CN110803903A - High-toughness cement-based composite wallboard with photocatalytic function and preparation method - Google Patents
High-toughness cement-based composite wallboard with photocatalytic function and preparation method Download PDFInfo
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5076—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with masses bonded by inorganic cements
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
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Abstract
The invention discloses a high-toughness cement-based composite wallboard with a photocatalytic function and a preparation method thereof, wherein the high-toughness cement-based composite wallboard consists of a photocatalytic coating layer and a high-toughness cement-based composite wallboard matrix; the high-toughness cement-based composite wallboard matrix is composed of the following raw materials in parts by weight: 90-130 parts of ordinary portland cement, 90-130 parts of fly ash, 6-12 parts of sulphoaluminate cement, 10-18 parts of silica fume, 10-16 parts of microbeads, 4-6 parts of polymer fibers, 0-0.2 part of cellulose ether, 0.8-2 parts of an additive, 54-70 parts of water and 60-80 parts of ultrafine powder. Compared with the prior art, the invention has excellent mechanical property and good durability, and the preparation method is simple and easy to operate; in addition, the prepared photocatalytic coating layer has excellent electron transmission capability, so that the photocatalytic degradation effect is better compared with other photocatalytic building materials, and self-cleaning and efficient removal of organic pollutants in the environment can be realized.
Description
Technical Field
The invention relates to a high-toughness cement-based composite wallboard with a photocatalytic function and a preparation method thereof, belonging to the technical field of functional building materials.
Background
The high-toughness cement-based composite material has the characteristics of strain hardening and multi-joint cracking, and has excellent performances in the aspects of safety, durability, applicability and the like. The high-toughness cement-based composite material can well solve various defects caused by brittleness and weak stretchability of the traditional concrete. The traditional wallboard material has the defects of large thickness, low strength, easy cracking, poor durability and the like, and the wallboard prepared by adopting the high-toughness cement-based composite material can well solve the problems.
The photocatalytic technology is one of effective methods for solving environmental problems due to the advantages of high degradation rate, complete degradation and the like of degrading organic matters through oxidation-reduction reaction by utilizing solar energy. There have been many patents and scientific researches for developing building materials with photocatalytic function to self-clean and degrade organic pollutants in the environment starting from the conventional building materials. The most important ability for photocatalytic materials is electron transport ability, and the existing photocatalytic building materials generally have weak electron transport ability and poor photocatalytic effect. The graphene oxide material has strong electron transmission capability, can effectively improve the electron transmission capability of a composite material system, improves the separation efficiency of photoproduction electrons and holes, expands the photoresponse range and improves the photocatalysis efficiency.
Based on the above, there is a need to develop a high-toughness cement-based composite wallboard with a photocatalytic function, which not only has excellent mechanical properties, but also has a high photocatalytic capability, and realizes self-cleaning and efficient degradation of organic pollutants in the environment.
Disclosure of Invention
The invention mainly overcomes the defects in the prior art, and provides the high-toughness cement-based composite wallboard with the photocatalytic function and the preparation method thereof.
The technical scheme provided by the invention for solving the technical problems is as follows: a high-toughness cement-based composite wallboard with a photocatalytic function comprises a high-toughness cement-based composite wallboard matrix and a photocatalytic coating layer;
the high-toughness cement-based composite wallboard matrix is composed of the following raw materials in parts by weight: 90-130 parts of ordinary portland cement, 90-130 parts of fly ash, 6-12 parts of sulphoaluminate cement, 10-18 parts of silica fume, 10-16 parts of microbeads, 4-6 parts of polymer fibers, 0-0.2 part of cellulose ether, 0.8-2 parts of an additive, 54-70 parts of water and 60-80 parts of ultrafine powder;
the photocatalytic coating layer is prepared from the following raw materials in parts by weight: 40-55 parts of polymer emulsion, 10-22 parts of magnesium phosphate cement, 5-11 parts of nano zinc oxide, 0.05-0.15 part of dispersing agent, 0.05-0.15 part of defoaming agent, 2-4 parts of graphene oxide and 5-9 parts of water.
