系数为0.082W/(m·K)，记录于表1中。The test shows that the compressive strength of the thermal insulation gypsum of this embodiment is 2.45 MPa, and the thermal conductivity is 0.082 W/(m·K), which are recorded in Table 1.
实施例4Example 4
本实施例的保温石膏的制备方法基本同实施例1，不同在于，步骤2)中混合气凝胶为15份，其中，亲水改性气凝胶添加量7.5份，亲水改性气凝胶和疏水气凝胶的质量比1:1。The preparation method of the thermal insulation gypsum of this embodiment is basically the same as that of Embodiment 1, except that in step 2), the mixed aerogel is 15 parts, of which the hydrophilic modified aerogel is added in an amount of 7.5 parts, and the mass ratio of the hydrophilic modified aerogel to the hydrophobic aerogel is 1:1.
经测试可知，本实施例的保温石膏的抗压强度4.14Mpa，导热系数为0.098W/(m·K)，记录于表1中。The test shows that the compressive strength of the thermal insulation gypsum of this embodiment is 4.14 MPa, and the thermal conductivity is 0.098 W/(m·K), which are recorded in Table 1.
实施例4-1Example 4-1
本实施例的保温石膏的制备方法基本同实施例4，不同在于，步骤2)中混合气凝胶为15份，其中，亲水改性气凝胶添加量10份，亲水改性气凝胶和疏水气凝胶的质量比2:1。The preparation method of the thermal insulation gypsum of this embodiment is basically the same as that of Embodiment 4, except that in step 2), the mixed aerogel is 15 parts, of which the hydrophilic modified aerogel is added in an amount of 10 parts, and the mass ratio of the hydrophilic modified aerogel to the hydrophobic aerogel is 2:1.
经测试可知，本实施例的保温石膏的抗压强度3.64Mpa，导热系数为0.089W/(m·K)，记录于表1中。 The test shows that the compressive strength of the thermal insulation gypsum of this embodiment is 3.64 MPa, and the thermal conductivity is 0.089 W/(m·K), which are recorded in Table 1.
实施例5Example 5
本实施例的保温石膏的制备方法基本同实施例1，不同在于，步骤2)中，混合气凝胶为25份，其中，亲水改性气凝胶添加量12.5份，亲水改性气凝胶和疏水气凝胶的质量比1:1。The preparation method of the thermal insulation gypsum of this embodiment is basically the same as that of Embodiment 1, except that in step 2), the mixed aerogel is 25 parts, of which the hydrophilic modified aerogel is added in an amount of 12.5 parts, and the mass ratio of the hydrophilic modified aerogel to the hydrophobic aerogel is 1:1.
经测试可知，本实施例的保温石膏的抗压强度1.93Mpa，导热系数为0.085W/(m·K)，记录于表1中。The test shows that the compressive strength of the thermal insulation gypsum of this embodiment is 1.93 MPa, and the thermal conductivity is 0.085 W/(m·K), which are recorded in Table 1.
实施例5-1Example 5-1
本实施例的保温石膏的制备方法基本同实施例5，不同在于，步骤2)中，混合气凝胶为25份，其中，亲水改性气凝胶添加量16.7份，亲水改性气凝胶和疏水气凝胶的质量比2:1。The preparation method of the thermal insulation gypsum of this embodiment is basically the same as that of Embodiment 5, except that in step 2), the mixed aerogel is 25 parts, of which the hydrophilic modified aerogel is added in an amount of 16.7 parts, and the mass ratio of the hydrophilic modified aerogel to the hydrophobic aerogel is 2:1.
经测试可知，本实施例的保温石膏的抗压强度1.71Mpa，导热系数为0.077W/(m·K)，记录于表1中。The test shows that the compressive strength of the thermal insulation gypsum of this embodiment is 1.71 MPa, and the thermal conductivity is 0.077 W/(m·K), which are recorded in Table 1.
实施例6Example 6
本实施例的保温石膏的制备方法基本同实施例1，不同在于，步骤A中仅采用制备例1的亲水改性气凝胶；The preparation method of the thermal insulation gypsum of this embodiment is basically the same as that of Example 1, except that only the hydrophilic modified aerogel of Preparation Example 1 is used in step A;
步骤B中，步骤2)使用的是制备例1的亲水改性气凝胶。In step B, step 2) uses the hydrophilic modified aerogel of Preparation Example 1.
