CN114195963A - Halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin and preparation method thereof - Google Patents
Halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin and preparation method thereof Download PDFInfo
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Abstract
The invention provides a halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin and a preparation method thereof, wherein the halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin comprises the following components in parts by weight: 50.0-80.0 parts of diisocyanate, 6.0-12.0 parts of epoxy resin, 4.5-10.0 parts of 1, 4-cyclohexanediol, 1.0-3.0 parts of trimethylolpropane, 35.0-85.0 parts of oligomer polyol, 4.0-8.0 parts of dimethylolpropionic acid, 0.01-0.1 part of dibutyltin dilaurate, 2.5-4.0 parts of hydroxyethyl acrylate, 3.5-8.0 parts of allyl polyoxyethylene ether phosphate, 1.5-5.0 parts of ethanol, 30.0-60.0 parts of acetone, 0.3-0.6 part of ammonium persulfate, 3.0-10.0 parts of neutralizer and 200.0-450.0 parts of deionized water; the halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin prepared by the invention is characterized in that allyl polyoxyethylene ether phosphate and polyurethane resin are connected through chemical bonds, so that the structure is stable; the modified polyurethane has the advantages of good wettability, permeability, high crosslinking density, good storage performance, good flame retardance and the like.
Description
Technical Field
The invention relates to a modified waterborne polyurethane-epoxy resin and a preparation method thereof, in particular to a halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin, belonging to the technical field of waterborne synthetic resins.
Background
The polyurethane is prepared by the reaction of oligomer polyol, micromolecular polyol, polyisocyanate and a chain extender, the reaction raw materials and process factors have great influence on the form of a polyurethane material, and the polyurethane resin has excellent wear resistance, temperature resistance, scratch resistance, solvent resistance, radiation resistance and low-temperature elasticity, and is widely applied to the fields of foam plastics, rubber, fibers, coatings, printing ink, adhesives, leather and the like.
Most polyurethane materials are flammable materials, and in order to protect the safety of lives and properties of people, the development of flame retardant polyurethane has become a hotspot in recent years. In order to achieve the required flame retardant performance or grade of the product, the traditional technology often uses halogen-containing flame retardant substances added into the material system, and although the flame retardant performance is better, the usage amount of the halogen-containing flame retardant substances is larger, which causes higher content of halogen elements in the product, and the content of the halogen elements in the product also brings some adverse effects, such as environment pollution and human and animal health influence caused by harmful substances which are difficult to degrade, such as dioxin organic halogen chemical substances, generated at high temperature or during combustion. In addition, the flame retardant is 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.
Chinese patent CN110951042A discloses an oleyl polyether-2 phosphate terminated waterborne polyurethane resin, which 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.
Chinese patent CN109400837A discloses a halogen-free, non-dripping, non-migrating and flame-retardant polyurethane resin, which comprises the following raw materials in percentage by weight: 20-25% of hydroxyl-terminated high polymer polyol, 5-10% of phosphorus-containing high polymer polyol, 1-3% of small molecular chain extender, 0.05-0.1% of antioxidant, 6-10% of diisocyanate and 60-65% of urethane-grade solvent; chinese patent CN105504225A discloses a preparation method of flame-retardant waterborne polyurethane resin, which comprises the following steps: uniformly mixing organophosphorus polyester polyol and modified tetramethylxylylene diisocyanate, heating, preserving heat, cooling, adding 1, 4-butanediol, dimethylolpropionic acid, trimethylolpropane and N, N-dimethylformamide, uniformly mixing, adding zinc naphthenate, heating and preserving heat to obtain a material a; after the material a is cooled, dropwise adding a solution containing triethanolamine and N-methyldiethanolamine, heating, and keeping the temperature to obtain a material b; after the pH value of the material b is adjusted to be neutral, removing the N, N-dimethylformamide in vacuum to obtain the flame-retardant waterborne polyurethane resin; said invention possesses a certain flame-retarding property, but its wettability is poor and permeability is poor.
