CN113402965A - High-bio-based-content single-component polyurethane waterproof coating and preparation method thereof - Google Patents
High-bio-based-content single-component polyurethane waterproof coating and preparation method thereof Download PDFInfo
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- CN113402965A CN113402965A CN202110882011.7A CN202110882011A CN113402965A CN 113402965 A CN113402965 A CN 113402965A CN 202110882011 A CN202110882011 A CN 202110882011A CN 113402965 A CN113402965 A CN 113402965A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a high-bio-based content single-component polyurethane waterproof coating and a preparation method thereof, and the high-bio-based content single-component polyurethane waterproof coating is prepared from the following components in parts by mass: 2-functionality polyether polyol, 3-functionality polyether polyol, castor oil, a bio-based plasticizer, isophorone diisocyanate, an environment-friendly high-efficiency catalyst, a non-silicon defoaming agent, polyamide wax and high-purity oleic acid. The high-biobased-content single-component polyurethane waterproof coating disclosed by the invention meets the tensile property and mechanical property of GB/T19250-2013I-type standard, is high in biobased content, transparent in film layer, good in light transmission and color permeability, can be used in a decorative material, is compact in film coating and excellent in mechanical property, and can be stored at 30 ℃ for 6 months. The high-biobased-content single-component polyurethane waterproof coating has the A-type standard requirement of JC/T1066-2008, and the biobased content is more than 70%.
Description
Technical Field
The invention relates to a high-bio-based content single-component polyurethane waterproof coating and a preparation method thereof.
Background
The key of the competition of comprehensive national power of all countries in the world lies in knowledge innovation, technical innovation and high-tech industrialization. As a high and new technology, the technology of bio-based polyurethane has been developed and produced in many countries, and it is said that the most advanced technology is the future development market, the polyurethane waterproof coating is the first developed and used in the united states, and the technology of the united states is introduced in 1964 in japan for production. The industrial production of polyurethane is started in the early stage of the 20 th century in China, and the polyurethane material is applied to the waterproof coating in the early 80 th, so that the polyurethane waterproof coating has good environment adaptability. When it is contacted with the moisture in the air, it can be solidified, so that a seamless integral anti-film is formed on the surface of the base layer, the tensile strength of the coating film is high, the flexibility is strong, and the base layer can not be affected even if it is cracked and stretched, so that the adaptability is strong, and the anti-water coating film is shown according to the viscosity development report of the water-proofing association: the total yield of the building waterproof material in 2019 is expected to reach 24.2 hundred million square meters, and the same-proportion growth rate is expected to be 9.4%. The waterproof coating accounts for 28.09%, and the polyurethane waterproof coating accounts for 30.26% of the total amount of the waterproof coating. The demand of waterproof paint is continuously increased and the quantity is huge, but the raw materials mostly adopt common petroleum products, and with the continuous expansion of the scale of global bio-based chemicals, the bio-based polyurethane industry in China will be rapidly developed. The China polyurethane industry Association indicates that the China polyurethane industry currently focuses on developing renewable resource type bio-based polyurethane raw materials which utilize renewable resources and are suitable for circular economy, and particularly the technical research and development of non-edible vegetable oil base.
Disclosure of Invention
The high-biobased-content single-component polyurethane waterproof coating disclosed by the invention meets the tensile property and mechanical property of GB/T19250-2013I type standard, is high in biobased content, transparent in film layer, good in light transmission and color permeability, can be used in a decorative material, is compact in film coating, excellent in mechanical property and can be stored for 6 months at 30 ℃ through detection.
