CN110951304A - Self-flame-retardant oleyl polyether-2 phosphate terminated polyurethane water-based paint - Google Patents
Self-flame-retardant oleyl polyether-2 phosphate terminated polyurethane water-based paint Download PDFInfo
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Abstract
The invention relates to a self-flame-retardant oleyl polyether-2 phosphate ester end-capped polyurethane water-based paint, which comprises the following basic formula in parts by weight: 100.0-150.0 parts of oleyl polyether-2 phosphate ester end-capped aqueous polyurethane resin, 30.0-60.0 parts of fluorine modified aqueous polyurethane resin, 10-50.0 parts of filler, 5.0-20.0 parts of aqueous nano color paste, 0.3-1.0 part of wetting agent, 0.5-1.5 parts of dispersing agent, 0.3-1.0 part of defoaming agent, 0.3-1.2 parts of thickening and leveling agent, 0.5-2.0 parts of pH regulator, 6.0-15.0 parts of film-forming assistant and 15.0-50.0 parts of deionized water; according to the self-flame-retardant oleyl polyether-2 phosphate ester end-capped polyurethane water-based paint prepared by the invention, phosphorus elements are positioned at two ends of water-based polyurethane and are not easy to coat; the leveling property of the coating film is good in the film forming process, sagging is not generated, a flame retardant is not required to be added, and the flame retardant property is durable; the coating film has good adhesive force, hardness, fullness and corrosion resistance; it is widely used for surface protection and decoration of woodware, metal and the like.
Description
Technical Field
The invention relates to a modified polyurethane flame-retardant coating, in particular to a self-flame-retardant oleyl polyether-2 phosphate terminated polyurethane water-based coating, belonging to the technical field of water-based functional coatings.
Background
The polyurethane coating has excellent performances of abrasion resistance, flexibility, adhesive force, chemical resistance and the like, and is widely used as wood paint, building paint, automobile paint, waterproof paint and the like at present. Most of polyurethane is flammable material, and in order to protect the safety of people's lives and properties, the development of flame retardant polyurethane has become a hotspot in recent years. At present, the flame retardant is mainly added to achieve the purpose of flame retardance, and the small molecular flame retardant has the defects of easy migration, non-lasting flame retardant effect and the like, and even can damage the physical properties of the polyurethane resin. In recent years, when polyurethane is prepared, a part of monomer with flame retardant elements is added, so that intrinsic flame retardant polyurethane can be prepared, the defect of the addition type flame retardant polyurethane can be overcome, and simultaneously, excellent comprehensive performance is endowed to polyurethane resin.
The water-based polyurethane coating is a water-based coating which takes water-dispersed polyurethane resin as a base material and takes water as a dispersing agent in the construction application process. Compared with the traditional solvent-based paint, the water-based polyurethane paint has the greatest advantage of greatly reducing the using amount of volatile organic solvent or basically eliminating the existence of the solvent, thereby meeting the requirement of environmental protection. Therefore, the method has wide application prospect. Meanwhile, in order to improve the living standard of people and meet the industrial requirements, the development of the water-based flame-retardant polyurethane coating is urgently needed, and the water-based flame-retardant polyurethane coating is applied to the surfaces of high-grade kitchen furniture, chemical equipment and the like.
Chinese patent CN109705719A discloses a flame-retardant waterborne polyurethane coating which comprises the following raw materials in parts by weight: 40-65 parts of diisocyanate, 10-25 parts of polytetrahydrofuran ether glycol, 15-30 parts of phosphorus modified dihydric alcohol, 2-5.5 parts of hydrophilic chain extender, 2-5 parts of dimethyl silicone oil, 3-5.5 parts of pentaerythritol, 0.1-0.2 part of dibutyltin dilaurate, 0.5-2 parts of triethylamine, 0.1-1.5 parts of ethylenediamine, 9-13 parts of gelatin, 0.1-1 part of calcium alginate, 2-3.8 parts of hollow glass beads, 0.3-1.5 parts of cellulose nanocrystals, 0.1-0.8 part of graphene oxide, 3-8 parts of hexamethoxy methyl melamine resin, 0.1-0.8 part of defoaming agent and 10-35 parts of water. However, the phosphorus element is located in the middle of the polymer resin, and is easily coated to affect the flame retardant property.
