A bio-based hyperbranched fluorine-free water-repellent finishing agent

Abstract

The invention discloses a kind of bio-based hyperbranched fluorine-free water-repellent finishing agent, and the following method is prepared: step one: extract bio-based acid from camphor seed powder; step two: chlorination of the obtained bio-based acid to obtain bio-based acyl chloride; step three: reacting bio-based acyl chloride with hyperbranched polyester to obtain modified hyperbranched polyester; step four: 2,2-dimethylol propionic acid, polytetrahydrofuran, diisocyanate, catalyst reaction, adding small molecule diol and modified hyperbranched polyester after the reaction is completed, continuing reaction, adding neutralizing agent to neutralize after the reaction is completed, and finally adding solvent to be configured into fluorine-free water-repellent finishing agent. The biomass acid in camphor seed powder is raw material, and the water repellent obtained is more environmentally friendly and pollution-free, and does not contain fluorine, is conducive to the achievement of "carbon peak", "carbon neutrality" goals, is conducive to alleviating the problem of climate warming and lack of resources, and is of great significance to improving the current environment and meeting the long-term energy strategy development of mankind.

Description

Technical Field

[0001] The invention relates to the field of fabric finishing agents, and more particularly to a bio-based hyperbranched fluorine-free water-repellent finishing agent. Background Art

[0002] Water repellency is often used as a basic and necessary function for medical protective fabrics, military clothing, special operation clothing and civilian outdoor products. It can not only effectively improve the stain resistance and comfort of the fabric, but also effectively isolate liquid pollutants, playing a vital protective role. Using low surface energy chemicals to finish fabrics is the most effective way to improve the water repellent performance of fabrics. However, on the one hand, as people pay more and more attention to ecology and health, the environmental protection of these chemicals has become the focus of industry attention. On the other hand, the raw materials of these water repellent finishing agents are almost all derived from petrochemicals. Due to the large amount of use, it is a huge consumption of petroleum resources, which seriously deviates from the concept of "carbon neutrality".

[0003] The water-repellent finishing agent used in water-repellent functional fabrics usually uses C8 (containing 8 carbon chains) perfluorinated segments as functional groups. The reason is that the CF bonds have a very strong polarization effect, repel each other, and are distributed along the main chain spirally to form a strong shielding layer for external substances (including water and oil), thus showing extremely low surface energy, extremely high chemical stability and heat resistance. Therefore, in terms of performance alone, the water repellency and durability of fluorinated C8 finishing agents are unique.

[0004] However, fluorinated C8 water repellents have two serious drawbacks. On the one hand, fluorinated C8 water repellents will produce perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) byproducts during the production and degradation process. Both substances are clearly carcinogenic. At the same time, its extremely strong chemical stability leads to permanent bioaccumulation. It is considered to be one of the most difficult organic pollutants to degrade at present, and it poses a serious threat to the ecological environment and human health. As a result, fluorinated C8 water repellents are gradually abandoned and their substitutes are urgently needed. On the other hand, the raw materials for the production of all water repellents on the market, including fluorinated finishing agents, come from petroleum, which not only exacerbates the crisis of oil depletion to a certain extent, but also brings continuous pollution to the environment due to their poor degradability. Summary of the invention

[0005] In view of the shortcomings of the prior art, the object of the present invention is to provide a fluorine-free water-repellent finishing agent prepared by extracting bio-based acids from biomass.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] A bio-based hyperbranched fluorine-free water-repellent finishing agent.

[0008] The following method is used to prepare:

[0009] Step 1: extracting bio-based acid from camphor seed powder;

[0010] Step 2: chlorinating the obtained bio-based acid to obtain bio-based acid chloride;

[0011] Step 3: reacting the bio-based acyl chloride with the hyperbranched polyester to obtain a modified hyperbranched polyester;

[0012] Step 4: 2,2-dimethylolpropionic acid, polytetrahydrofuran, diisocyanate and catalyst react, and after the reaction is completed, small molecule diol and modified hyperbranched polyester are added to continue the reaction, and after the reaction is completed, a neutralizing agent is added for neutralization, and finally a solvent is added to prepare a fluorine-free water-repellent finishing agent.