Modified waterborne polyurethane becomes a trend of industry development, and waterborne polyurethane resin with single performance is difficult to meet the requirement.
Disclosure of Invention
In order to solve the technical problems, the invention adds the allyl polyoxyethylene ether phosphate which contains double bonds and can be connected with the polyurethane resin through chemical bonds, and the performance is stable and durable.
The invention mainly aims to provide a halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin.
The invention also aims to provide a preparation method of the halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin.
In order to solve the technical problems, the invention adopts the following technical scheme: the invention relates to a halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin which comprises the following components in parts by weight: 50.0-80.0 parts of diisocyanate, 6.0-12.0 parts of epoxy resin, 4.5-10.0 parts of 1, 4-cyclohexanediol, 1.0-3.0 parts of trimethylolpropane, 35.0-85.0 parts of oligomer polyol, 4.0-8.0 parts of dimethylolpropionic acid, 0.01-0.1 part of dibutyltin dilaurate, 2.5-4.0 parts of hydroxyethyl acrylate, 3.5-8.0 parts of allyl polyoxyethylene ether phosphate, 1.5-5.0 parts of ethanol, 30.0-60.0 parts of acetone, 0.3-0.6 part of ammonium persulfate, 3.0-10.0 parts of neutralizer and 200.0-450.0 parts of deionized water.
The allyl polyoxyethylene ether phosphate is prepared by the following method:
in the invention, allyl polyoxyethylene ether and P are selected2O5The amount ratio of the substances of (a) to (b) is 2.5: 1; adding weighed allyl polyoxyethylene ether into a three-neck flask provided with a thermometer, a temperature control device and a stirrer, and slowly adding P under the condition of high-speed stirring2O5Controlling the temperature below 50 ℃ in the feeding process, and finishing the feeding of P2O5Then slowly raising the temperature to 70 ℃, keeping the temperature and continuously reacting for 4 hours, adding quantitative water for hydrolysis for 2 hours to complete the synthesis of the phosphate, sampling and measuring the acid value. And (3) cooling to below 50 ℃, neutralizing with 20% sodium hydroxide solution according to the measured acid value result until the PH value is 6-8, keeping the temperature for reaction for a period of time to obtain a crude product, and purifying to obtain the allyl polyoxyethylene ether phosphate.
The oligomer dihydric alcohol is one or a combination of more of polytetrahydrofuran ether glycol, polycarbonate dihydric alcohol, polycaprolactone dihydric alcohol and polypropylene oxide polyhydric alcohol with the molecular weight of 800-3000.
The neutralizing agent is one or a combination of more of triethylamine, ammonia water and dimethylethanolamine.
The diisocyanate is one or a combination of toluene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
The preparation method of the halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin comprises the following steps:
a. sequentially adding 1, 4-cyclohexanediol, trimethylolpropane and oligomer polyol in parts by weight of the formula into a multifunctional reaction kettle, heating to 115-120 ℃, vacuum dehydrating for 1.5h, cooling, adding dimethylolpropionic acid, and uniformly stirring;
b. then, dropwise adding diisocyanate, heating is not needed before dropwise adding is completed, after dropwise adding is completed, adding epoxy resin and dibutyltin dilaurate, controlling the temperature to be 82-84 ℃, stirring and reacting for 2 hours, then adding hydroxyethyl acrylate to continue reacting, supplementing acetone according to the viscosity of the system, determining the NCO value, and when the determined value is close to the theoretical design value;
c. cooling, adding ethanol, slowly dropwise adding a neutralizing agent under the stirring condition, adding a calculated amount of deionized water, continuously stirring for dispersion, and removing acetone to obtain the aqueous polyurethane-epoxy resin prepolymer;
d. preparing a 5% ammonium persulfate aqueous solution in advance, heating the aqueous polyurethane-epoxy resin prepolymer to 80-82 ℃, simultaneously adding the ammonium persulfate aqueous solution and allyl polyoxyethylene ether phosphate for 1.5-2.0 h, then heating to 86-88 ℃, stirring for reaction for 1h, discharging, and filtering to obtain the halogen-free self-flame-retardant modified aqueous polyurethane-epoxy resin.
