CN119708422A - Flame-retardant waterborne polyurethane coating agent and preparation method thereof - Google Patents
Flame-retardant waterborne polyurethane coating agent and preparation method thereof Download PDFInfo
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- CN119708422A CN119708422A CN202411918696.6A CN202411918696A CN119708422A CN 119708422 A CN119708422 A CN 119708422A CN 202411918696 A CN202411918696 A CN 202411918696A CN 119708422 A CN119708422 A CN 119708422A
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Abstract
The application belongs to the technical field of surface treatment agent production, and discloses a flame-retardant waterborne polyurethane coating agent, which is obtained by carrying out chain extension on a prepolymer obtained by nucleophilic reaction on polyester polyol and diisocyanate through a chain extender, wherein the chain extender contains organic molecules carrying hydroxyl groups and phosphorus elements simultaneously, and the number of the hydroxyl groups in a single organic molecule is not less than 2.
Description
Technical Field
The application relates to the technical field of surface treatment agent production, in particular to a flame-retardant waterborne polyurethane coating agent and a preparation method thereof.
Background
Polyurethane has been developed to date, and is widely applied to the fields of construction, traffic, household appliances, furniture and the like due to the characteristics of high strength, high wear resistance and the like. The synthesis of polyurethanes generally requires the use of large amounts of organic solvents, which can be harmful to the environment and to the personnel in contact. In recent years, with the enhancement of environmental awareness and the strict national restrictions on volatile organic compounds, aqueous polyurethane which hardly needs organic solvents in the preparation process is gaining importance. Compared with the traditional solvent-based polyurethane, the waterborne polyurethane has the remarkable advantages of strong adhesive force, no volatile organic compounds, no energy waste and the like, greatly reduces the market demand of the traditional solvent-based polyurethane, and gradually shows the trend of replacing the traditional solvent-based polyurethane.
In recent years, the demand for aqueous coating materials has increased, and in addition to pursuing high performance, "multifunctionalization" has become a major development hotspot for aqueous coating materials. The waterborne polyurethane is used as a high-end product in the waterborne coating, various modified coating varieties are common, and the waterborne polyurethane is widely applied in the fields of furniture, buildings, traffic and the like. However, the molecular chain of the aqueous polyurethane mainly comprises C, N, O, H and other elements, and the Limiting Oxygen Index (LOI) is only about 18 percent, which belongs to inflammable substances, so that the flame retardant modification of the aqueous polyurethane becomes a current research hot spot.
The flame-retardant waterborne polyurethane can be divided into a physical additive type and a chemical reaction type according to different preparation modes, the additive type does not generate chemical reaction in the preparation process, and the modification effect can be achieved only by physically blending a sufficient amount of flame retardant with the waterborne polyurethane emulsion.
However, the addition amount of the added flame retardant often needs to reach a certain proportion to improve the flame retardant effect, and due to the characteristics of the waterborne polyurethane, the addition amount of the flame retardant is too large, so that emulsion demulsification, precipitation, poor film forming property and the like are easily caused, and meanwhile, the original performance of the waterborne polyurethane such as mechanical performance, light transmittance and the like can be lost.
The chemical reaction type polyurethane comprises aqueous polyurethane obtained by modifying a soft segment, aqueous polyurethane obtained by modifying a hard segment and a chain extender containing a flame retardant element introduced into the polyurethane chain in a chain extension stage.