[0013] As a further improvement of the present invention,

[0014] The step one is:

[0015] Take camphor seed powder and distilled water and add them to a conical flask. Irradiate with 400W microwave for 10-30s. Add xylanase, cellulase and alkaline endoproteinase and react at 50℃ for 1-4h. Raise the temperature to 70-100℃ to inactivate the enzyme. Separate the product into oil and water layers in a high-speed centrifuge. The extracted oil layer is the bio-based acid.

[0016] As a further improvement of the present invention,

[0017] In the step 1, the mass ratio of camphor seed powder, distilled water, xylanase, cellulase and alkaline endoproteinase is 1:4-10:0.02:0.02:0.00002.

[0018] As a further improvement of the present invention,

[0019] The second step is:

[0020] The bio-based acid and dimethylformamide obtained in step 1 are added to toluene and bis(trichloromethyl) carbonate solution, the temperature is controlled at 25-30°C, the reaction is carried out for 1-4 hours, and toluene and dimethylformamide are fractionated under reduced pressure to obtain bio-based acid chloride.

[0021] As a further improvement of the present invention,

[0022] The mass ratio of the bio-based acid, dimethylformamide, toluene and bis(trichloromethyl) carbonate is 200:10:80-120:110-150.

[0023] As a further improvement of the present invention,

[0024] The step three is:

[0025] The hyperbranched polyester, bio-based acyl chloride and triethylamine are mixed, nitrogen is introduced, the temperature is controlled at 10-40° C., and the reaction is carried out for 1-3 hours to obtain a modified hyperbranched polyester.

[0026] As a further improvement of the present invention,

[0027] In the step 3, the mass ratio of the hyperbranched polyester, the bio-based acyl chloride and the triethylamine is 1:5-10:5-15.

[0028] As a further improvement of the present invention,

[0029] The step four is:

[0030] Add 2,2-dihydroxymethylpropionic acid and polytetrahydrofuran to a reaction container, heat to 60-80°C, stir continuously, react for 2 hours, add a catalyst and diisocyanate, react for 2 hours, add a small molecule diol and a modified hyperbranched polyester, react for 2 hours, cool to 50°C, add triethylamine for neutralization, and add a solvent to prepare a fluorine-free water-repellent finishing agent.

[0031] As a further improvement of the present invention,

[0032] The mass ratio of the 2,2-dimethylol propionic acid, polytetrahydrofuran, modified hyperbranched polyester, small molecule diol and diisocyanate is 3-10:3-10:5-20:2-5:13-20.

[0033] As a further improvement of the present invention,

[0034] In the step 4:

[0035] The degree of polymerization of the polytetrahydrofuran is 1000;

[0036] The diisocyanate is isophorone diisocyanate;

[0037] The small molecule diol is 1,4-butanediol;

[0038] The catalyst is dibutyltin dilaurate.

[0039] In the present invention, firstly, bio-based acid is extracted from camphor seed powder, then the bio-based acid is chlorinated, and then the bio-based acid chloride is obtained to modify the hyperbranched polyester, and the modified hyperbranched acid chloride is reacted with diisocyanate, polytetrahydrofuran, 2,2-dimethylol propionic acid and small molecule diol to prepare a bio-based hyperbranched macromolecular fluorine-free water-repellent finishing agent. The bio-based acid in the camphor seed powder is used as a raw material, and the prepared water-repellent is more environmentally friendly and pollution-free, and does not contain fluorine, which is conducive to the achievement of the goals of "carbon peak" and "carbon neutrality", and is conducive to alleviating the problems of climate warming and resource shortage, and is of great significance to improving the current environment and meeting the long-term energy strategy development of mankind.

[0040] In the process of extracting camphor seed powder, the micro-blog-assisted enzyme method is used in a water solvent. The surface of the camphor seed powder is first destroyed by xylan, cellulase, and alkaline endoproteinase, and the internal bio-based acid flows out for extraction.

[0041] In the subsequent chlorination process, dimethylformamide is used as a catalyst to react with bis(trichloromethyl) carbonate (triphosgene) in a toluene solution to carry out chlorination.