1) The halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin prepared by the invention is formed by connecting allyl polyoxyethylene ether phosphate with polyurethane resin through chemical bonds, and has a stable structure and lasting performance;
2) the halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin prepared by the invention has the advantages of good wettability, permeability, high crosslinking density, good storage performance, good flame retardance and the like.
Detailed Description
The halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin of the present invention is further described with reference to the following examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
Example 1
A halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin is prepared by the following steps:
the embodiment of the invention relates to a halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin, which comprises the following components in parts by weight: 65.0 parts of toluene diisocyanate, 8.0 parts of epoxy resin, 7.0 parts of 1, 4-cyclohexanediol, 1.5 parts of trimethylolpropane, 55.0 parts of polycarbonate diol, 5.0 parts of dimethylolpropionic acid, 0.04 part of dibutyltin dilaurate, 3.0 parts of hydroxyethyl acrylate, 6.0 parts of allyl polyoxyethylene ether phosphate, 3.0 parts of ethanol, 50.0 parts of acetone, 0.5 part of ammonium persulfate, 4.0 parts of ammonia water and 320.0 parts of deionized water.
The preparation method of the halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin comprises the following steps:
a. sequentially adding 1, 4-cyclohexanediol, trimethylolpropane and polycarbonate dihydric alcohol according to the weight part of the formula into a multifunctional reaction kettle, heating to 115-120 ℃, vacuum dehydrating for 1.5h, cooling, adding dimethylolpropionic acid, and uniformly stirring;
b. then, dropwise adding toluene diisocyanate, heating is not needed before dropwise adding, after dropwise adding, epoxy resin and dibutyltin dilaurate are added, the temperature is controlled to be 82-84 ℃, stirring and reacting are carried out for 2 hours, then hydroxyethyl acrylate is added for continuing reaction, acetone is added according to the system viscosity, the NCO value is measured, and when the measured value is close to the theoretical design value;
c. cooling, adding ethanol, slowly dropwise adding ammonia water under the stirring condition, adding a calculated amount of deionized water, continuously stirring and dispersing, and removing acetone to obtain the aqueous polyurethane-epoxy resin prepolymer;
d. preparing a 5% ammonium persulfate aqueous solution in advance, heating the aqueous polyurethane-epoxy resin prepolymer to 80-82 ℃, simultaneously adding the ammonium persulfate aqueous solution and allyl polyoxyethylene ether phosphate for 1.5h, heating to 84-86 ℃, stirring for reacting for 1h, discharging, and filtering to obtain the halogen-free self-flame-retardant modified aqueous polyurethane-epoxy resin.
Example 2
A halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin is prepared by the following steps:
the embodiment of the invention relates to a halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin, which comprises the following components in parts by weight: 75.0 parts of isophorone diisocyanate, 10.0 parts of epoxy resin, 5.0 parts of 1, 4-cyclohexanediol, 2.5 parts of trimethylolpropane, 70.0 parts of polytetrahydrofuran ether glycol, 6.0 parts of dimethylolpropionic acid, 0.06 part of dibutyltin dilaurate, 3.0 parts of hydroxyethyl acrylate, 7.0 parts of allyl polyoxyethylene ether phosphate, 4.0 parts of ethanol, 60.0 parts of acetone, 0.5 part of ammonium persulfate, 5.8 parts of triethylamine and 340.0 parts of deionized water.