The further technical scheme is that the high-toughness cement-based composite wallboard matrix consists of the following components in parts by weight: 105 parts of ordinary portland cement, 110 parts of fly ash, 8 parts of sulphoaluminate cement, 12 parts of silica fume, 13 parts of microbeads, 5 parts of polymer fibers, 0.1 part of cellulose ether, 1 part of an additive, 60 parts of water and 68 parts of ultrafine powder.
The photocatalytic coating layer is prepared from the following raw materials in parts by weight: 50 parts of polymer emulsion, 18 parts of magnesium phosphate cement, 9 parts of nano zinc oxide, 0.07 part of dispersing agent, 0.11 part of defoaming agent, 4 parts of graphene oxide and 8 parts of water.
The further technical scheme is that the additive is a water reducing agent, the water reducing agent is a naphthalene-based or polycarboxylic acid-based high-efficiency water reducing agent, and the polycarboxylic acid-based high-efficiency water reducing agent is preferred.
The technical scheme is that the polymer fiber is one or a combination of two or more of polypropylene fiber, polyacrylonitrile fiber, polyvinyl alcohol fiber and aramid fiber, the diameter range of the polymer fiber is 30-60um, and the length of the polymer fiber is 6-16 mm; the tensile strength of the fiber needs to be more than 1300MPa, the elastic modulus needs to be more than or equal to 35GPa, the elongation at break is more than or equal to 8 percent, and the polymer fiber is preferably one or the combination of two of polyacrylonitrile fiber and polyvinyl alcohol fiber.
The further technical scheme is that the fly ash is I-grade fly ash.
The further technical scheme is that the defoaming agent is one of organic silicon defoaming agents, polyether defoaming agents, fatty acids defoaming agents and phosphate defoaming agents.
The further technical scheme is that the dispersant is one of fatty acid, fatty acid amide and ester dispersant, wherein the fatty acid amide dispersant is preferable.
A preparation method of a high-toughness cement-based composite wallboard with a photocatalytic function comprises the following steps:
(1) preparation of high-toughness cement-based composite wallboard matrix
Weighing ordinary portland cement, fly ash, sulphoaluminate cement, silica fume, micro-beads, ultrafine powder and cellulose ether according to the weight part ratio of the raw materials, adding the raw materials into a stirrer, and stirring the mixture at a low speed for 2 to 3 minutes until the mixture is uniform; weighing an additive and water according to a proportion, dissolving the additive in the water, pouring the mixture into a stirrer, and stirring at a low speed for 2-3 minutes to form uniform cement paste; weighing polymer fibers, adding the polymer fibers into the cement slurry, stirring at a low speed for 2-3 minutes, and then stirring at a high speed for 1-2 minutes until the polymer fibers are uniformly dispersed in the slurry; injecting the stirred slurry into a wallboard mould prepared in advance, removing the mould after pre-curing for 1 day, and continuing curing for 28 days to prepare a high-toughness cement-based composite wallboard matrix;
(2) preparing a photocatalytic coating layer:
weighing magnesium phosphate cement, nano zinc oxide and graphene oxide according to the weight parts of the raw materials, adding the raw materials into a stirrer, and stirring at a low speed for 3-5 minutes to obtain uniformly mixed powder; weighing polymer emulsion, a dispersing agent, a defoaming agent and water, and mixing and stirring for 4-6 minutes to obtain organic liquid; mixing and stirring the powder and the organic liquid for 4-5 minutes to prepare the photocatalytic coating;
(3) coating the photocatalytic coating on the outer side of the high-toughness cement-based composite wallboard matrix, and controlling the total thickness to be 0.7-2mm to prepare the high-toughness cement-based composite wallboard with the photocatalytic function.
Compared with the prior art, the invention has the following advantages:
(1) the high-toughness cement-based composite wallboard with the photocatalytic function has excellent mechanical property and good durability;
(2) by utilizing the characteristic of high electron transmission capability of the graphene oxide material, the high-toughness cement-based composite wallboard with the photocatalytic function has high photocatalytic capability, and can self-clean and efficiently degrade organic pollutants in the environment.