Chinese patent CN108329823A discloses a flame retardant polyurethane coating, which consists of 75% of component A and 25% of component B, wherein the component A comprises 60-70 parts by weight of waterborne polyether resin, 0.1-0.5 part by weight of aluminum oxide, 1-3 parts by weight of dispersant, 0.1-0.5 part by weight of flatting agent, 0.1-0.5 part by weight of defoaming agent, 0.5-1.0 part by weight of thickening agent, 10-15 parts by weight of pigment, 10-15 parts by weight of modifier and 1-5 parts by weight of flame retardant; the flame retardant comprises, by weight, 20-30 parts of ammonium polyphosphate, 40-50 parts of melamine, 10-15 parts of guanylurea phosphate, 5-10 parts of tea saponin and 10-20 parts of magnesium aluminum hydrotalcite. The invention adopts the external addition of the flame retardant to achieve the flame retardant effect, and the flame retardant has the defects of easy migration, non-lasting flame retardant effect and the like, and even can damage the physical properties of the high polymer resin.
The polyurethane resin has low oxygen index, is a flammable material, has low smoke during combustion, is accompanied with melting and dropping, and needs to be subjected to flame retardant modification treatment along with the continuous improvement of the application range and flame retardant requirements. How to prepare a flame-retardant polyurethane coating with excellent performance is a technical problem which is urgently needed to be solved at present.
Disclosure of Invention
The invention aims to provide a self-flame-retardant oleyl polyether-2 phosphate terminated polyurethane water-based paint.
The self-flame-retardant oleyl polyether-2 phosphate ester end-capped polyurethane water-based paint does not need to be added with a flame retardant, and thoroughly solves the problems that the flame retardant is not uniformly dispersed in the paint and is easy to settle, and the influence of overhigh or overlow pH value of part of the flame retardant on the performance of the paint. Effectively solves the problems that the flame-retardant substance in the film-forming substance of the existing self-flame-retardant coating is easily coated by macromolecular resin, the flame-retardant efficiency is not high, and the like.
In order to solve the problems, the invention adopts oleyl polyether-2 phosphate terminated waterborne polyurethane resin with good flame retardant function as a film forming substance, and phosphorus element with flame retardant function is connected with the waterborne polyurethane resin structure through a chemical bond; and the phosphorus element is positioned at the two ends of the waterborne polyurethane resin and is not easy to be coated.
The invention relates to a self-flame-retardant oleyl polyether-2 phosphate ester end-capped polyurethane water-based paint, which comprises the following basic formula in parts by weight: 100.0-150.0 parts of oleyl polyether-2 phosphate ester end-capped aqueous polyurethane resin, 30.0-60.0 parts of fluorine modified aqueous polyurethane resin, 10-50.0 parts of filler, 5.0-20.0 parts of aqueous nano color paste, 0.3-1.0 part of wetting agent, 0.5-1.5 parts of dispersing agent, 0.3-1.0 part of defoaming agent, 0.3-1.2 parts of thickening and leveling agent, 0.5-2.0 parts of pH regulator, 6.0-15.0 parts of film forming additive and 15.0-50.0 parts of deionized water.
The fluorine modified waterborne polyurethane resin is prepared by reacting fluorine-containing polyether polyol, oligomer polyol, dimethylolpropionic acid, 1, 4-butanediol, ethylenediamine, polyisocyanate and a neutralizing agent.
The filler is one or a combination of several of red mud micro powder, silicon carbide, zeolite powder, mica powder, barium sulfate, bentonite, kaolin, calcium carbonate and titanium dioxide.
The pH regulator is one or a combination of more of AMP-95, sodium bicarbonate, ammonia water and triethylamine.
The oleyl polyether-2 phosphate ester terminated waterborne polyurethane resin comprises the following components in parts by weight: 22.0-48.0 parts of polyisocyanate, 20.0-42.0 parts of oligomer polyether polyol, 5.0-9.0 parts of oleyl polyether-2 phosphate, 4.0-10.0 parts of 1, 4-cyclohexane dimethanol, 1.0-3.0 parts of hydroxyethyl acrylate, 2.2-5.0 parts of dimethylolpropionic acid, 0.03-0.08 part of dibutyltin dilaurate, 1.5-2.5 parts of ethanol, 2.0-10.0 parts of a neutralizer and 100.0-200.0 parts of deionized water.