[0042] The reaction of bio-based acid chloride with hyperbranched polyester mainly modifies two hyperbranched polyesters, wherein the hyperbranched polyester is hyperbranched bis-MPA polyester-16-hydroxy. DETAILED DESCRIPTION Example

[0043] Step 1: Take 1 part of camphor seed powder and 5 parts of distilled water, add them to a conical flask, irradiate with 400W microwave for 15s, add 0.02 parts of xylanase, 0.02 parts of cellulase and 0.00002 parts of alkaline endoproteinase (the alkaline endoproteinase may be small in mass, so the dilution method can be used, for example, 1g of alkaline endoproteinase is dissolved in 4999g of water, and 1g of the mixed solution is taken to obtain 20μg of alkaline endoproteinase), react at 50℃ for 3h, and heat to 100℃ to inactivate the enzyme. Separate the product into oil and water in a high-speed centrifuge, and the separated oil layer is the bio-based acid.

[0044] Step 2:

[0045] Take 200 parts by weight of the bio-based acid obtained in step 1 and 10 parts by weight of dimethylformamide, add them to a solution of 90 parts by weight of toluene and 118 parts by weight of bis(trichloromethyl)carbonate, control the temperature at 25°C, react for 2 hours, and distill the reactants under reduced pressure to remove toluene and dimethylformamide to obtain bio-based acid chloride.

[0046] Step 3:

[0047] Take hyperbranched polyester, bio-based acid chloride and triethylamine in a mass ratio of 1:8:8.8, add hyperbranched polyester and triethylamine into a four-necked flask, pass nitrogen, stir, raise the temperature to 25°C, add bio-based acid chloride dropwise at a uniform rate, complete the dropwise addition within 25 minutes, react for 1 hour, and obtain modified hyperbranched polyester.

[0048] Step 4:

[0049] By mass, 5 parts of 2,2-dihydroxymethylpropionic acid and 5 parts of polytetrahydrofuran with a degree of polymerization of 1000 were added to a four-necked flask, the temperature was raised to 65°C, stirring continuously, reacted for 2 hours, 0.05 parts of dibutyltin dilaurate and 15 parts of isophorone diisocyanate were added, the reaction was continued for 2 hours, 2 parts of 1,4-butanediol and 10 parts of modified hyperbranched polyester were added, the reaction was continued for 2 hours, the temperature was lowered to 50°C, triethylamine was added for neutralization, the pH was neutralized, water was added as a solvent, and a fluorine-free water-repellent finishing agent with a solid content of 30% was prepared. Example

[0050] Step 1: Take 1 part of camphor seed powder and 5 parts of distilled water, add them to a conical flask, irradiate with 400W microwave for 15s, add 0.02 parts of xylanase, 0.02 parts of cellulase and 0.00002 parts of alkaline endoproteinase (the alkaline endoproteinase may be small in mass, so the dilution method can be used, for example, 1g of alkaline endoproteinase is dissolved in 4999g of water, and 1g of the mixed solution is taken to obtain 20μg of alkaline endoproteinase), react at 50℃ for 3h, and heat to 100℃ to inactivate the enzyme. Separate the product into oil and water in a high-speed centrifuge, and the separated oil layer is the bio-based acid.

[0051] Step 2:

[0052] Take 200 parts by weight of the bio-based acid obtained in step 1 and 10 parts by weight of dimethylformamide, add them to a solution of 90 parts by weight of toluene and 118 parts by weight of bis(trichloromethyl)carbonate, control the temperature at 25°C, react for 2.5 hours, and distill the reactants under reduced pressure to remove toluene and dimethylformamide to obtain bio-based acid chloride.

[0053] Step 3:

[0054] Take hyperbranched polyester, bio-based acid chloride and triethylamine in a mass ratio of 1:8:9.6, add hyperbranched polyester and triethylamine into a four-necked flask, pass nitrogen, stir, heat to 20°C, add bio-based acid chloride dropwise at a uniform rate, complete the dropwise addition within 25 minutes, react for 1.5 hours, and obtain modified hyperbranched polyester.

[0055] Step 4:

[0056] By mass, 3 parts of 2,2-dihydroxymethylpropionic acid and 3 parts of polytetrahydrofuran with a polymerization degree of 1000 were added to a four-necked flask, the temperature was raised to 65°C, stirring continuously, reacted for 2 hours, 0.05 parts of dibutyltin dilaurate and 15 parts of isophorone diisocyanate were added, the reaction was continued for 2 hours, 2 parts of 1,4-butanediol and 15 parts of modified hyperbranched polyester were added, the reaction was continued for 2 hours, the temperature was lowered to 50°C, triethylamine was added for neutralization, the pH was neutralized, water was added as a solvent, and a fluorine-free water-repellent finishing agent with a solid content of 30% was prepared. Example