The preparation method of the halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin comprises the following steps:
a. sequentially adding 1, 4-cyclohexanediol, trimethylolpropane and polytetrahydrofuran ether glycol according to the weight part of the formula into a multifunctional reaction kettle, heating to 115-120 ℃, dehydrating for 1.5h in vacuum, cooling, adding dimethylolpropionic acid, and stirring uniformly;
b. then, dripping isophorone diisocyanate (IPDI), without heating before dripping is finished, after dripping is finished, adding epoxy resin and dibutyltin dilaurate, controlling the temperature to be 82-84 ℃, stirring and reacting for 2 hours, then adding hydroxyethyl acrylate to continue reacting, supplementing acetone according to the system viscosity, measuring the NCO value, and when the measured value is close to the theoretical design value;
c. cooling, adding ethanol, slowly dropwise adding triethylamine under the stirring condition, adding a calculated amount of deionized water, continuously stirring and dispersing, and removing acetone to obtain the aqueous polyurethane-epoxy resin prepolymer;
d. preparing a 5% ammonium persulfate aqueous solution in advance, heating the aqueous polyurethane-epoxy resin prepolymer to 80-82 ℃, simultaneously adding the ammonium persulfate aqueous solution and allyl polyoxyethylene ether phosphate for 2.0 hours, heating to 84-86 ℃, stirring for reaction for 1 hour, discharging, and filtering to obtain the halogen-free self-flame-retardant modified aqueous polyurethane-epoxy resin.
Example 3
A halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin is prepared by the following steps:
the embodiment of the invention relates to a halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin, which comprises the following components in parts by weight: 60.0 parts of hexamethylene diisocyanate, 10.0 parts of epoxy resin, 4.5 parts of 1, 4-cyclohexanediol, 3.0 parts of trimethylolpropane, 62.0 parts of polycaprolactone diol, 6.0 parts of dimethylolpropionic acid, 0.07 part of dibutyltin dilaurate, 3.5 parts of hydroxyethyl acrylate, 7.0 parts of allyl polyoxyethylene ether phosphate, 3.0 parts of ethanol, 55.0 parts of acetone, 0.5 part of ammonium persulfate, 8.0 parts of dimethylethanolamine and 290.0 parts of deionized water.
The preparation method of the halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin comprises the following steps:
a. sequentially adding 1, 4-cyclohexanediol, trimethylolpropane and polycaprolactone diol in parts by weight of the formula into a multifunctional reaction kettle, heating to 115-120 ℃, vacuum dehydrating for 1.5h, cooling, adding dimethylolpropionic acid, and uniformly stirring;
b. then, dropwise adding hexamethylene diisocyanate, heating is not needed before dropwise adding is completed, after dropwise adding is completed, epoxy resin and dibutyltin dilaurate are added, the temperature is controlled to be 82-84 ℃, stirring and reacting are carried out for 2 hours, then hydroxyethyl acrylate is added for continuous reaction, acetone is added according to the system viscosity, the NCO value is measured, and when the measured value is close to the theoretical design value;
c. cooling, adding ethanol, slowly dropwise adding dimethylethanolamine under the stirring condition, adding a calculated amount of deionized water, continuously stirring for dispersion, and removing acetone to obtain a waterborne polyurethane-epoxy resin prepolymer;
d. preparing a 5% ammonium persulfate aqueous solution in advance, heating the aqueous polyurethane-epoxy resin prepolymer to 80-82 ℃, simultaneously adding the ammonium persulfate aqueous solution and allyl polyoxyethylene ether phosphate for 2.0 hours, heating to 84-86 ℃, stirring for reaction for 1 hour, discharging, and filtering to obtain the halogen-free self-flame-retardant modified aqueous polyurethane-epoxy resin.
Comparative example 1
The embodiment of the invention relates to a conventional modified waterborne polyurethane resin, which comprises the following components in parts by weight: 68.0 parts of isophorone diisocyanate, 9.0 parts of epoxy resin, 8.0 parts of 1, 4-cyclohexanediol, 1.5 parts of trimethylolpropane, 65.0 parts of polytetrahydrofuran ether glycol, 6.0 parts of dimethylolpropionic acid, 0.06 part of dibutyltin dilaurate, 3.0 parts of hydroxyethyl acrylate, 4.0 parts of ethanol, 50.0 parts of acetone, 0.3-0.6 part of ammonium persulfate, 8.0 parts of butyl acrylate, 5.8 parts of triethylamine and 320.0 parts of deionized water.