The preparation process of the oleyl polyether-2 phosphate ester terminated waterborne polyurethane resin comprises the following steps:
a) sequentially adding oligomer polyether polyol, 1, 4-cyclohexanedimethanol and dimethylolpropionic acid in parts by weight of the formula into a multifunctional reactor, heating to 110-120 ℃, and carrying out vacuum dehydration;
b) cooling to 65 ℃, adding polyisocyanate and introducing N2Stirring and reacting at 75 ℃ for 1.0h, then heating to 88-90 ℃ for reacting for 2.0-2.5 h, and adding a proper amount of solvent to adjust viscosity;
c) reducing the temperature to 78-82 ℃, adding hydroxyethyl acrylate and dibutyltin dilaurate in a formula amount, stirring for reaction for 1.0-1.5 h, then adding oleyl polyether-2 phosphate for heat preservation for reaction for 1.5-2.0 h, and detecting until the NCO value is consistent with a designed value;
d) cooling to below 50 ℃, adding a neutralizing agent, continuing stirring for reaction, adding a calculated amount of deionized water, dispersing uniformly at a high speed, finally adding ethanol, removing a solvent, and filtering to obtain the oleyl polyether-2 phosphate ester terminated waterborne polyurethane resin.
The solvent is acetone, and the solvent added in the invention only plays a role in adjusting the viscosity of a reaction system and is added according to the change of the viscosity.
The invention relates to a oleyl polyether-2 phosphate ester terminated waterborne polyurethane resin, which is based on the applied invention patent of 'a oleyl polyether-2 phosphate ester terminated waterborne polyurethane resin and a preparation method thereof', and is described in detail.
According to the self-flame-retardant oleyl polyether-2 phosphate ester end-capped polyurethane water-based paint prepared by the invention, phosphorus elements are positioned at two ends of water-based polyurethane and are not easy to coat; the leveling property of the coating film is good in the film forming process, sagging is not generated, a flame retardant is not required to be added, and the flame retardant property is durable; the coating film has good adhesive force, hardness, fullness and corrosion resistance; it is widely used for surface protection and decoration of woodware, metal and the like.
Detailed Description
The present invention is further described with reference to the following examples in which a self-flame retardant oleyl polyether-2 phosphate terminated polyurethane waterborne coating is described. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
In the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
A self-flame-retardant oleyl polyether-2 phosphate ester end-capped polyurethane water-based paint comprises the following basic formula in parts by weight: 100.0-150.0 parts of oleyl polyether-2 phosphate ester end-capped aqueous polyurethane resin, 30.0-60.0 parts of fluorine modified aqueous polyurethane resin, 10-50.0 parts of filler, 5.0-20.0 parts of aqueous nano color paste, 0.3-1.0 part of wetting agent, 0.5-1.5 parts of dispersing agent, 0.3-1.0 part of defoaming agent, 0.3-1.2 parts of thickening and leveling agent, 0.5-2.0 parts of pH regulator, 6.0-15.0 parts of film forming additive and 15.0-50.0 parts of deionized water.
In a further embodiment, the fluorine-modified aqueous polyurethane resin is prepared by reacting fluorine-containing polyether polyol, oligomer polyol, dimethylolpropionic acid, 1, 4-butanediol, ethylenediamine, polyisocyanate and a neutralizing agent.
As a further implementation mode, the filler is one or a combination of several of red mud micro powder, silicon carbide, zeolite powder, mica powder, barium sulfate, bentonite, kaolin, calcium carbonate and titanium dioxide.
In a further embodiment, the pH regulator is one or a combination of more of AMP-95, sodium bicarbonate, ammonia water and triethylamine.
Example 1
An oleyl polyether-2 phosphate ester terminated waterborne polyurethane resin A is prepared by the following steps:
a) sequentially adding 30.0 parts of polytetrahydrofuran diol, 6.5 parts of 1, 4-cyclohexanedimethanol and 3.6 parts of dimethylolpropionic acid in the multifunctional reactor according to the weight part of the formula, heating to 115 ℃, and performing vacuum dehydration;
b) cooling to 65 ℃, adding 38.0 parts of isophorone diisocyanate, and introducing N2Stirring and reacting at 75 ℃ for 1.0h, then heating to 88-90 ℃ for reacting for 2.0, and adding a proper amount of solvent to adjust viscosity;
c) reducing the temperature to 78-82 ℃, adding 2.0 parts of hydroxyethyl acrylate and 0.05 part of dibutyltin dilaurate according to the formula amount, stirring for reaction for 1.5h, then adding 8.0 parts of oleyl polyether-2 phosphate, keeping the temperature for reaction for 2.0h, and detecting until the NCO value is consistent with the designed value;
d) cooling to 45 ℃, adding 4.2 parts of triethylamine, continuing stirring for reaction, adding 170.0 parts of deionized water according to the calculated amount, uniformly dispersing at a high speed, finally adding 2.0 parts of ethanol, removing a solvent, and filtering to obtain the oleyl polyether-2 phosphate ester terminated waterborne polyurethane resin A.