经测试可知，本实施例的保温石膏的抗压强度7.18Mpa，导热系数为0.154W/(m·K)，记录于表1中。The test shows that the compressive strength of the thermal insulation gypsum of this embodiment is 7.18 Mpa, and the thermal conductivity is 0.154 W/(m·K), which are recorded in Table 1.
实施例7Example 7
本实施例的保温石膏的制备方法基本同实施例1，不同在于，步骤A中仅采用市购的疏水气凝胶；The preparation method of the thermal insulation gypsum of this embodiment is basically the same as that of Embodiment 1, except that only commercially available hydrophobic aerogel is used in step A;
步骤B中，步骤2)使用的是市购的疏水气凝胶。In step B, step 2) uses commercially available hydrophobic aerogel.
经测试可知，本实施例的保温石膏的抗压强度8.45Mpa，导热系数为0.171W/(m·K)，记录于表1中。The test shows that the compressive strength of the thermal insulation gypsum of this embodiment is 8.45 MPa, and the thermal conductivity is 0.171 W/(m·K), which are recorded in Table 1.
对比例1Comparative Example 1
本对比例基本同实施例2，不同在于： This comparative example is basically the same as Example 2, except that:
步骤3)中还加入0.2份引气剂十二烷基硫酸钠，并不进行抽真空操作，直接进行常压搅拌，搅拌时间5分钟，直接得到浆料B。In step 3), 0.2 parts of an air entraining agent, sodium dodecyl sulfate, was also added, and no vacuum operation was performed. The mixture was directly stirred at normal pressure for 5 minutes to obtain slurry B.
经测试可知，本对比例的保温石膏的抗压强度5.63Mpa，导热系数为0.118W/(m·K)，记录于表1中。The test shows that the compressive strength of the thermal insulation gypsum of this comparative example is 5.63 MPa, and the thermal conductivity is 0.118 W/(m·K), which are recorded in Table 1.
对比例2Comparative Example 2
本对比例基本同实施例2-1，不同在于：This comparative example is basically the same as Example 2-1, except that:
步骤3)中还加入0.2份引气剂十二烷基硫酸钠，并不进行抽真空操作，直接进行常压搅拌，搅拌时间5分钟，直接得到浆料B。In step 3), 0.2 parts of an air entraining agent, sodium dodecyl sulfate, was also added, and no vacuum operation was performed. The mixture was directly stirred at normal pressure for 5 minutes to obtain slurry B.
经测试可知，本对比例的保温石膏的抗压强度5.43Mpa，导热系数为0.116W/(m·K)，记录于表1中。The test shows that the compressive strength of the thermal insulation gypsum of this comparative example is 5.43 MPa, and the thermal conductivity is 0.116 W/(m·K), which are recorded in Table 1.
对比例3Comparative Example 3
本对比例基本同实施例2，不同在于，步骤2)中仅使用亲水改性气凝胶，其添加量10份。This comparative example is basically the same as Example 2, except that in step 2), only hydrophilic modified aerogel is used, and the addition amount thereof is 10 parts.
步骤3)中还加入0.2份引气剂十二烷基硫酸钠，并不进行抽真空操作，直接进行常压搅拌，搅拌时间5分钟，直接得到浆料B。In step 3), 0.2 parts of an air entraining agent, sodium dodecyl sulfate, was also added, and no vacuum operation was performed. The mixture was directly stirred at normal pressure for 5 minutes to obtain slurry B.
经测试可知，本对比例的保温石膏的抗压强度5.23Mpa，导热系数为0.111W/(m·K)，记录于表1中。The test shows that the compressive strength of the thermal insulation gypsum of this comparative example is 5.23 MPa, and the thermal conductivity is 0.111 W/(m·K), which are recorded in Table 1.
对比例4Comparative Example 4
本对比例基本同实施例2，不同在于，步骤2)中仅使用疏水气凝胶，其添加量10份。This comparative example is basically the same as Example 2, except that in step 2), only hydrophobic aerogel is used, and the addition amount thereof is 10 parts.