Drawings
FIG. 1 is a schematic structural diagram of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
Example 1
As shown in fig. 1, the high-toughness cement-based composite wallboard with a photocatalytic function of the invention comprises a high-toughness cement-based composite wallboard substrate 1 and a photocatalytic coating layer 2.
The preparation method comprises the following steps:
(1) preparation of high-toughness cement-based composite wallboard matrix
1050g of ordinary portland cement, 1100g of fly ash, 80g of sulphoaluminate cement, 120g of silica fume, 130g of microbeads, 680g of ultrafine powder and 1g of cellulose ether are weighed and added into a stirrer, and the mixture is stirred at low speed for 3 minutes until the mixture is uniform; weighing 10g of polycarboxylic acid water reducing agent and 600g of water, dissolving the polycarboxylic acid water reducing agent in the water, pouring the solution into a stirrer, and stirring the solution at a low speed for 3 minutes to form uniform cement paste; weighing 50g of polyvinyl alcohol fiber, adding the fiber into the cement slurry, stirring at a low speed for 3 minutes, and then stirring at a high speed for 2 minutes until the polyvinyl alcohol fiber is uniformly dispersed in the slurry; and injecting the stirred slurry into a mold, carrying out precuring for 1 day, then removing the mold, and continuing curing for 28 days.
(2) Preparation of photocatalytic coatings
Weighing 18g of magnesium phosphate cement, 9g of nano zinc oxide and 4g of graphene oxide, adding into a stirrer, and stirring at a low speed for 5 minutes to obtain uniformly mixed powder; weighing 50g of polymer emulsion, 0.07g of fatty acid amide dispersing agent, 0.11g of polyether defoaming agent and 8g of water, and mixing and stirring for 6 minutes to obtain organic liquid; and mixing and stirring the powder and the organic liquid for 5 minutes to prepare the photocatalytic coating.
(3) Coating the photocatalytic coating on the outer side of the high-toughness cement-based composite wallboard matrix, and controlling the total thickness to be about 0.7mm to prepare the high-toughness cement-based composite wallboard with the photocatalytic function.
Example 2
The invention relates to a high-toughness cement-based composite wallboard with a photocatalytic function, which is prepared by the following steps:
(1) preparation of high-toughness cement-based composite wallboard matrix
Weighing 900g of ordinary portland cement, 1250g of fly ash, 120g of sulphoaluminate cement, 100g of silica fume, 155g of micro-beads, 750g of ultrafine powder and 1.5g of cellulose ether, adding into a stirrer, and stirring at low speed for 2 minutes until the mixture is uniform; weighing 8g of naphthalene water reducer and 750g of water, dissolving the naphthalene water reducer in the water, pouring the mixture into a stirrer, and stirring at a low speed for 3 minutes to form uniform cement paste; weighing 45g of polyacrylonitrile fibers, adding the fibers into the cement slurry, stirring at a low speed for 3 minutes, and then stirring at a high speed for 1 minute until the polyvinyl alcohol fibers are uniformly dispersed in the slurry; and injecting the stirred slurry into a mold, carrying out precuring for 1 day, then removing the mold, and continuing curing for 28 days.
(2) Preparation of photocatalytic coatings
Weighing 13g of magnesium phosphate cement, 8g of nano zinc oxide and 3g of graphene oxide, adding into a stirrer, and stirring at a low speed for 4 minutes to obtain uniformly mixed powder; weighing 45g of polymer emulsion, 0.05g of ester dispersant, 0.14g of phosphate defoamer and 7g of water, and mixing and stirring for 5 minutes to obtain organic liquid; and mixing and stirring the powder and the organic liquid for 5 minutes to prepare the photocatalytic coating.
(3) Coating the photocatalytic coating on the outer side of the high-toughness cement-based composite wallboard matrix, and controlling the total thickness to be about 1.0mm to prepare the high-toughness cement-based composite wallboard with the photocatalytic function.