Example 2
A preparation process of the oleyl polyether-2 phosphate ester terminated waterborne polyurethane resin B comprises the following steps:
a) adding 25.0 parts of polyether glycol, 8.0 parts of 1, 4-cyclohexanedimethanol and 4.0 parts of dimethylolpropionic acid in a multifunctional reactor in sequence according to the weight parts of the formula, heating to 110 ℃, and carrying out vacuum dehydration;
b) cooling to 65 ℃, adding 34.0 parts of hexamethylene diisocyanate, and introducing N2Stirring and reacting at 75 ℃ for 1.0h, then heating to 88-90 ℃ for reacting for 2.5h, and adding a proper amount of solvent to adjust viscosity;
c) reducing the temperature to 78-82 ℃, adding 1.8 parts of hydroxyethyl acrylate and 0.06 part of dibutyltin dilaurate in a formula amount, stirring for reaction for 1.0-1.5 h, adding 7.0 parts of oleyl polyether-2 phosphate, keeping the temperature for reaction for 2.0h, and detecting until the NCO value is consistent with a designed value;
d) cooling to 48 ℃, adding 3.8 parts of ammonia water, continuing stirring for reaction, adding 165.0 parts of deionized water according to the calculated amount, uniformly dispersing at a high speed, finally adding 1.9 parts of ethanol, removing a solvent, and filtering to obtain the oleyl polyether-2 phosphate ester terminated waterborne polyurethane resin B.
Example 3
A self-flame-retardant oleyl polyether-2 phosphate ester end-capped polyurethane water-based paint comprises the following components in parts by weight: 125.0 parts of oleyl polyether-2 phosphate terminated aqueous polyurethane resin A, 45.0 parts of fluorine modified aqueous polyurethane resin, 10.0 parts of kaolin, 10.0 parts of calcium carbonate, 10.0 parts of titanium dioxide, 10.0 parts of aqueous nano color paste, 0.6 part of wetting agent, 1.1 parts of dispersing agent, 0.7 part of defoaming agent, 0.6 part of thickening and leveling agent, 12.5 parts of AMP-951.2 parts of film forming auxiliary agent and 30.0 parts of deionized water.
1) Uniformly stirring the oleyl polyether-2 phosphate ester terminated waterborne polyurethane resin A, the fluorine modified waterborne polyurethane resin and the film-forming additive according to the weight part of the formula to obtain waterborne premixed resin;
2) putting deionized water, a wetting agent, a dispersing agent and a defoaming agent into a dispersing tank according to the weight part of the formula, and uniformly stirring; adding kaolin, calcium carbonate and titanium dioxide under the condition of low-speed stirring, and then dispersing at a high speed until the fineness is less than or equal to 20 mu m;
3) then adding the aqueous nano color paste to disperse uniformly, slowly adding the aqueous premixed resin under low-speed stirring, stirring for 30min, adding the film-forming assistant, AMP-95 and the thickening and leveling agent, stirring for 20 min, filtering and packaging.
Example 4
A self-flame-retardant oleyl polyether-2 phosphate ester end-capped polyurethane water-based paint comprises the following components in parts by weight: 110.0 parts of oleyl polyether-2 phosphate terminated waterborne polyurethane resin B, 50.0 parts of fluorine modified waterborne polyurethane resin, 5.0 parts of silicon carbide, 5.0 parts of zeolite powder, 10.0 parts of mica powder, 15.0 parts of aqueous nano color paste, 0.5 part of wetting agent, 0.8 part of dispersing agent, 0.5 part of defoaming agent, 0.8 part of thickening and leveling agent, 1.0 part of triethylamine, 10.0 parts of film forming auxiliary agent and 30.0 parts of deionized water.
1) Uniformly stirring the oleyl polyether-2 phosphate ester terminated waterborne polyurethane resin B, the fluorine modified waterborne polyurethane resin and the film-forming additive according to the weight part of the formula to obtain waterborne premixed resin;
2) putting deionized water, a wetting agent, a dispersing agent and a defoaming agent into a dispersing tank according to the weight part of the formula, and uniformly stirring; adding silicon carbide, zeolite powder and mica powder under the condition of low-speed stirring, and then dispersing at a high speed until the fineness is less than or equal to 20 mu m;
3) then adding the aqueous nano color paste to disperse uniformly, slowly adding the aqueous premixed resin by low-speed stirring, stirring for 30min, then adding the film-forming assistant, triethylamine and the thickening and leveling agent, stirring for 20 min, filtering and packaging.
