CN115403729B - Fluorine-containing modified polyurethane curing agent and preparation method thereof - Google Patents
Fluorine-containing modified polyurethane curing agent and preparation method thereof Download PDFInfo
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Abstract
The application relates to the technical field of coating curing agents, in particular to a fluorine-containing modified polyurethane curing agent and a preparation method thereof. The fluorine-containing modified polyurethane curing agent is prepared by reacting the following components in percentage by weight: 40-60% of isocyanate; 10-20% of fluorine-containing block copolymer; 0.01-0.02% of catalyst; 2-5% of a regulator; the balance being solvent; the fluorine-containing segmented copolymer is formed by covalent connection reaction of a carboxyl-containing perfluoroalkyl carbon chain and a polyethylene glycol/polyacrylate segmented copolymer; the polyethylene glycol/polyacrylate block copolymer is prepared by the reaction of polyethylene glycol and polyacrylate. The application realizes shortening the curing time and simultaneously can effectively endow the polyurethane resin with excellent hardness and acid and alkali resistance through modifying the curing agent.
Description
Technical Field
The application relates to the technical field of coating curing agents, in particular to a fluorine-containing modified polyurethane curing agent and a preparation method thereof.
Background
The curing agent, also called a setting agent, is a generic term for a substance or mixture that enhances or controls the curing reaction, and can achieve the curing purpose by promoting the irreversible transformation of the thermosetting resin, and is an essential additive in the resin field, wherein the polyurethane curing agent that is most widely used is taken as an example.
Polyurethane curing agents in the related art can be generally classified into TDI, HDI, IPDI and the like according to the selection of an isocyanate main body thereof, and mainly comprise-OH and-NH through-NCO functional groups 2 and-COOH and other functional groups, thereby achieving the purpose of crosslinking and curing.
The curing agent can play a role of crosslinking and meet the actual use requirement, but the common curing construction time is longer, and the drying time of a paint film is about 2-3 hours; and the modification and performance improvement of polyurethane cannot be realized, namely the hardness and acid and alkali resistance of polyurethane resin are further improved.
Disclosure of Invention
In order to solve the technical problems, the application provides the fluorine-containing modified polyurethane curing agent and the preparation method thereof, wherein the curing time of the curing agent is only 50-80min, and the hardness and acid and alkali resistance of polyurethane resin can be effectively improved when the curing agent is applied to polyurethane resin.
In a first aspect, the application provides a fluorine-containing modified polyurethane curing agent, which adopts the following technical scheme:
the fluorine-containing modified polyurethane curing agent is characterized by being prepared by reacting the following components in percentage by weight: 40-60% of isocyanate; 10-20% of fluorine-containing block copolymer; 2-5% of a regulator; the balance being solvent;
the fluorine-containing segmented copolymer is formed by covalent connection reaction of a carboxyl-containing perfluoroalkyl carbon chain and a polyethylene glycol/polyacrylate segmented copolymer; the polyethylene glycol/polyacrylate block copolymer is prepared by the reaction of polyethylene glycol and polyacrylate.
By adopting the technical scheme, the curing agent with the components can endow polyurethane resin with excellent mechanical property and weather resistance by increasing the relative molecular mass of the polyurethane curing agent and utilizing the characteristics of organic fluorine by introducing fluorine elements and/or long fluorocarbon chains in the fluorine-containing segmented copolymer;
the reasons for this analysis may be: fluorine atoms spirally distributed and connected to the main chain of the C-C bond of the fluorine-containing segmented copolymer can effectively protect the main chain, shield and reduce the influence of external adverse factors, so that the acid and alkali resistance of the final resin is improved; and the bond energy of the C-F bond is larger, which is beneficial to improving the hardness of the paint film.
In addition, the method is particularly characterized in that compared with the method for directly introducing fluorine element into polyurethane resin, the method is easier to realize, simultaneously facilitates the quality control of a finished product and the production cost, and can realize the improvement of the performance only by mixing the obtained curing agent with the polyurethane resin to be cured.