步骤3)中还加入0.2份引气剂十二烷基硫酸钠，并不进行抽真空操作，直接进行常压搅拌，搅拌时间5分钟，直接得到浆料B。In step 3), 0.2 parts of an air entraining agent, sodium dodecyl sulfate, was also added, and no vacuum operation was performed. The mixture was directly stirred at normal pressure for 5 minutes to obtain slurry B.
经测试可知，本对比例的保温石膏的抗压强度6.16Mpa，导热系数为0.130W/(m·K)，记录于表1中。The test shows that the compressive strength of the thermal insulation gypsum of this comparative example is 6.16 MPa, and the thermal conductivity is 0.130 W/(m·K), which are recorded in Table 1.
表1
Table 1
以上对本发明示例性的实施方式进行了说明。但是，本申请的保护范围不拘囿于上述实施方式。本领域技术人员在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。 The above is a description of the exemplary embodiments of the present invention. However, the protection scope of the present application is not limited to the above embodiments. Any modification, equivalent substitution, improvement, etc. made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims (10)

  1. 一种气凝胶改性石膏的制备方法，其特征在于，所述制备方法包括：将气凝胶与石膏的原料、辅料在真空搅拌的条件下混合后，再在常压条件下加入引气剂混合均匀，得到所述气凝胶改性石膏。A method for preparing aerogel-modified gypsum, characterized in that the preparation method comprises: mixing aerogel with raw materials and auxiliary materials of gypsum under vacuum stirring conditions, and then adding an air entraining agent under normal pressure conditions to mix evenly to obtain the aerogel-modified gypsum.
  2. 根据权利要求1所述的制备方法，其特征在于，真空搅拌的条件具体包括：在绝对压强小于1KPa的条件下，进行搅拌；搅拌时间为不大于5min；搅拌温度为8℃～10℃；The preparation method according to claim 1 is characterized in that the vacuum stirring conditions specifically include: stirring under an absolute pressure of less than 1 KPa; the stirring time is no more than 5 minutes; the stirring temperature is 8°C to 10°C;
    和/或，气凝胶的添加方式是将所述气凝胶加入石膏的原料中。And/or, the aerogel is added into the raw materials of gypsum.
  3. 根据权利要求1所述的制备方法，其特征在于，所述石膏的原料选自熟石膏粉；The preparation method according to claim 1, characterized in that the raw material of the gypsum is selected from gypsum powder;
    所述气凝胶改性石膏中，气凝胶与石膏的质量比为(0～30):100且所述气凝胶的含量不为0；In the aerogel-modified gypsum, the mass ratio of aerogel to gypsum is (0-30):100 and the content of the aerogel is not 0;
    所述气凝胶改性石膏中，气凝胶的粒径为1nm-50nm；In the aerogel-modified gypsum, the particle size of the aerogel is 1nm-50nm;
    气凝胶选自亲水改性气凝胶和/或疏水气凝胶。The aerogel is selected from hydrophilically modified aerogels and/or hydrophobic aerogels.
  4. 根据权利要求3所述的制备方法，其特征在于，所述气凝胶包括亲水改性气凝胶和疏水气凝胶，其中，亲水改性气凝胶与疏水气凝胶的质量比为100:(0～100)且所述疏水气凝胶的含量不为0。The preparation method according to claim 3 is characterized in that the aerogel comprises hydrophilic modified aerogel and hydrophobic aerogel, wherein the mass ratio of hydrophilic modified aerogel to hydrophobic aerogel is 100:(0-100) and the content of the hydrophobic aerogel is not 0.
  5. 根据权利要求3所述的制备方法，其特征在于，所述亲水改性气凝胶是一种亲水改性气凝胶颗粒；The preparation method according to claim 3, characterized in that the hydrophilic modified aerogel is a hydrophilic modified aerogel particle;
    所述亲水改性气凝胶与水的接触角小于90°；The contact angle between the hydrophilic modified aerogel and water is less than 90°;
    所述疏水气凝胶与水的接触角大于90°。The contact angle between the hydrophobic aerogel and water is greater than 90°.
  6. 根据权利要求1所述的制备方法，其特征在于，所述辅料包括水，和下述物质中的至少一种：玻化微珠、增强剂、分散剂、增强纤维和缓凝剂；The preparation method according to claim 1, characterized in that the auxiliary materials include water and at least one of the following substances: glass microspheres, reinforcing agents, dispersants, reinforcing fibers and retarder;
    和/或，以每100质量份石膏的原料计，所述辅料的添加量为0.1～200质量份。 And/or, the amount of the auxiliary material added is 0.1 to 200 parts by mass per 100 parts by mass of the gypsum raw material.