The examples of the present invention and the conventional aqueous polyurethane coating (comparative example 1) were subjected to performance index tests in accordance with the relevant standards of water resistance (GB/T1733-1993), adhesion (GB/T9286-1998), salt spray resistance (GB/T1771-2007), pencil hardness (GB/T6739-1996), flexibility (GB/T1731-1993), acid resistance ((10% HCl) GB/T1763-1979), alkali resistance ((10% NaOH) GB/1763-1979), filiform corrosion (GB/T13452.4-92), impact resistance (GB/T1732-1993), contact angle (GB/T30693-2014), etc., and the results of the tests are shown in Table 1.
Table 1: performance specification of coating
| Detecting items | Example 3 | Coating 4 | Comparative example 1 |
| Water resistance | 30d | 30d | 10d |
| Adhesion force | Level 0 | Level 0 | Level 1 |
| Hardness of pencil | 2H | 2H | H |
| Resistance to salt fog | 1000h | 920h | 480h |
| Acid resistance | 960h | 840h | 480h |
| Alkali resistance | 960h | 840h | 480h |
| Filiform corrosion | Light and slight | Light and slight | Severe severity of disease |
| Impact resistance | Normal paint film | Normal paint film | Color loss of paint film |
| Flexibility/mm | 1 | 1 | 2 |
| Contact angle | 128° | 120° | 75° |
It can be seen from table 1 that the adhesion, salt spray resistance, filiform corrosion, water resistance, acid and alkali resistance and other properties of the samples of the examples of the present invention far exceed those of the conventional waterborne polyurethane coating, and the contact angle of the examples of the present invention is greater than 90 °, whereas the contact angle of the conventional waterborne polyurethane coating (comparative example 1) is less than 90 °, which indicates that the self-flame retardant oleyl polyether-2 phosphate ester terminated polyurethane waterborne coating of the present invention has low surface tension and good stain resistance.
According to the relevant GB12441-2005 standard, the flame retardant performance of the embodiment of the invention and the flame retardant coating (comparative example 2) on the market is tested, and the test results are shown in Table 2.
Table 2: technical index of flame retardant property of coating
| Detecting items | Technical index | Example 3 | Example 4 | Comparative example 2 |
| Flame resistance time/min | ≥15min | 33min | 31min | 21min |
| Ratio of flame propagation | ≤25 | 15.8 | 16.1 | 21.8 |
| Loss of mass | ≤5.0g | 3.1 | 3.4 | 4.3 |
| Carbonization volume | ≤25cm3 | 15.6 | 15.9 | 21.5 |
It can be seen from table 2 that the flame retardant properties of the example samples of the present invention and the comparative example samples are qualified, but the flame retardant time of the example samples of the present invention far exceeds the flame retardant time of the flame retardant coating on the market (comparative example 2), and the mass loss, the flame propagation ratio and the carbonization volume are smaller than those of the flame retardant coating on the market (comparative example 2), which indicates that the self-flame retardant oleyl polyether-2 phosphate ester terminated polyurethane water-based coating of the present invention has good flame retardant properties, and the flame retardant properties of the self-flame retardant oleyl polyether-2 phosphate ester terminated polyurethane water-based coating are far better than those of the flame retardant coating on the market.
The self-flame-retardant oleyl polyether-2 phosphate terminated polyurethane water-based paint disclosed by the invention does not need an additional flame retardant, and has good flame retardant performance, the content of free flame retardant monomers in a paint sample is detected by adopting a gas chromatography and an element analysis in the embodiment of the invention, and the test result is shown in table 3.
Table 3: free flame retardant monomer content in the examples
| Item | Example 3 | Example 4 |
| Initial testing: free flame retardant monomer content | 0.02% | 0.03% |
| Simulating 3 years of natural aging: free flame retardant monomer content | 0.08% | 0.09% |
As shown in Table 3, the self-flame-retardant oleyl polyether-2 phosphate terminated polyurethane water-based paint disclosed by the invention is not easy to decompose and fall off as oleyl polyether-2 phosphate is fixed on a resin structure in a chemical bond mode, and the paint has lasting self-flame retardant property without additionally adding other flame retardants, so that the defects that the externally added flame retardant is easy to decompose, fall off, and is not uniformly dispersed and the like are overcome; the flame retardant property is durable and stable.