Example 3
The invention relates to a high-toughness cement-based composite wallboard with a photocatalytic function, which is prepared by the following steps:
(1) preparation of high-toughness cement-based composite wallboard matrix
(2) Weighing 1150g of ordinary portland cement, 950g of fly ash, 70g of sulphoaluminate cement, 130g of silica fume, 110g of micro-beads, 800g of ultrafine powder and 0.5g of cellulose ether, adding into a stirrer, and stirring at low speed for 3 minutes until the mixture is uniform; weighing 12g of polycarboxylic acid water reducing agent and 700g of water, dissolving the polycarboxylic acid water reducing agent in the water, pouring the solution into a stirrer, and stirring the solution at a low speed for 3 minutes to form uniform cement paste; weighing 60g of aramid fiber, adding the fiber into the cement slurry, stirring at a low speed for 4 minutes, and then stirring at a high speed for 1 minute until the polyvinyl alcohol fiber is uniformly dispersed in the slurry; and injecting the stirred slurry into a mold, carrying out precuring for 1 day, then removing the mold, and continuing curing for 28 days.
(3) Preparation of photocatalytic coatings
Weighing 20g of magnesium phosphate cement, 10g of nano zinc oxide and 2g of graphene oxide, adding into a stirrer, and stirring at a low speed for 4 minutes to obtain uniformly mixed powder; weighing 55g of polymer emulsion, 0.15g of fatty acid dispersant, 0.12g of silicone defoaming agent and 9g of water, and mixing and stirring for 5 minutes to obtain organic liquid; and mixing and stirring the powder and the organic liquid for 5 minutes to prepare the photocatalytic coating.
(3) And coating the photocatalytic coating on the outer side of the high-toughness cement-based composite wallboard matrix, and controlling the total thickness to be about 1.4mm to prepare the high-toughness cement-based composite wallboard with the photocatalytic function.
Example 4
The invention relates to a high-toughness cement-based composite wallboard with a photocatalytic function, which is prepared by the following steps:
(1) preparation of high-toughness cement-based composite wallboard matrix
Weighing 1000g of ordinary portland cement, 1100g of fly ash, 80g of sulphoaluminate cement, 120g of silica fume, 100g of microbeads, 700g of ultrafine powder and 0.6g of cellulose ether, adding into a stirrer, and stirring at a low speed for 3 minutes until the mixture is uniform; weighing 13g of polycarboxylic acid water reducing agent and 800g of water, dissolving the polycarboxylic acid water reducing agent in the water, pouring the solution into a stirrer, and stirring the solution at a low speed for 3 minutes to form uniform cement paste; weighing 40g of polypropylene fiber, adding the fiber into the cement slurry, stirring at a low speed for 3 minutes, and then stirring at a high speed for 1 minute until the polyvinyl alcohol fiber is uniformly dispersed in the slurry; and injecting the stirred slurry into a mold, carrying out precuring for 1 day, then removing the mold, and continuing curing for 28 days.
(2) Preparation of photocatalytic coatings
Weighing 19g of magnesium phosphate cement, 11g of nano zinc oxide and 3g of graphene oxide, adding into a stirrer, and stirring at a low speed for 4 minutes to obtain uniformly mixed powder; weighing 48g of polymer emulsion, 0.10g of fatty acid amide dispersing agent, 0.11g of phosphate defoaming agent and 8g of water, and mixing and stirring for 4 minutes to obtain organic liquid; and mixing and stirring the powder and the organic liquid for 3 minutes to prepare the photocatalytic coating.
(3) And coating the photocatalytic coating on the outer side of the high-toughness cement-based composite wallboard matrix, and controlling the total thickness to be about 1.7mm to prepare the high-toughness cement-based composite wallboard with the photocatalytic function.
And (3) performance detection: the composite wall boards prepared in the embodiments 1-4 are detected according to GB/T50081-2002 'test method for mechanical property of common concrete' and JGJ 1-2014 'technical specification of prefabricated concrete structure'; the composite wallboards prepared in examples 1-4 were used to catalyze and degrade 100mL of 5mg/L rhodamine solution, and 400W xenon lamp was used as the photocatalytic light source.
Table 1 the examples have the following test items and results:
in conclusion, the high-toughness cement-based composite wallboard with the photocatalytic function consists of the photocatalytic coating layer 2 and the high-toughness cement-based composite wallboard matrix 1. The high-toughness cement-based composite wallboard with the photocatalytic function has excellent mechanical property and good durability, and the preparation method is simple and easy to operate. In addition, the prepared photocatalytic coating layer has excellent electron transmission capability, has better photocatalytic degradation effect compared with other photocatalytic building materials, and can realize self-cleaning and high-efficiency removal of organic pollutants in the environment.