Chinese patent application 201610012662.X discloses a rear chain-extended flame-retardant high hydrostatic pressure resistant aqueous polyurethane fabric coating agent, which is prepared by the following specific steps:
Dehydrating polyether glycol or polyester glycol and polyether triol at 100-120 ℃, wherein the mass ratio of the polyether glycol or polyester glycol to the polyether triol is 4:1-9:1;
Step two, cooling to 50-90 ℃, adding a solvent for dilution under the protection of nitrogen, and then adding aromatic isocyanate after dilution until the hydroxyl group is reacted completely to obtain a prepolymer, wherein the mass ratio of isocyanate groups to hydroxyl groups of the aromatic isocyanate is 1.2-3.0;
Adding a lipophilic chain extender into the prepolymer obtained in the step II until the hydroxyl groups in the lipophilic chain extender react completely to obtain a solution A, wherein the addition amount of the lipophilic chain extender is 1-2% of the total mass of a system, and the total mass of the system is the sum of the masses of monomer polyether glycol or polyester glycol, polyether triol, aromatic isocyanate, lipophilic chain extender, hydrophilic chain extender and triethylamine;
Adding a hydrophilic chain extender into the solution A obtained in the step three until the hydroxyl groups in the hydrophilic chain extender react completely to obtain a solution B, wherein the addition amount of the hydrophilic chain extender is 3-6% of the total mass of the system;
step five, cooling to room temperature, adding triethylamine into the solution B obtained in the step four for neutralization, and obtaining a solution C after complete reaction;
Step six, stirring the solution C obtained in the step five, adding deionized water at 0-10 ℃ for emulsification, adding a phosphorus-containing diamine flame retardant for post-chain extension reaction, and removing a solvent after the reaction is completed to obtain aqueous polyurethane emulsion, wherein the mass ratio of the amino group of the phosphorus-containing diamine flame retardant to the residual isocyanate groups in the solution C is 0.2-1.0;
When the waterborne polyurethane prepared by the scheme is applied to terylene low stretch yarn cloth, the waterborne polyurethane not only has high hydrostatic pressure resistance (the hydrostatic pressure resistance value is within the range of 20-100 kPa), but also has a certain flame retardant effect (B1 grade in the vertical method of the GB/T5455-1997 textile combustion performance test). The emulsion has good storage stability, and the adhesive film has excellent comprehensive performance, and when the adhesive film is applied to fabric finishing, the coating is transparent, has good hand feeling and good cohesiveness, and is nontoxic and environment-friendly;
further observing step six of the scheme, the scheme realizes the improvement of flame retardant property by introducing phosphorus element into the phosphorus diamine flame retardant in the post chain extension stage.
The scheme needs to solve the problem of how to develop a flame-retardant aqueous polyurethane coating agent which is different from the prior art and has good flame-retardant capability.
Disclosure of Invention
The application aims to provide a flame-retardant aqueous polyurethane coating agent, which is characterized in that a prepolymer is obtained by the reaction between polyester polyol and isocyanate, hydrophilic groups are introduced into the prepolymer, and finally, a chain extender containing phosphorus elements and hydroxyl groups is used for carrying out chain extension treatment to obtain the flame-retardant aqueous polyurethane coating agent with even phosphorus element distribution.
In order to achieve the aim, the application discloses a flame-retardant waterborne polyurethane finishing agent, which is obtained by chain extension of a prepolymer obtained by nucleophilic reaction of polyester polyol and diisocyanate through a chain extender;
the chain extender is an organic molecule containing hydroxyl groups and phosphorus elements, and the number of the hydroxyl groups in the single organic molecule is not less than 2.
Preferably, the organic molecule has a general structural formula as shown in formula 1:
Wherein the R 1 group is selected from alkane or benzene ring with 1-6 carbon atoms.
Preferably, the chain extender comprises at least an organic molecule of the formula shown in formula 2:
Preferably, the chain extender is a mixture of an organic molecule of the structural formula shown in formula 2 and an organic molecule of the structural formula shown in formula 3:
preferably, the composition comprises the following components in parts by weight:
Preferably, the polyester polyol is selected from any one of polyethylene glycol adipate glycol, polybutylene glycol adipate glycol, polycaprolactone glycol.
Preferably, the diisocyanate is at least one selected from dicyclohexylmethane diisocyanate, isophorone diisocyanate and xylylene diisocyanate.
Preferably, the solvent is at least one selected from toluene and acetone.
In addition, the application also discloses a preparation method for preparing the flame-retardant waterborne polyurethane coating agent, which comprises the steps of mixing and reacting ester polyol and diisocyanate to obtain a prepolymer, and then using a chain extender to chain-extend the prepolymer to obtain the flame-retardant waterborne polyurethane coating agent.
Further preferably, the method specifically comprises the following steps:
Step 1, mixing polyester polyol, diisocyanate and a solvent to react for 2-5 hours at the temperature of 70-80 ℃ to obtain a prepolymer;
Step 2, mixing a chain extender and the prepolymer at a temperature of 60-105 ℃ for reaction for 1-3 hours to obtain a chain-extended prepolymer;
And 3, adding 2, 2-dimethylolpropionic acid into the chain-extended prepolymer, reacting for 1-2 hours, adding triethylamine to perform neutralization reaction for 30-50 minutes, and adding deionized water to emulsify to obtain the flame-retardant waterborne polyurethane finishing agent.