Preferably, the isocyanate is selected from one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI) and Hexamethylene Diisocyanate (HDI).
Preferably, the fluorine-containing segmented copolymer is prepared by covalent reaction of carboxyl-containing perfluoroalkyl carbon chains and polyethylene glycol/polyacrylate segmented copolymer according to a feeding ratio of 1 (1.2-1.5) at 27-42 ℃.
Preferably, the carboxyl-containing perfluoroalkyl carbon chain is selected from one or more of perfluoropentanoic acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid and perfluorodecanoic acid
Preferably, the covalent reaction comprises the following specific steps:
firstly, dehydrating a polyethylene glycol/polyacrylate block copolymer, sequentially adding DMF, a carboxyl-containing perfluoroalkyl carbon chain, DMAP and DCC, reacting for 20-28 hours at 27-42 ℃ under argon atmosphere, and then filtering and dialyzing to obtain the fluorine-containing block copolymer;
wherein the feeding ratio of the polyethylene glycol/polyacrylate block copolymer, DMF, carboxyl-containing perfluoroalkyl carbon chain, DMAP and DCC is 1 (3-5) (1.2-1.5) (0.1-0.2) (0.3-0.5).
By adopting the technical scheme, the fluorine-containing segmented copolymer is obtained by covalent reaction under the above conditions and the feeding ratio, and the perfluoroalkyl carbon chain containing carboxyl can be bonded to a plurality of sites of the polyethylene glycol/polyacrylate segmented copolymer through combination, so that the stable introduction of fluorine elements and/or long fluorine carbon chains is realized.
Preferably, the polyethylene glycol/polyacrylate block copolymer is prepared by reacting polyethylene glycol and polyacrylate monomers according to the weight ratio of 1 (2-2.4).
Preferably, the specific preparation steps of the polyethylene glycol/polyester block copolymer are as follows:
firstly, drying polyethylene glycol to remove water, then adding polyacrylate monomers and stannous octoate, and reacting for 4-8 hours at 120-150 ℃ under argon atmosphere;
then removing impurities, washing and freeze-drying to react to obtain the polyethylene glycol/polyacrylate block copolymer; wherein the feeding ratio of the polyethylene glycol to the polyacrylate monomer to the stannous octoate is 1 (2-2.4) (0.01-0.02).
By adopting the technical scheme, the polyethylene glycol/polyacrylate block copolymer prepared by the process and the feeding ratio can be stably and efficiently bonded with the perfluoroalkyl carbon chain, and the analysis is probably due to the fact that the unreacted monomer and the low-boiling point product after the reaction are less, and the bonding site of the perfluoroalkyl carbon chain is stable, so that the introduction amount of fluorine element and/or long-fluorine carbon chain is ensured.
In a second aspect, the application provides a preparation method of a fluorine-containing modified polyurethane curing agent, which adopts the following technical scheme:
the preparation method of the fluorine-containing modified polyurethane curing agent comprises the following specific preparation steps:
the isocyanate and the fluorine-containing segmented copolymer are dehydrated respectively, then mixed at 60-72 ℃, then added with the regulator and the solvent, and reacted at constant temperature for 60-90min to obtain the fluorine-containing modified polyurethane curing agent.
By adopting the technical scheme, the fluorine-containing modified polyurethane curing agent prepared by the steps and the conditions has stable and uniform properties, is easy to control the cost and the quality, can effectively endow polyurethane resin with excellent hardness, acid-base resistance and heat resistance, and can achieve the curing purpose within 50-80 min.