Although the present invention has been described with reference to the above embodiments, it should be understood that the present invention is not limited to the above embodiments, and those skilled in the art can make various changes and modifications without departing from the scope of the present invention.
Claims (10)
1. A high-toughness cement-based composite wallboard with a photocatalytic function is characterized in that the high-toughness cement-based composite wallboard consists of a high-toughness cement-based composite wallboard matrix and a photocatalytic coating layer;
the high-toughness cement-based composite wallboard matrix is composed of the following raw materials in parts by weight: 90-130 parts of ordinary portland cement, 90-130 parts of fly ash, 6-12 parts of sulphoaluminate cement, 10-18 parts of silica fume, 10-16 parts of microbeads, 4-6 parts of polymer fibers, 0-0.2 part of cellulose ether, 0.8-2 parts of an additive, 54-70 parts of water and 60-80 parts of ultrafine powder;
the photocatalytic coating layer is prepared from the following raw materials in parts by weight: 40-55 parts of polymer emulsion, 10-22 parts of magnesium phosphate cement, 5-11 parts of nano zinc oxide, 0.05-0.15 part of dispersing agent, 0.05-0.15 part of defoaming agent, 2-4 parts of graphene oxide and 5-9 parts of water.
2. The high-toughness cement-based composite wallboard with photocatalytic function according to claim 1, wherein the high-toughness cement-based composite wallboard matrix is composed of the following components in parts by weight: 105 parts of ordinary portland cement, 110 parts of fly ash, 8 parts of sulphoaluminate cement, 12 parts of silica fume, 13 parts of microbeads, 5 parts of polymer fibers, 0.1 part of cellulose ether, 1 part of an additive, 60 parts of water and 68 parts of ultrafine powder.
The photocatalytic coating layer is prepared from the following raw materials in parts by weight: 50 parts of polymer emulsion, 18 parts of magnesium phosphate cement, 9 parts of nano zinc oxide, 0.07 part of dispersing agent, 0.11 part of defoaming agent, 4 parts of graphene oxide and 8 parts of water.
3. The high-toughness cement-based composite wallboard with a photocatalytic function according to claim 1 or 2, characterized in that the admixture is a water reducing agent, and the water reducing agent is one of a naphthalene-based or polycarboxylic acid-based high-efficiency water reducing agent.
4. The high-toughness cement-based composite wallboard with photocatalytic function according to claim 2, wherein said water reducing agent is a polycarboxylic acid high-efficiency water reducing agent.
5. The high-toughness cement-based composite wallboard with the photocatalytic function as claimed in claim 3, wherein the polymer fiber is one or a combination of two or more of polypropylene fiber, polyacrylonitrile fiber, polyvinyl alcohol fiber and aramid fiber, the diameter range of the polymer fiber is 30-60um, and the length of the polymer fiber is 6-16 mm; the tensile strength of the fiber needs to be more than 1300MPa, the elastic modulus needs to be more than or equal to 35GPa, and the elongation at break is more than or equal to 8%.
6. The high-toughness cement-based composite wallboard with photocatalytic function as claimed in claim 5, wherein said fly ash is class I fly ash.
7. The high-toughness cement-based composite wallboard with photocatalytic function as claimed in claim 6, wherein said defoamer is one of silicone defoamer, polyether defoamer, fatty acid defoamer and phosphate defoamer.
8. The high toughness cement-based composite wallboard with photocatalytic function as claimed in claim 7, wherein said dispersant is one of fatty acid, fatty acid amide and ester dispersant.
9. The high toughness cement-based composite wallboard with photocatalytic function as claimed in claim 8, wherein said dispersant is fatty acid amide dispersant.