[0057] Step 1: Take 1 part of camphor seed powder and 5 parts of distilled water, add them to a conical flask, irradiate with 400W microwave for 15s, add 0.02 parts of xylanase, 0.02 parts of cellulase and 0.00002 parts of alkaline endoproteinase (the alkaline endoproteinase may be small in mass, so the dilution method can be used, for example, 1g of alkaline endoproteinase is dissolved in 4999g of water, and 1g of the mixed solution is taken to obtain 20μg of alkaline endoproteinase), react at 50℃ for 3h, and heat to 100℃ to inactivate the enzyme. Separate the product into oil and water in a high-speed centrifuge, and the separated oil layer is the bio-based acid.

[0058] Step 2:

[0059] Take 200 parts by weight of the bio-based acid obtained in step 1 and 10 parts by weight of dimethylformamide, add them to a solution of 90 parts by weight of toluene and 118 parts by weight of bis(trichloromethyl)carbonate, control the temperature at 25°C, react for 3 hours, and distill the reactants under reduced pressure to remove toluene and dimethylformamide to obtain bio-based acid chloride.

[0060] Step 3:

[0061] Take hyperbranched polyester, bio-based acid chloride and triethylamine in a mass ratio of 1:8:6.4, add hyperbranched polyester and triethylamine into a four-necked flask, pass nitrogen, stir, heat to 15°C, add bio-based acid chloride dropwise at a uniform rate, complete the dropwise addition within 25 minutes, react for 2 hours, and obtain modified hyperbranched polyester.

[0062] Step 4:

[0063] By mass, 3 parts of 2,2-dihydroxymethylpropionic acid and 3 parts of polytetrahydrofuran with a polymerization degree of 1000 were added to a four-necked flask, the temperature was raised to 65°C, stirring continuously, reacted for 2 hours, 0.05 parts of dibutyltin dilaurate and 15 parts of isophorone diisocyanate were added, the reaction was continued for 2 hours, 2 parts of 1,4-butanediol and 13 parts of modified hyperbranched polyester were added, the reaction was continued for 2 hours, the temperature was lowered to 50°C, triethylamine was added for neutralization, the pH was neutralized, water was added as a solvent, and a fluorine-free water-repellent finishing agent with a solid content of 30% was prepared. Example

[0064] Step 1: Take 1 part of camphor seed powder and 5 parts of distilled water, add them to a conical flask, irradiate with 400W microwave for 15s, add 0.02 parts of xylanase, 0.02 parts of cellulase and 0.00002 parts of alkaline endoproteinase (the alkaline endoproteinase may be small in mass, so the dilution method can be used, for example, 1g of alkaline endoproteinase is dissolved in 4999g of water, and 1g of the mixed solution is taken to obtain 20μg of alkaline endoproteinase), react at 50℃ for 3h, and heat to 100℃ to inactivate the enzyme. Separate the product into oil and water in a high-speed centrifuge, and the separated oil layer is the bio-based acid.

[0065] Step 2:

[0066] Take 200 parts by weight of the bio-based acid obtained in step 1 and 10 parts by weight of dimethylformamide, add them to a solution of 90 parts by weight of toluene and 118 parts by weight of bis(trichloromethyl)carbonate, control the temperature at 25°C, react for 2 hours, and distill the reactants under reduced pressure to remove toluene and dimethylformamide to obtain bio-based acid chloride.

[0067] Step 3:

[0068] Take hyperbranched polyester, bio-based acid chloride and triethylamine in a mass ratio of 1:8:8, add hyperbranched polyester and triethylamine into a four-necked flask, pass nitrogen, stir, heat to 25°C, add bio-based acid chloride dropwise at a uniform rate, complete the dropwise addition within 25 minutes, react for 1 hour, and obtain modified hyperbranched polyester.