In summary, the application has the following beneficial effects:
1. according to the application, by introducing fluorine elements and/or long fluorocarbon chains in the fluorine-containing segmented copolymer and utilizing the characteristics of a fluorine-philic effect, a C-F bond energy-bond position and the like, excellent mechanical properties and weather resistance can be effectively endowed to a paint film after polyurethane resin is cured into a film;
2. the perfluoroalkyl carbon chain containing carboxyl can be bonded to a plurality of sites of the polyethylene glycol/polyacrylate block copolymer through stable combination, so that the stable introduction of fluorine elements and/or long fluorocarbon chains is realized, and the improvement effect on the performance of a final paint film is ensured;
3. the polyethylene glycol/polyacrylate block copolymer prepared by specific conditions and the feeding ratio can provide a more stable binding site for the binding of perfluoroalkyl carbon chains, so that the introduction amount of fluorine elements and/or long fluorocarbon chains is ensured;
4. the preparation steps of the application are easy to control the cost and the quality, and the obtained fluorine-containing modified polyurethane curing agent has stable and uniform performances, can quickly promote the curing of a paint film when being applied to the curing of polyurethane resin, and endows the paint film with excellent hardness and acid-alkali resistance.
Detailed Description
The present application will be described in further detail with reference to examples.
Application example
Application example 1
A fluorine-containing segmented copolymer is prepared by the following steps:
polyethylene glycol/polyacrylate block copolymer preparation:
firstly, polyethylene glycol PEG1000 is dried and dehydrated for 2 hours at 120 ℃, then polyacrylate monomers and stannous octoate are added, and the mixture reacts for 4 hours at 150 ℃ under argon atmosphere to obtain a crude product;
then removing unreacted monomers and low boiling point products in the crude product through vacuum suction filtration for 1h, washing with deionized water at 60 ℃ for 3 times, and freeze-drying to obtain the polyethylene glycol/polyacrylate block copolymer;
wherein the feeding ratio of polyethylene glycol PEG1000, polyacrylate monomer and stannous octoate is 1:2:0.02.
Covalent ligation reaction:
firstly, carrying out secondary dehydration on a polyethylene glycol/polyacrylate block copolymer at 120 ℃ for 2 hours, sequentially adding DMF, carboxyl-containing perfluoroalkyl carbon chains, DMAP and DCC, reacting at 42 ℃ under argon atmosphere for 20 hours, and then filtering and dialyzing to obtain a fluorine-containing block copolymer;
wherein the feeding ratio of the polyethylene glycol/polyacrylate block copolymer, DMF, carboxyl-containing perfluoroalkyl carbon chain, DMAP and DCC is 1:4:1.2:0.2:0.4;
the carboxyl-containing perfluoroalkyl carbon chain is perfluoro valeric acid.
Application example 2
A fluorine-containing block copolymer was obtained by reacting a polyethylene glycol/polyacrylate block copolymer, DMF, a carboxyl group-containing perfluoroalkyl carbon chain, DMAP and DCC at 36℃under an argon atmosphere for 20 hours, which was different from application example 1.
Application example 3
A fluorine-containing block copolymer was obtained by reacting polyethylene glycol/polyacrylate block copolymer, DMF, carboxyl group-containing perfluoroalkyl carbon chain, DMAP and DCC under argon atmosphere at 27℃for 28 hours, which was different from application example 1.
Application example 4
A fluorine-containing block copolymer was obtained by reacting a polyethylene glycol/polyacrylate block copolymer, DMF, a carboxyl group-containing perfluoroalkyl carbon chain, DMAP and DCC at 60℃under an argon atmosphere for 16 hours, which was different from application example 1.
Application example 5
A fluorine-containing block copolymer was different from application example 1 in that the feeding ratio of polyethylene glycol/polyacrylate block copolymer, DMF, carboxyl group-containing perfluoroalkyl carbon chain, DMAP and DCC was 1:4:1.4:0.2:0.4.
Application example 6
A fluorine-containing block copolymer was different from application example 1 in that the feeding ratio of polyethylene glycol/polyacrylate block copolymer, DMF, carboxyl group-containing perfluoroalkyl carbon chain, DMAP and DCC was 1:4:1.5:0.2:0.4.
Application example 7
A fluorine-containing block copolymer was different from application example 1 in that the feeding ratio of polyethylene glycol/polyacrylate block copolymer, DMF, carboxyl group-containing perfluoroalkyl carbon chain, DMAP and DCC was 1:2:1:0.1:0.1.