The invention is realized by the following technical scheme:
a high-bio-based-content single-component polyurethane waterproof coating is prepared from the following components in parts by mass:
a preparation method of a high-bio-based-content single-component polyurethane waterproof coating comprises the following steps:
putting 2-functionality polyether polyol, castor oil, high-purity oleic acid and a bio-based plasticizer into a negative pressure reaction kettle, setting the stirring speed to be 300-0 r/min (keeping the stirring speed in the following steps), and then draining for 2-4h at the temperature of 115-125 ℃ and the pressure of-0.09-0.1 MPa;
then closing the negative pressure, adding isophorone diisocyanate at the temperature of 75-85 ℃, and then stirring for 1-3h at the constant temperature of 80-90 ℃;
then adding polyamide wax at the temperature of 55-65 ℃ and stirring for 10-30min at constant temperature; then adding an environment-friendly high-efficiency catalyst and a non-silicon defoaming agent, and stirring at constant temperature for 20-40 min;
and maintaining at 45-55 deg.C under-0.03-0.05 mpa for 25-35 min.
The traditional polyurethane waterproof coating mainly comprises isocyanate, polyether polyol, a plasticizer, inorganic powder, a functional assistant and a diluent, wherein the bio-based polyurethane is generally prepared by reacting bio-based polyol with synthetic isocyanate, because the instability and complex functionality of the bio-based polyol are difficult to be used in the polyurethane waterproof coating, the addition amount of the polyol in the actual polyurethane waterproof coating formula is not more than 30 percent, and even if all the bio-based polyol is adopted, the bio-based content is not high. Meanwhile, the problem of TDI free content is solved by adopting isophorone diisocyanate as the isocyanate raw material, the solid content of the product can reach 99.8 percent, the severe environment-friendly requirement can be met, and a product with high bio-based content can be obtained.
In the aspect of performance, polyether with 2 functionality and polyether with 3 functionality and isophorone diisocyanate which is excessive according to a certain proportion are adopted to be crosslinked to form a prepolymer with excessive-NCO, the prepolymer containing the-NCO group reacts with air and moisture on a contact surface in the using process to generate unstable carbamate, then the carbamate is decomposed to continue to react with the excessive-NCO, and finally the polyurethane elastomer waterproof coating is formed.
Compared with the prior art, the invention has the following beneficial effects: the high-biobased-content single-component polyurethane waterproof coating disclosed by the invention meets the tensile property and mechanical property of GB/T19250-2013I-type standard, is high in biobased content, transparent in film layer, good in light transmission and color permeability, can be used in a decorative material, is compact in film coating and excellent in mechanical property, and can be stored at 30 ℃ for 6 months.
The high-biobased-content single-component polyurethane waterproof coating has the A-type standard requirement of JC/T1066-2008, and the biobased content is more than 70%.
Detailed description of the preferred embodiments
Example 1
A high-bio-based-content single-component polyurethane waterproof coating is prepared from the following components in parts by mass:
a preparation method of a high-bio-based-content single-component polyurethane waterproof coating comprises the following steps:
putting 2-functionality polyether polyol, castor oil, a bio-based plasticizer and high-purity oleic acid into a negative pressure reaction kettle, setting the stirring speed to be 400r/min, and draining for 3 hours at the temperature of 120 ℃ and the pressure of-0.095 Mpa;
then closing the negative pressure, adding isophorone diisocyanate at the temperature of 80 ℃, and then stirring for 2 hours at the constant temperature of 85 ℃;
then adding polyamide wax at 60 ℃, and stirring for 20min at constant temperature; then adding an environment-friendly high-efficiency catalyst and a non-silicon defoaming agent, and stirring for 30min at constant temperature;
and maintaining at 50 deg.C under-0.04 mpa for 30 min.
Example 2
A high-bio-based-content single-component polyurethane waterproof coating is prepared from the following components in parts by mass:
a preparation method of a high-bio-based-content single-component polyurethane waterproof coating comprises the following steps:
putting 2-functionality polyether polyol, castor oil, a bio-based plasticizer and high-purity oleic acid into a negative pressure reaction kettle, setting the stirring speed to be 300r/min, and then draining for 2 hours at the temperature of 115 ℃ and the pressure of-0.09 Mpa;
then closing the negative pressure, adding isophorone diisocyanate at the temperature of 75 ℃, and then stirring for 1h at the constant temperature of 80 ℃;
then adding polyamide wax at 55 ℃, and stirring for 10min at constant temperature; then adding an environment-friendly high-efficiency catalyst and a non-silicon defoaming agent, and stirring at constant temperature for 20 min;
and maintaining at 45 deg.C under-0.03 mpa for 25 min.