[0069] Step 4:

[0070] By mass, 5 parts of 2,2-dihydroxymethylpropionic acid and 5 parts of polytetrahydrofuran with a degree of polymerization of 1000 were added to a four-necked flask, the temperature was raised to 65°C, stirring continuously, reacted for 2 hours, 0.05 parts of dibutyltin dilaurate and 15 parts of isophorone diisocyanate were added, the reaction was continued for 2 hours, 2 parts of 1,4-butanediol and 10 parts of modified hyperbranched polyester were added, the reaction was continued for 2 hours, the temperature was lowered to 50°C, triethylamine was added for neutralization, the pH was neutralized, water was added as a solvent, and a fluorine-free water-repellent finishing agent with a solid content of 30% was prepared. Example

[0071] Step 1: Take 1 part of camphor seed powder and 5 parts of distilled water, add them to a conical flask, irradiate with 400W microwave for 15s, add 0.02 parts of xylanase, 0.02 parts of cellulase and 0.00002 parts of alkaline endoproteinase (the alkaline endoproteinase may be small in mass, so the dilution method can be used, for example, 1g of alkaline endoproteinase is dissolved in 4999g of water, and 1g of the mixed solution is taken to obtain 20μg of alkaline endoproteinase), react at 50℃ for 3h, and heat to 100℃ to inactivate the enzyme. Separate the product into oil and water in a high-speed centrifuge, and the separated oil layer is the bio-based acid.

[0072] Step 2:

[0073] Take 200 parts by weight of the bio-based acid obtained in step 1 and 10 parts by weight of dimethylformamide, add them to a solution of 90 parts by weight of toluene and 118 parts by weight of bis(trichloromethyl)carbonate, control the temperature at 25°C, react for 2 hours, and distill the reactants under reduced pressure to remove toluene and dimethylformamide to obtain bio-based acid chloride.

[0074] Step 3:

[0075] Take hyperbranched polyester, bio-based acid chloride and triethylamine in a mass ratio of 1:8:8.8, add hyperbranched polyester and triethylamine into a four-necked flask, pass nitrogen, stir, raise the temperature to 25°C, add bio-based acid chloride dropwise at a uniform rate, complete the dropwise addition within 25 minutes, react for 1 hour, and obtain modified hyperbranched polyester.

[0076] Step 4:

[0077] By mass, 5 parts of 2,2-dihydroxymethylpropionic acid and 5 parts of polytetrahydrofuran with a degree of polymerization of 1000 were added to a four-necked flask, the temperature was raised to 65°C, stirring continuously, reacted for 2 hours, 0.05 parts of dibutyltin dilaurate and 15 parts of isophorone diisocyanate were added, the reaction was continued for 2 hours, 2 parts of 1,4-butanediol and 18 parts of modified hyperbranched polyester were added, the reaction was continued for 2 hours, the temperature was lowered to 50°C, triethylamine was added for neutralization, the pH was neutralized, water was added as a solvent, and a fluorine-free water-repellent finishing agent with a solid content of 30% was prepared.

[0078]

[0079]

[0080] test:

[0081] The finishing agents obtained in Examples 1 to 5 were used to perform water repellency finishing on polyester fabrics by a one-dip-one-roll process, with a rolling pressure of 0.1 kg, at 170° C., for 40 seconds, to determine the water repellency level of the fabric. A blank group was set, i.e., polyester fabrics that were not treated with one-dip-one-roll.

[0082] The test method refers to AATCC 22-2005 Textile Water Repellency Test Spray Method

[0083]

[0084] In the present invention, firstly, bio-based acid is extracted from camphor seed powder, then the bio-based acid is chlorinated, and then the hyperbranched polyester is modified by the obtained bio-based acid chloride, and the obtained modified hyperbranched acid chloride is reacted with diisocyanate, polytetrahydrofuran, 2,2-dimethylol propionic acid and small molecule diol to prepare a bio-based hyperbranched macromolecular fluorine-free water-repellent finishing agent. The bio-based acid in the camphor seed powder is used as a raw material, and the prepared water-repellent is more environmentally friendly and pollution-free, and does not contain fluorine, which is conducive to the achievement of the goals of "carbon peak" and "carbon neutrality", and is conducive to alleviating the problems of climate warming and resource shortage, and is of great significance to improving the current environment and meeting the long-term energy strategic development of mankind.

[0085] In the process of extracting camphor seed powder, the micro-blog-assisted enzyme method is used in a water solvent. The surface of the camphor seed powder is first destroyed by xylan, cellulase, and alkaline endoproteinase, and the internal bio-based acid flows out for extraction.

[0086] In the subsequent chlorination process, dimethylformamide is used as a catalyst to react with bis(trichloromethyl) carbonate (triphosgene) in a toluene solution to carry out chlorination.