The beneficial effects of the application are as follows:
The flame-retardant aqueous polyurethane finishing agent disclosed by the application is characterized in that a prepolymer is obtained through the reaction between polyester polyol and isocyanate, the chain extender containing phosphorus elements and hydroxyl groups is used for carrying out chain extension treatment to obtain the chain-extended prepolymer with uniformly distributed phosphorus elements, and hydrophilic groups are introduced into the prepolymer to obtain the flame-retardant aqueous polyurethane finishing agent with good flame retardant property.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which specific conditions, either conventional or manufacturer-suggested, are not explicitly shown. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Before the examples are shown, the following essential description is first made of the raw materials and the preparation methods involved in the examples:
The raw material information of each example is shown in table 1:
TABLE 1
The preparation method of the polyurethane coating agent in the examples and the comparative examples comprises the following steps:
Step 1, mixing polyester polyol, diisocyanate and a solvent to react for 3.5+/-1 h at the temperature of 75+/-5 ℃ to obtain a prepolymer;
step 2, mixing a chain extender and the prepolymer to react for 2+/-0.5 hours at the temperature of 80+/-15 ℃ to obtain the prepolymer after chain extension;
and 3, adding 2, 2-dimethylolpropionic acid into the chain-extended prepolymer, reacting for 1.5+/-0.5 h, adding triethylamine according to the mass of which is 10+/-2% of the total mass of the prepolymer, performing neutralization reaction for 30-50 min, and adding deionized water for emulsification to obtain the flame-retardant waterborne polyurethane coating agent.
Further, specific formulations are described in the specific description of each example and comparative example.
Examples 1 to 4
The formula of the flame-retardant waterborne polyurethane coating agent is shown in table 2:
TABLE 2
In examples 1 to 4, the polyester polyol was specifically polycaprolactone diol;
the diisocyanate is specifically dicyclohexylmethane diisocyanate;
the solvent is acetone;
The chain extender is an organic molecule with a structural formula shown in a formula II:
example 5
Substantially the same as in example 1, except that an organic molecule having a structural formula shown in formula III was used as the chain extender;
Example 6
Substantially the same as in example 1, except that a mixture of an organic molecule having a structural formula shown in formula II and an organic molecule having a structural formula shown in formula III was used, and the mass ratio of the organic molecule having a structural formula shown in formula II to the organic molecule having a structural formula shown in formula III was 3:1.
Example 7
Substantially the same as in example 1, except that a mixture of an organic molecule having a structural formula shown in formula II and an organic molecule having a structural formula shown in formula III was used, and the mass ratio of the organic molecule having a structural formula shown in formula II to the organic molecule having a structural formula shown in formula III was 4:1.
Example 8
Substantially the same as in example 1, except that a mixture of an organic molecule having a structural formula shown in formula II and an organic molecule having a structural formula shown in formula III was used, and the mass ratio of the organic molecule having a structural formula shown in formula II to the organic molecule having a structural formula shown in formula III was 2:1.
Example 9
Substantially the same as in example 1, except that polyethylene glycol adipate diol was used instead of polycaprolactone diol.
Example 10
Substantially the same as in example 1, except that a mixture of polyethylene glycol adipate glycol and polycaprolactone glycol was used instead of polycaprolactone glycol, and the mass ratio of the polyethylene glycol adipate glycol and the polycaprolactone glycol was 0.8:1.
Example 11
Substantially the same as in example 1, except that isophorone diisocyanate was used instead of dicyclohexylmethane diisocyanate.
Example 12
Substantially the same as in example 1, except that a mixture of isophorone diisocyanate and dicyclohexylmethane diisocyanate was used instead of dicyclohexylmethane diisocyanate, and the mass ratio of isophorone diisocyanate to dicyclohexylmethane diisocyanate was 1:1.
Comparative example 1
Substantially the same as in example 1, except that 1, 2-propanediol was used instead of the organic molecule having the structural formula shown in formula II.
Comparative example 2
Substantially the same as in example 1, except that pentaerythritol phosphate having only one hydroxyl group in a single organic molecule was used instead of the organic molecule shown in formula II.