The preparation method of the conventional modified waterborne polyurethane resin described in this embodiment includes the following steps:
a. sequentially adding 1, 4-cyclohexanediol, trimethylolpropane and polytetrahydrofuran ether glycol according to the weight part of the formula into a multifunctional reaction kettle, heating to 115-120 ℃, dehydrating for 1.5h in vacuum, cooling, adding dimethylolpropionic acid, and stirring uniformly;
b. then, dripping isophorone diisocyanate (IPDI), without heating before dripping is finished, after dripping is finished, adding epoxy resin and dibutyltin dilaurate, controlling the temperature to be 82-84 ℃, stirring and reacting for 2 hours, then adding hydroxyethyl acrylate to continue reacting, supplementing acetone according to the system viscosity, measuring the NCO value, and when the measured value is close to the theoretical design value;
c. cooling, adding ethanol, slowly dropwise adding triethylamine under the stirring condition, adding a calculated amount of deionized water, continuously stirring and dispersing, and removing acetone to obtain the aqueous polyurethane-epoxy resin prepolymer;
d. preparing a 5% ammonium persulfate aqueous solution in advance, heating the aqueous polyurethane-epoxy resin prepolymer to 80-82 ℃, simultaneously adding the ammonium persulfate aqueous solution and butyl acrylate for 2.0h, heating to 84-86 ℃, stirring for reacting for 1h, discharging, and filtering to obtain the conventional modified aqueous polyurethane resin.
And (3) testing performance indexes: the samples of example 1, example 2, example 3 and comparative example 1 were prepared into coatings according to the raw material formulation in table 1, and the corresponding coating samples were respectively designated as coating 1, coating 2, coating 3 and coating 4, and the properties thereof were respectively tested.
Table 1: coating formulation
The prepared coating is tested for performance indexes according to relevant standards, and the test results are shown in table 2.
Wherein, the adhesive force is as follows: testing was carried out as specified in GB/T1720-1988;
hardness: detecting according to the regulation of GB/T6739-2006;
water resistance: detecting according to the regulation of GB/T1733-93;
flame-retardant time: detecting according to the regulation of GB 12441-2005;
acid resistance (10% HCl): detection is carried out according to the regulations of GB/T1763-1979.
Table 2: performance specification of coating
It can be seen from table 2 that the adhesion, hardness, wettability and flame retardant time of the coating 1, the coating 2 and the coating 3 of the present invention in the examples 1, 2 and 3 are significantly better than those of the coating 4 in the comparative example 1 (conventional modified waterborne polyurethane resin), which shows that the halogen-free self-flame retardant modified waterborne polyurethane-epoxy resin of the present invention has good adhesion, hardness, wettability and flame retardant properties.
The foregoing description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed; it will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.