Application example 8
A fluorine-containing block copolymer is different from application example 1 in that the carboxyl group-containing perfluoroalkyl carbon chain is composed of perfluoro valeric acid and perfluoro caproic acid in a weight ratio of 1:0.4.
Application example 9
A fluorine-containing block copolymer is different from application example 1 in that the polyethylene glycol/polyacrylate block copolymer is prepared by reacting polyethylene glycol PEG1000, polyacrylate monomer and stannous octoate for 6 hours at 132 ℃ under argon atmosphere.
Application example 10
A fluorine-containing block copolymer is different from the block copolymer of application example 1 in that the fluorine-containing block copolymer is prepared by reacting polyethylene glycol PEG1000, polyacrylate monomer and stannous octoate for 8 hours at 120 ℃ under argon atmosphere.
Application example 11
A fluorine-containing block copolymer is different from the block copolymer of application example 1 in that the fluorine-containing block copolymer is prepared by reacting polyethylene glycol PEG1000, polyacrylate monomer and stannous octoate for 12 hours at 100 ℃ under argon atmosphere.
Application example 12
The fluorine-containing block copolymer is different from application example 1 in that the feeding ratio of polyethylene glycol PEG1000, polyacrylate monomer and stannous octoate is 1:2:0.01.
Application example 13
The fluorine-containing block copolymer is different from application example 1 in that the feeding ratio of polyethylene glycol PEG1000, polyacrylate monomer and stannous octoate is 1:2.2:0.02.
Application example 14
The fluorine-containing block copolymer is different from application example 1 in that the feeding ratio of polyethylene glycol PEG1000, polyacrylate monomer and stannous octoate is 1:2.4:0.02.
Application example 15
The fluorine-containing block copolymer is different from application example 1 in that the feeding ratio of polyethylene glycol PEG1000, polyacrylate monomer and stannous octoate is 1:2.8:0.02.
Performance test
Three groups of curing agents prepared in examples and comparative examples are selected as test objects, and then mixed with aqueous polyurethane resin according to the weight ratio of 1:100, and then the mixture is subjected to the following stepsCuring and forming a film (film thickness 2 mm) under construction conditions of 25 ℃ and 50% humidity; recording the surface drying time T of the paint film 1 min and drying time T 2 min, testing according to GB/T1728-1979 method for determining drying time of paint film and putty film;
and testing pencil hardness and acid and alkali resistance of the paint film, wherein specific detection steps and standards refer to GB/T6739-2006, paint film hardness determination by color paint and varnish pencil method, and GB 1763-1979 (89), paint film chemical resistance determination method.
Examples
Examples 1 to 6
The fluorine-containing modified polyurethane curing agent is prepared by the following preparation steps, wherein the components and the corresponding weights are shown in the following table (calculated according to each 100 kg):
firstly, respectively dehydrating isocyanate and fluorine-containing segmented copolymer, then mixing the isocyanate and the fluorine-containing segmented copolymer at 72 ℃, then adding a regulator and a solvent, and reacting at constant temperature for 60min to obtain the fluorine-containing modified polyurethane curing agent;
wherein the isocyanate is toluene diisocyanate (TDI-100); the fluorine-containing block copolymer was produced in production example 1; the regulator is calcium carbonate with an average particle size of 2 um; the solvent is N, N-Dimethylformamide (DMF).
Table: the fluorine-containing modified polyurethane curing agent in examples 1 to 6 comprises the components and the weight (kg) thereof.
Comparative example 1
A polyurethane curing agent is different from example 1 in that the fluorine-containing block copolymer is not contained in the component and is replaced with an equivalent amount of solvent.
The fluorine-containing modified polyurethane curing agents obtained in examples 1 to 6 and comparative example 1 were extracted as test subjects, and their tack-free times T were then tested according to the above-mentioned measurement procedures and criteria 1 min, time of actual drying T 2 min, pencil hardness and acid and alkali resistance, and the average value of the test results is shown in the following table.