Although the present invention has been described in detail and with reference to exemplary embodiments thereof, it will be apparent to one skilled in the art that various changes, modifications and variations can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (4)
1. A self-flame-retardant oleyl polyether-2 phosphate ester end-capped polyurethane water-based paint is characterized in that: the basic formula comprises the following components in parts by weight: 100.0-150.0 parts of oleyl polyether-2 phosphate ester end-capped aqueous polyurethane resin, 30.0-60.0 parts of fluorine modified aqueous polyurethane resin, 10-50.0 parts of filler, 5.0-20.0 parts of aqueous nano color paste, 0.3-1.0 part of wetting agent, 0.5-1.5 parts of dispersing agent, 0.3-1.0 part of defoaming agent, 0.3-1.2 parts of thickening and leveling agent, 0.5-2.0 parts of pH regulator, 6.0-15.0 parts of film-forming assistant and 15.0-50.0 parts of deionized water;
the fluorine modified waterborne polyurethane resin is prepared by reacting fluorine-containing polyether polyol, oligomer polyol, dimethylolpropionic acid, 1, 4-butanediol, ethylenediamine, polyisocyanate and a neutralizing agent.
2. The self-flame-retardant oleyl polyether-2 phosphate terminated polyurethane waterborne coating of claim 1, wherein: the oleyl polyether-2 phosphate ester terminated waterborne polyurethane resin comprises the following components in parts by weight: 22.0-48.0 parts of polyisocyanate, 20.0-42.0 parts of oligomer polyether polyol, 5.0-9.0 parts of oleyl polyether-2 phosphate, 4.0-10.0 parts of 1, 4-cyclohexane dimethanol, 1.0-3.0 parts of hydroxyethyl acrylate, 2.2-5.0 parts of dimethylolpropionic acid, 0.03-0.08 part of dibutyltin dilaurate, 1.5-2.5 parts of ethanol, 2.0-10.0 parts of a neutralizer and 100.0-200.0 parts of deionized water.
3. The self-flame-retardant oleyl polyether-2 phosphate terminated polyurethane waterborne coating of claim 1, wherein: the filler is one or a combination of several of red mud micro powder, silicon carbide, zeolite powder, mica powder, barium sulfate, bentonite, kaolin, calcium carbonate and titanium dioxide.
4. The self-flame-retardant oleyl polyether-2 phosphate terminated polyurethane waterborne coating of claim 1, wherein: the pH regulator is one or a combination of more of AMP-95, sodium bicarbonate, ammonia water and triethylamine.
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| CN112323517A (en) * | 2020-12-04 | 2021-02-05 | 静宁县恒达有限责任公司 | Phosphorus-boron heterochain hydroxyl-terminated prepolymer segmented polyurethane copolymer water-based printing and dyeing fireproof coating as well as preparation method and application thereof |
| CN112662296A (en) * | 2020-12-18 | 2021-04-16 | 合众（佛山）化工有限公司 | Polyphenylene sulfide ketone modified polyurethane resin water-based paint |
| CN113061418A (en) * | 2021-03-31 | 2021-07-02 | 海南必凯水性新材料有限公司 | Flame-retardant polyurethane water-based emulsion and preparation method thereof |
| CN114106677A (en) * | 2021-12-09 | 2022-03-01 | 合众（佛山）化工有限公司 | Hydroxypropyl distarch phosphate modified polyurethane resin water-based functional coating |
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| CN115725229A (en) * | 2021-12-06 | 2023-03-03 | 烟台大学 | Self-repairing flame-retardant, molten drop-resistant and abrasion-resistant polyurethane coating material |
| CN115725229B (en) * | 2021-12-06 | 2023-05-23 | 烟台大学 | Self-repairing flame-retardant, anti-dripping and anti-abrasion polyurethane coating material |
| CN114106677A (en) * | 2021-12-09 | 2022-03-01 | 合众（佛山）化工有限公司 | Hydroxypropyl distarch phosphate modified polyurethane resin water-based functional coating |
| CN114133823A (en) * | 2021-12-23 | 2022-03-04 | 合众（佛山）化工有限公司 | Self-flame-retardant modified polyurethane-epoxy resin water-based paint with good wettability |
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