Example 3
A high-bio-based-content single-component polyurethane waterproof coating is prepared from the following components in parts by mass:
a preparation method of a high-bio-based-content single-component polyurethane waterproof coating comprises the following steps:
putting 2-functionality polyether polyol, castor oil, a bio-based plasticizer and high-purity oleic acid into a negative pressure reaction kettle, setting the stirring speed to be 500r/min, and draining for 4 hours at the temperature of 125 ℃ and the pressure of-0.1 Mpa;
then closing the negative pressure, adding isophorone diisocyanate at the temperature of 85 ℃, and then stirring for 3 hours at the constant temperature of 90 ℃;
then adding polyamide wax at 65 ℃, and stirring for 30min at constant temperature; then adding an environment-friendly high-efficiency catalyst and a non-silicon defoaming agent, and stirring for 40min at constant temperature;
and maintaining at 55 deg.C under-0.05 mpa for 35 min.
The tensile property and mechanical property of the waterproof coating of the embodiment after coating is measured according to GB/T19250-2013 type I standard, the waterproof coating meets the standard requirement, and the product can pass the A-type standard requirement through the detection according to the test of the JC/T1066-2008 method, and the result is shown in Table 1.
In the above embodiments of the present invention, the preferred sources of the components are as follows: the 2-functionality polyether polyol is WANOL C2020 of Wanhua chemical group Co., Ltd, the 3-functionality polyether polyol is WANOL F3135 of Wanhua chemical group Co., Ltd, the bio-based plasticizer is commercially available methyl chloropalmitolate, and the isophorone diisocyanate is Wanhua chemical group Co., Ltd
The environment-friendly high-efficiency catalyst is GuangzhouWCAT-WS2 drier from Youngen synthetic materials Co., Ltd, wherein the defoamer is a commercially available non-silicon defoamer, the polyamide wax is a commercially available product, and the high-purity oleic acid is vegetable oleic acid.
Table 1 results of performance testing of examples 1-3
Claims (4)
1. A high-bio-based-content single-component polyurethane waterproof coating is characterized in that: the composition is prepared from the following components in parts by mass:
2. the high-biobased-content one-component polyurethane waterproof coating material as claimed in claim 1, wherein: the environment-friendly high-efficiency catalyst is a WCAT-WS2 drier from Guangzhou Youyun synthetic materials Co.
3. The high-biobased-content one-component polyurethane waterproof coating material as claimed in claim 1, wherein: the high-purity oleic acid is vegetable oleic acid.
4. A method for preparing the high bio-based content one-component polyurethane waterproof coating material according to any one of claims 1 to 3, characterized in that: the method comprises the following steps:
putting 2-functionality polyether polyol, 3-functionality polyether polyol, castor oil, high-purity oleic acid and a bio-based plasticizer into a negative pressure reaction kettle, setting the stirring speed at 300-;
then closing the negative pressure, adding isophorone diisocyanate at the temperature of 75-85 ℃, and then stirring for 1-3h at the constant temperature of 80-90 ℃;
then adding polyamide wax at 55-65 ℃, and stirring for 10-30min at constant temperature; then adding an environment-friendly high-efficiency catalyst and a non-silicon defoaming agent, and stirring at constant temperature for 20-40 min;
and maintaining at 45-55 deg.C under-0.03-0.05 mpa for 25-35 min.
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Cited By (2)
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| CN114213958A (en) * | 2021-12-20 | 2022-03-22 | 胜利油田大明新型建筑防水材料有限责任公司 | Biomass oil-based single-component polyurethane waterproof paint and preparation method thereof |
| CN117659349A (en) * | 2023-12-14 | 2024-03-08 | 广东华博润材料科技有限公司 | Bio-based moisture-hardening polyurethane and preparation method and application thereof |
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Cited By (3)
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