Claims (5)
1. A halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin is characterized in that: the halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin comprises the following components in parts by weight: 50.0-80.0 parts of diisocyanate, 6.0-12.0 parts of epoxy resin, 4.5-10.0 parts of 1, 4-cyclohexanediol, 1.0-3.0 parts of trimethylolpropane, 35.0-85.0 parts of oligomer polyol, 4.0-8.0 parts of dimethylolpropionic acid, 0.01-0.1 part of dibutyltin dilaurate, 2.5-4.0 parts of hydroxyethyl acrylate, 3.5-8.0 parts of allyl polyoxyethylene ether phosphate, 1.5-5.0 parts of ethanol, 30.0-60.0 parts of acetone, 0.3-0.6 part of ammonium persulfate, 3.0-10.0 parts of neutralizer and 200.0-450.0 parts of deionized water; the allyl polyoxyethylene ether phosphate is prepared by the following method; selecting allyl polyoxyethylene ether and P2O5The amount ratio of the substances of (a) to (b) is 2.5: 1; adding weighed allyl polyoxyethylene ether into a three-neck flask provided with a thermometer, a temperature control device and a stirrer, and slowly adding P under the condition of high-speed stirring2O5Controlling the temperature below 50 ℃ in the feeding process, and finishing the feeding of P2O5Then slowly raising the temperature to 70 ℃, preserving the temperature and continuously reacting for 4 hours, and then adding quantitativeHydrolyzing the water for 2h to complete the synthesis of the phosphate, sampling and measuring the acid value. And (3) cooling to below 50 ℃, neutralizing with 20% sodium hydroxide solution according to the measured acid value result until the PH value is 6-8, keeping the temperature for reaction for a period of time to obtain a crude product, and purifying to obtain the allyl polyoxyethylene ether phosphate.
2. The halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin of claim 1, wherein: the oligomer dihydric alcohol is one or a combination of more of polytetrahydrofuran ether glycol, polycarbonate dihydric alcohol, polycaprolactone dihydric alcohol and polypropylene oxide polyhydric alcohol with the molecular weight of 800-3000.
3. The halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin of claim 1, wherein: the neutralizing agent is one or a combination of more of triethylamine, ammonia water and dimethylethanolamine.
4. The halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin of claim 1, wherein: the diisocyanate is one or a combination of toluene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
5. The halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin of claim 1, wherein: the preparation method of the halogen-free self-flame-retardant modified waterborne polyurethane-epoxy resin comprises the following steps:
a. sequentially adding 1, 4-cyclohexanediol, trimethylolpropane and oligomer polyol in parts by weight of the formula into a multifunctional reaction kettle, heating to 115-120 ℃, vacuum dehydrating for 1.5h, cooling, adding dimethylolpropionic acid, and uniformly stirring;
b. then, dropwise adding diisocyanate, heating is not needed before dropwise adding is completed, after dropwise adding is completed, adding epoxy resin and dibutyltin dilaurate, controlling the temperature to be 82-84 ℃, stirring and reacting for 2 hours, then adding hydroxyethyl acrylate to continue reacting, supplementing acetone according to the viscosity of the system, determining the NCO value, and when the determined value is close to the theoretical design value;
c. cooling, adding ethanol, slowly dropwise adding a neutralizing agent under the stirring condition, adding a calculated amount of deionized water, continuously stirring for dispersion, and removing acetone to obtain the aqueous polyurethane-epoxy resin prepolymer;
d. preparing a 5% ammonium persulfate aqueous solution in advance, heating the aqueous polyurethane-epoxy resin prepolymer to 80-82 ℃, simultaneously adding the ammonium persulfate aqueous solution and allyl polyoxyethylene ether phosphate for 1.5-2.0 h, then heating to 86-88 ℃, stirring for reaction for 1h, discharging, and filtering to obtain the halogen-free self-flame-retardant modified aqueous polyurethane-epoxy resin.
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| CN110951042A (en) * | 2019-12-07 | 2020-04-03 | 合众（佛山）化工有限公司 | Oleyl polyether-2 phosphate ester terminated waterborne polyurethane resin and preparation method thereof |
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| CN109608610A (en) * | 2018-12-13 | 2019-04-12 | 合众（佛山）化工有限公司 | A kind of graphene modified aqueous polyurethane-epoxy resin and preparation method thereof |
| CN109627950A (en) * | 2018-12-14 | 2019-04-16 | 合众（佛山）化工有限公司 | A kind of graphene anticorrosion water-soluble coating |
| CN110452608A (en) * | 2019-09-01 | 2019-11-15 | 合众（佛山）化工有限公司 | A kind of antifouling radiation protection water-base resin of rare earth modified polyurethane-epoxy and preparation method thereof |
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