Table: results of Performance test of examples 1-6 and comparative example 1
As can be seen from the table, the fluorine-containing modified polyurethane curing agent prepared in the examples 1-6 can effectively endow the paint film with excellent mechanical properties and acid and alkali resistance after being applied to polyurethane resin, and the pencil hardness is 3H-4H;96h (50 g/L NaOH/50g/L H) 2 SO 4 ) The paint films are all normal;
the curing agent has better curing performance, the surface drying time is only 6-8min, and compared with the comparative example 1 without the fluorine-containing segmented copolymer, the curing agent is shortened by 66-75 percent; the drying time is only 60-71min, which is shortened by 50-58% compared with comparative example 1 without adding fluorine-containing block copolymer;
the curing agent with the components can increase the relative molecular mass of the polyurethane curing agent and endow the polyurethane resin paint film with excellent hardness and acid and alkali resistance by utilizing the characteristics of organic fluorine by introducing fluorine elements and/or long fluorocarbon chains in the fluorine-containing segmented copolymer;
moreover, as can be seen from the data in the above table, example 4 is a preferred example, when the isocyanate amount is constant, the hardness and acid and alkali resistance of the paint film are slightly improved along with the increase of the amount of the fluorine-containing segmented copolymer, but the curing performance of the curing agent is affected correspondingly, and the examples 1-3 are referred to; this can be overcome by increasing the isocyanate usage, see examples 4-6;
in summary, the analysis may be that: fluorine atoms spirally distributed and connected to the main chain of the C-C bond of the fluorine-containing segmented copolymer can effectively protect the main chain, shield and reduce the influence of external adverse factors, so that the acid and alkali resistance of the final resin is improved; and the bond energy of the C-F bond is larger, the thermal stability is high, the heat resistance of the resin is improved, and the hardness and the curing rate of the final paint film are both considered.
Example 7
A fluorine-containing modified polyurethane curing agent is different from example 1 in that the isocyanate is isophorone diisocyanate (IPDI).
Example 8
A fluorine-containing modified polyurethane curing agent is different from example 1 in that the isocyanate is Hexamethylene Diisocyanate (HDI).
The fluorine-containing modified polyurethane curing agents obtained in examples 7 to 8 above were extracted as test subjects, and their tack-free times T were then tested according to the above-mentioned measurement procedures and criteria 1 min, time of actual drying T 2 min, pencil hardness and acid and alkali resistance, and the average value of the test results is shown in the following table.
Table: examples 7-8 Performance test results
As can be seen from the above table, the fluorine-containing modified polyurethane curing agent prepared in examples 1 and 7-8 can effectively endow the paint film with excellent mechanical properties and acid and alkali resistance after being applied to polyurethane resin, and the pencil hardness is 3H;96h (50 g/L NaOH/50g/L H) 2 SO 4 ) The paint films are all normal; the curing performance is also better, and the surface drying time is only 7min; the actual drying time is only 61-65min;
it can be seen that the above-mentioned selection of isocyanate can effectively achieve the crosslinking curing of polyurethane resin and the compounding with fluorine-containing block copolymer, and has a weak influence on practical properties, and in other embodiments, other isocyanates may be used, except that the effect is inferior to the selection of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI) and Hexamethylene Diisocyanate (HDI).
Examples 9 to 15
The difference between the fluorine-containing modified polyurethane curing agent and the example 1 is that the fluorine-containing block copolymer used is different in use condition, and the specific corresponding relation is shown in the following table.
Table: comparison of the use cases of the fluorine-containing Block copolymers in examples 9 to 15
The fluorine-containing modified polyurethane curing agents obtained in examples 9 to 15 above were extracted as test subjects, and their tack-free times T were then tested according to the above-mentioned measurement procedures and criteria 1 min, time of actual drying T 2 min, pencil hardness and acid and alkali resistance, and the average value of the test results is shown in the following table.