10. A preparation method of a high-toughness cement-based composite wallboard with a photocatalytic function is characterized by comprising the following steps:
(1) preparation of high-toughness cement-based composite wallboard matrix
Weighing ordinary portland cement, fly ash, sulphoaluminate cement, silica fume, micro-beads, ultrafine powder and cellulose ether according to the weight part ratio of the raw materials, adding the raw materials into a stirrer, and stirring the mixture at a low speed for 2 to 3 minutes until the mixture is uniform; weighing an additive and water according to a proportion, dissolving the additive in the water, pouring the mixture into a stirrer, and stirring at a low speed for 2-3 minutes to form uniform cement paste; weighing polymer fibers, adding the polymer fibers into the cement slurry, stirring at a low speed for 2-3 minutes, and then stirring at a high speed for 1-2 minutes until the polymer fibers are uniformly dispersed in the slurry; injecting the stirred slurry into a wallboard mould prepared in advance, removing the mould after pre-curing for 1 day, and continuing curing for 28 days to prepare a high-toughness cement-based composite wallboard matrix;
(2) preparing a photocatalytic coating layer:
weighing magnesium phosphate cement, nano zinc oxide and graphene oxide according to the weight parts of the raw materials, adding the raw materials into a stirrer, and stirring at a low speed for 3-5 minutes to obtain uniformly mixed powder; weighing polymer emulsion, a dispersing agent, a defoaming agent and water, and mixing and stirring for 4-6 minutes to obtain organic liquid; mixing and stirring the powder and the organic liquid for 4-5 minutes to prepare the photocatalytic coating;
(3) coating the photocatalytic coating on the outer side of the high-toughness cement-based composite wallboard matrix, and controlling the total thickness to be 0.7-2mm to prepare the high-toughness cement-based composite wallboard with the photocatalytic function.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911056707.3A CN110803903A (en) | 2019-10-31 | 2019-10-31 | High-toughness cement-based composite wallboard with photocatalytic function and preparation method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911056707.3A CN110803903A (en) | 2019-10-31 | 2019-10-31 | High-toughness cement-based composite wallboard with photocatalytic function and preparation method |
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| CN110803903A true CN110803903A (en) | 2020-02-18 |
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| CN201911056707.3A Pending CN110803903A (en) | 2019-10-31 | 2019-10-31 | High-toughness cement-based composite wallboard with photocatalytic function and preparation method |
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| JPH10158079A (en) * | 1996-11-25 | 1998-06-16 | Fujita Corp | Concrete block having air cleaning function |
| CN104211358A (en) * | 2014-09-11 | 2014-12-17 | 中国中材国际工程股份有限公司 | Rapid-hardening early strength high-ductility cement-based composite material and preparation method thereof |
| CN107035092A (en) * | 2017-03-31 | 2017-08-11 | 中民筑友科技投资有限公司 | A kind of ultra-high performance concrete Decorative hanging board and its manufacture craft with automatically cleaning photo-catalysis function |
| CN108439938A (en) * | 2018-04-20 | 2018-08-24 | 南京倍立达欧陆装饰艺术工程有限公司 | A kind of photocatalysis glass magnesium board and preparation method thereof |
| CN108587441A (en) * | 2018-03-27 | 2018-09-28 | 华豹（天津）新材料科技发展股份有限公司 | A kind of watersoluble plumbago alkene acroleic acid polyurethane coating and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10158079A (en) * | 1996-11-25 | 1998-06-16 | Fujita Corp | Concrete block having air cleaning function |
| CN104211358A (en) * | 2014-09-11 | 2014-12-17 | 中国中材国际工程股份有限公司 | Rapid-hardening early strength high-ductility cement-based composite material and preparation method thereof |
| CN107035092A (en) * | 2017-03-31 | 2017-08-11 | 中民筑友科技投资有限公司 | A kind of ultra-high performance concrete Decorative hanging board and its manufacture craft with automatically cleaning photo-catalysis function |
| CN108587441A (en) * | 2018-03-27 | 2018-09-28 | 华豹（天津）新材料科技发展股份有限公司 | A kind of watersoluble plumbago alkene acroleic acid polyurethane coating and preparation method thereof |
| CN108439938A (en) * | 2018-04-20 | 2018-08-24 | 南京倍立达欧陆装饰艺术工程有限公司 | A kind of photocatalysis glass magnesium board and preparation method thereof |
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