Comparative example 3
Substantially the same as in example 1, except that phenylphospholamide was used instead of the organic molecule represented by formula II.
Performance test:
with reference to GB/T5454-1997 oxygen index method for textile combustion performance test, limiting Oxygen Index (LOI) of terylene fabrics before and after finishing is measured by a limiting oxygen index analyzer, and the size of a sample is 150mm multiplied by 58mm.
Referring to GB/T5455-1997 vertical method for testing the flame retardant property of textiles, a flame retardant property tester (vertical method) is adopted to measure the flame retardant property of terylene fabrics before and after finishing, the sample size is 80mm multiplied by 300mm, and the test results are shown in Table 3:
TABLE 3 Table 3
Analysis of results:
1. As can be seen from examples 1 to 4, after the four additives are adjusted to a small extent, examples 1 to 4 show no obvious difference in the continuous burning time and smoldering burning time in the vertical burning performance test process, and no molten drop phenomenon is generated, but examples 1 to 4 show a certain difference in the damage length and limiting oxygen index, which is presumably related to the addition amount of the chain extender, the content of phosphorus element is improved along with the increase of the proportion of the chain extender in the polyurethane, so that the more advantageous flame retardant performance is generated;
2. As can be seen from examples 1 and 5, when the organic molecule having the structural formula shown in formula III is used as the chain extender, the damage length and limiting oxygen index thereof are improved to different degrees from those of example 1, and the organic molecule having the structural formula shown in formula III has a lower flame retardant effect than the organic molecule shown in formula II, presumably because the benzene ring structure of the organic molecule shown in formula II provides higher thermal stability and carbonization capability, and a relatively more stable carbon layer is generated during combustion, which can block oxygen and slow down the combustion process;
Further observations of example 6 show that when example 6 is used with a mixture of organic molecules of formula II and organic molecules of formula III as chain extender, the flame retardant properties are not only better than those of example 5, but even better than those of example 1, it is evident from examples 1, 5 that the flame retardant properties of the organic molecules of formula III are inferior to those of example 1, but that the flame retardant properties of the polyurethane of example 6 after mixing of the two are not only better than those of example 5, even example 1, presumably the reason for this is that the decomposition products of the two compounds may react chemically at high temperatures to give a substance with higher flame retardant properties. The chemical synergistic effect can further improve the flame retardant effect of the material;
Further observing examples 7-8 shows that when the mass ratio between the organic molecule shown in formula II and the organic molecule shown in formula III is further adjusted on the basis of example 6, the flame retardant ability of examples 7-8 is reduced compared with example 6, and when the mass ratio between the organic molecule shown in formula II and the organic molecule shown in formula III is 3:1, the chemical reaction of the decomposition products of the two is more sufficient at high temperature, and more substances with high flame retardant property are generated;
3. It can be seen from examples 1 and examples 9-10 that when the polyester polyol is a mixture of polyethylene glycol adipate glycol and polycaprolactone glycol, the flame retardant performance of example 10 further tends to be improved relative to examples 1 and 8, possibly because micro-phase separation structures may be formed inside the materials between the two, and the structures can provide physical barrier effect during combustion, slow heat and mass transfer, and further improve the flame retardant performance of polyurethane;
4. It can be seen from examples 1 and examples 11 to 12 that when the mixture of isophorone diisocyanate and dicyclohexylmethane diisocyanate is used in example 12, the flame retardant properties of the three examples 1, 11 and 12 show a certain tendency to fluctuate, and the flame retardant properties of example 12 show a certain tendency to rise relative to those of example 1 and 11, because the mixture of the two may change the thermal decomposition path of polyurethane to a certain extent, resulting in the generation of more charring products and nonflammable gases, and further improving the flame retardant properties of polyurethane;
5. as can be seen from examples 1 and comparative examples 1 to 2, when the organic molecule lacks phosphorus or the number of hydroxyl groups in the organic molecule is less than 2, the flame retardant properties of comparative examples 1 to 2 all tend to be significantly reduced, and further when comparative example 3 uses an organic compound having phosphorus and 2 amino groups to replace the organic molecule of formula II in example 1, the damage length and limiting oxygen index are still a certain distance from those of example 1, although they are significantly different from those of example 1 in terms of the after-flame time and smoldering time test.
Claims (10)
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