[0087] The reaction of bio-based acid chloride with hyperbranched polyester mainly modifies two hyperbranched polyesters, wherein the hyperbranched polyester is hyperbranched bis-MPA polyester-16-hydroxy.

[0088] The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments. All technical solutions under the concept of the present invention belong to the protection scope of the present invention. It should be pointed out that for ordinary technicians in this technical field, some improvements and modifications without departing from the principle of the present invention should also be regarded as the protection scope of the present invention.

Claims

1. A bio-based hyperbranched fluorine-free water-repellent finishing agent, characterized in that: The following method is used to prepare: Step 1: Extracting bio-based acid from camphor seed powder; Step 2: chlorinating the obtained bio-based acid to obtain bio-based acid chloride; Step 3: reacting the bio-based acyl chloride with the hyperbranched polyester to obtain a modified hyperbranched polyester; Step 4: 2,2-dimethylolpropionic acid, polytetrahydrofuran, diisocyanate, and catalyst react. After the reaction is completed, small molecule diol and modified hyperbranched polyester are added to continue the reaction. After the reaction is completed, a neutralizer is added to neutralize the reaction. Finally, a solvent is added to prepare a fluorine-free water-repellent finishing agent. The step 1 is: Take camphor seed powder and distilled water and add them to a conical flask. Irradiate it with a 400W microwave for 10-30s. Add xylanase, cellulase and alkaline endoproteinase and react at 50℃ for 1-4h. Raise the temperature to 70-100℃ to inactivate the enzyme. Separate the oil and water layers of the product in a high-speed centrifuge. The extracted oil layer is the bio-based acid.

2. A bio-based hyperbranched fluorine-free water-repellent finishing agent according to claim 1, characterized in that: In the step 1, the mass ratio of camphor seed powder, distilled water, xylanase, cellulase, and alkaline endoproteinase is 1:4-10:0.02:0.02:0.00002.

3. A bio-based hyperbranched fluorine-free water-repellent finishing agent according to claim 2, characterized in that: The second step is: The bio-based acid and dimethylformamide obtained in step 1 are added to a toluene and bis(trichloromethyl) carbonate solution, the temperature is controlled at 25-30°C, the reaction is carried out for 1-4 hours, and the reactants are decompressed to fractionate toluene and dimethylformamide to obtain a bio-based acid chloride.

4. A bio-based hyperbranched fluorine-free water-repellent finishing agent according to claim 3, characterized in that: The mass ratio of the bio-based acid, dimethylformamide, toluene, and bis(trichloromethyl) carbonate is 200:10:80-120:110-150.

5. The bio-based hyperbranched fluorine-free water-repellent finishing agent according to claim 4, characterized in that: The step three is: Hyperbranched polyester, bio-based acyl chloride and triethylamine are mixed, nitrogen is introduced, the temperature is controlled at 10-40° C., and the reaction is carried out for 1-3 hours to obtain modified hyperbranched polyester.

6. The bio-based hyperbranched fluorine-free water-repellent finishing agent according to claim 5, characterized in that: In the step 3, the mass ratio of the hyperbranched polyester, the bio-based acyl chloride, and the triethylamine is 1:5-10:5-15.

7. The bio-based hyperbranched fluorine-free water-repellent finishing agent according to claim 6, characterized in that: The step four is: Add 2,2-dihydroxymethylpropionic acid and polytetrahydrofuran to a reaction vessel, heat to 60-80°C, stir continuously, react for 2 hours, add catalyst and diisocyanate, react for 2 hours, add small molecule diol and modified hyperbranched polyester, react for 2 hours, cool to 50°C, add triethylamine for neutralization, and add solvent to prepare a fluorine-free water-repellent finishing agent.

8. The bio-based hyperbranched fluorine-free water-repellent finishing agent according to claim 7, characterized in that: The mass ratio of the 2,2-dimethylol propionic acid, polytetrahydrofuran, modified hyperbranched polyester, small molecule diol and diisocyanate is 3-10:3-10:5-20:2-5:13-20.

9. The bio-based hyperbranched fluorine-free water-repellent finishing agent according to claim 8, characterized in that: In the step 4: The degree of polymerization of the polytetrahydrofuran is 1000; The diisocyanate is isophorone diisocyanate; The small molecule diol is 1,4-butanediol; The catalyst is dibutyltin dilaurate.

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