Table: examples 9-15 Performance test results
As can be seen from the above table, the fluorine-containing modified polyurethane curing agent prepared in examples 1 and 9-15 can effectively endow the paint film with excellent mechanical properties and acid and alkali resistance after being applied to polyurethane resin, and the pencil hardness is 3H-4H;96h (50 g/L NaOH/50g/L H) 2 SO 4 ) The paint films are all normal; the curing performance is also better, and the surface drying time is only 7-8min; the real drying time is only 60-70min;
the fluorine-containing segmented copolymer is obtained by covalent reaction under the conditions and the feeding ratio, and the perfluoroalkyl carbon chain containing carboxyl can be bonded to a plurality of sites of the polyethylene glycol/polyacrylate segmented copolymer through combination, so that the stable introduction of fluorine elements and/or long fluorine carbon chains is realized;
as is clear from the data of examples 1 and 9-11, the preferable reaction conditions are 27-42 ℃ and the reaction is carried out for 20-28 hours under argon atmosphere, and when the reaction temperature exceeds the conditions and the time is correspondingly shortened, the curing performance is reduced;
as can be seen from the data of examples 1 and 12 to 14, the preferable feed ratio of the polyethylene glycol/polyacrylate block copolymer, DMF, carboxyl group-containing perfluoroalkyl carbon chain, DMAP and DCC is 1 (3-5): 1-2): 0.1-0.2: (0.3-0.5);
in summary, the reason for this analysis may be that the perfluoroalkyl carbon chain after exceeding the above conditions is unstable and/or insufficient in combination with the polyethylene glycol/polyacrylate block copolymer, which in turn affects the stable introduction of fluorine element and/or long fluorocarbon chain, and is unfavorable for the crosslinking curing and modification reinforcing operation of the polyurethane resin by the curing agent.
It should be further specifically noted that when the carboxyl group-containing perfluoroalkyl carbon chain is composed of perfluoro valeric acid and perfluoro caproic acid in a weight ratio of 1:0.4, the properties of the curing agent are improved to different extents, see examples 1 and 15;
therefore, the carboxyl-containing perfluoroalkyl carbon chain has better combination effect with the polyethylene glycol/polyacrylate block copolymer; the two have a compound effect, but other selected carboxyl-containing perfluoroalkyl carbon chains are compounded, so that the effect is generally inferior to a single use effect, and the analysis of the effect is probably influenced by steric hindrance effects among different carbon chains and acting forces of C-F bonds.
Examples 16 to 22
The difference between the fluorine-containing modified polyurethane curing agent and the example 1 is that the fluorine-containing block copolymer used is different in use condition, and the specific corresponding relation is shown in the following table.
Table: comparison of the use cases of the fluorine-containing Block copolymers in examples 16 to 22
The fluorine-containing modified polyurethane curing agents obtained in examples 16 to 22 above were extracted as test subjects, and their tack-free times T were then tested according to the above-mentioned measurement procedures and criteria 1 min, time of actual drying T 2 min, pencil hardness and acid and alkali resistance, and the average value of the test results is shown in the following table.
Table: examples 16 to 22 Performance test results
As can be seen from the above table, the fluorine-containing modified polyurethane curing agent prepared in examples 1 and 16-22 can effectively endow the paint film with excellent mechanical properties and acid and alkali resistance after being applied to polyurethane resin, and the pencil hardness is 3H;96h (50 g/L NaOH/50g/L H) 2 SO 4 ) The paint films are all normal; the curing performance is also better, and the surface drying time is only 6-7min; the real drying time is only 58-66min;
the polyethylene glycol/polyacrylate block copolymer prepared by the process and the feeding ratio can be stably and efficiently combined and bonded with the perfluoroalkyl carbon chain, so that the introduction amount of fluorine element and/or long fluorocarbon chain is ensured, and the crosslinking curing and modification reinforcing operation of the curing agent on polyurethane resin are facilitated.