  7. 根据权利要求6所述的制备方法，其特征在于，以每100质量份石膏的原料计，水为100～120质量份；The preparation method according to claim 6, characterized in that the water is 100 to 120 parts by mass per 100 parts by mass of the gypsum raw material;
    和/或，以每100质量份石膏的原料计，所述分散剂为0.01-5质量份；and/or, the dispersant is 0.01-5 parts by mass per 100 parts by mass of the gypsum raw material;
    和/或，以每100质量份石膏的原料计，所述玻化微珠为5～40质量份；And/or, the vitrified microspheres are 5 to 40 parts by mass per 100 parts by mass of the gypsum raw material;
    和/或，以每100质量份石膏的原料计，所述增强纤维为0.5-5质量份；And/or, the reinforcing fiber is 0.5-5 parts by mass per 100 parts by mass of the gypsum raw material;
    和/或，以每100质量份石膏的原料计，所述缓凝剂为0.01-0.5质量份。And/or, the retarder is 0.01-0.5 parts by mass per 100 parts by mass of the gypsum raw material.
  8. 根据权利要求6所述的制备方法，其特征在于，所述增强纤维选自无机纤维和有机纤维；The preparation method according to claim 6, characterized in that the reinforcing fibers are selected from inorganic fibers and organic fibers;
    和/或，所述缓凝剂选自有机酸及其可溶盐、碱性磷酸盐以及蛋白质类等缓凝剂。And/or, the retarder is selected from organic acids and soluble salts thereof, alkaline phosphates, proteins and other retarders.
  9. 根据权利要求1所述的制备方法，其特征在于，在所述真空搅拌前，石膏的原料、辅料和气凝胶还进行预混合以得到均匀预混料。The preparation method according to claim 1 is characterized in that, before the vacuum stirring, the raw materials, auxiliary materials and aerogel of the gypsum are also premixed to obtain a uniform premix.
  10. 根据权利要求1所述的制备方法，其特征在于，所述引气剂与所述石膏的原料的质量比为0.1～1：100。 The preparation method according to claim 1 is characterized in that the mass ratio of the air entraining agent to the raw material of the gypsum is 0.1 to 1:100.
PCT/CN2023/088650 2023-04-17 2023-04-17 Method for preparing aerogel modified gypsum WO2024216430A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3814968A1 (en) * 1988-05-03 1989-11-16 Basf Ag DENSITY DENSITY 0.1 TO 0.4 G / CM (UP ARROW) 3 (UP ARROW)
CN104369269A (en) * 2014-11-11 2015-02-25 李金盛 Vacuum stirrer
CN106747189A (en) * 2016-12-07 2017-05-31 苏州同玄新材料有限公司 Gypsum material of aerogel-congtg and preparation method thereof
CN107099117A (en) * 2016-02-20 2017-08-29 金承黎 A kind of fibre-reinforced aerogel-polymer composites and preparation method thereof
CN107265963A (en) * 2016-04-08 2017-10-20 南京唯才新能源科技有限公司 A kind of superthermal insulation aerogel foam concrete and preparation method thereof
CN107265964A (en) * 2016-04-08 2017-10-20 南京唯才新能源科技有限公司 A kind of superthermal insulation aeroge foamed concrete and preparation method thereof
CN109987960A (en) * 2017-12-30 2019-07-09 卢锋 A kind of aerogel composite and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3814968A1 (en) * 1988-05-03 1989-11-16 Basf Ag DENSITY DENSITY 0.1 TO 0.4 G / CM (UP ARROW) 3 (UP ARROW)
CN104369269A (en) * 2014-11-11 2015-02-25 李金盛 Vacuum stirrer
CN107099117A (en) * 2016-02-20 2017-08-29 金承黎 A kind of fibre-reinforced aerogel-polymer composites and preparation method thereof
CN107265963A (en) * 2016-04-08 2017-10-20 南京唯才新能源科技有限公司 A kind of superthermal insulation aerogel foam concrete and preparation method thereof
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CN109987960A (en) * 2017-12-30 2019-07-09 卢锋 A kind of aerogel composite and preparation method thereof

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