As can be seen from the data of examples 1 and 16-18, the preferable reaction conditions are 120-150 ℃ and the argon atmosphere, and when the reaction temperature is lower than the conditions, the original solidification performance is difficult to ensure even if the reaction time is prolonged;
as can be seen from the data of examples 1 and 19-22, the preferable feeding ratio of polyethylene glycol, polyacrylate monomer and stannous octoate is 1 (2-2.4): 0.01-0.02;
in summary, the reason for this analysis may be that under the above specific reaction conditions, the number of unreacted monomers and low boiling point products can be ensured to be small, and at the same time, the sites for the perfluoroalkyl carbon chain to be bonded on the polyethylene glycol/polyacrylate block copolymer are relatively stable, so that the introduction amount of fluorine element and/or long fluorocarbon chain is ensured.
The above description is provided for the purpose of enabling those skilled in the art to make modifications and obvious technical teaching of the present embodiment without any creative contribution, as required, after reading the present specification, and is protected by patent law within the scope of the claims of the present application.
Claims (5)
1. The fluorine-containing modified polyurethane curing agent is characterized by being prepared by reacting the following components in percentage by weight: 40-60% of isocyanate; 10-20% of fluorine-containing block copolymer; 2-5% of a regulator; the balance being solvent;
the fluorine-containing segmented copolymer is formed by covalent connection reaction of a carboxyl-containing perfluoroalkyl carbon chain and a polyethylene glycol/polyacrylate segmented copolymer; the polyethylene glycol/polyacrylate block copolymer is prepared by the reaction of polyethylene glycol and polyacrylate;
the isocyanate is selected from one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI) and Hexamethylene Diisocyanate (HDI);
the fluorine-containing segmented copolymer is prepared by covalent reaction of carboxyl-containing perfluoroalkyl carbon chains and polyethylene glycol/polyacrylate segmented copolymer according to a feeding ratio of 1 (1.2-1.5) at 27-42 ℃;
the carboxyl-containing perfluoroalkyl carbon chain is one or more selected from perfluorovaleric acid, perfluorocaproic acid, perfluoroheptanoic acid, perfluorooctanoic acid and perfluorodecanoic acid.
2. The fluorine-containing modified polyurethane curing agent according to claim 1, wherein the covalent reaction comprises the following specific steps:
firstly, dehydrating a polyethylene glycol/polyacrylate block copolymer, sequentially adding DMF, a carboxyl-containing perfluoroalkyl carbon chain, DMAP and DCC, reacting for 20-28 hours at 27-42 ℃ under argon atmosphere, and then filtering and dialyzing to obtain the fluorine-containing block copolymer;
wherein the feeding ratio of the polyethylene glycol/polyacrylate block copolymer, DMF, carboxyl-containing perfluoroalkyl carbon chain, DMAP and DCC is 1 (3-5) (1.2-1.5) (0.1-0.2) (0.3-0.5).
3. The fluorine-containing modified polyurethane curing agent according to claim 1, wherein the polyethylene glycol/polyacrylate block copolymer is prepared by reacting polyethylene glycol and polyacrylate monomers according to a weight ratio of 1 (2-2.4).
4. The fluorine-containing modified polyurethane curing agent according to claim 3, wherein the specific preparation steps of the polyethylene glycol/polyacrylate block copolymer are as follows:
firstly, drying polyethylene glycol to remove water, then adding polyacrylate monomers and stannous octoate, and reacting for 4-8 hours at 120-150 ℃ under argon atmosphere;
then removing impurities, washing and freeze-drying to react to obtain the polyethylene glycol/polyacrylate block copolymer; wherein the feeding ratio of the polyethylene glycol to the polyacrylate monomer to the stannous octoate is 1 (2-2.4) (0.01-0.02).
5. The method for preparing the fluorine-containing modified polyurethane curing agent according to any one of claims 1 to 4, which is characterized by comprising the following specific preparation steps:
the isocyanate and the fluorine-containing segmented copolymer are dehydrated respectively, then mixed at 60-72 ℃, then added with the regulator and the solvent, and reacted at constant temperature for 60-90min to obtain the fluorine-containing modified polyurethane curing agent.
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