CN102702465A - Preparation method for silicofluoride-contained polyurethane water repellent finishing agent - Google Patents

Abstract

The invention provides a method for preparing a silicon-fluorine-containing polyurethane water-repellent finishing agent, which is characterized in that the specific steps are: dissolving isocyanate and fluorine-containing alcohol in a solvent, and simultaneously stirring and reacting under nitrogen protection; mixing polyether glycol and At least one of the polyester diols and a catalyst are added to the reaction system of the first step to obtain a prepolymer R1; the organosiloxane is dissolved in a solvent, and the catalyst is added to obtain an organosiloxane solution, which is dripped The method of adding is added to the prepolymer R1 obtained in the second step to obtain the prepolymer R2; the diol or diamine is added as a chain extender to the prepolymer R2 obtained in the third step, and finally a small Molecular alcohol and the remaining isocyanate in the reaction system are stirred and reacted to block, and then silicon-containing fluorine polyurethane can be obtained. The silicon-fluorine-containing polyurethane of the invention can be used as fabric finishing agent, leather finishing agent, self-cleaning paint additive, etc., and has excellent water-repellent and oil-repellent finishing properties.

Description

A preparation method of silicon-fluorine polyurethane water-repellent finishing agent

technical field

The invention relates to a preparation method of a silicon-fluorine-containing polyurethane water-repellent finishing agent, which belongs to the field of chemical auxiliary agents.

Background technique

With the development of social economy and technology, people have more and more demands for high-quality, multi-functional materials, especially in the fields of textile leather finishing, coatings, construction, automobiles and papermaking, etc. The pollution effect requirements are getting higher and higher. Due to its excellent thermal stability, weather resistance and chemical inertness, as well as unique properties such as low surface free energy and low coefficient of friction, fluorine-containing polyurethane exhibits outstanding water and oil repellency and anti-adhesion properties. Fluorine-containing polyurethane finishing agents can not only be used for fabric finishing, but also have important applications in veneer carpets, wall coatings, wood, building materials, leather and paper.

At present, the introduction of fluorine into fluorine-containing polyurethane mainly includes the introduction of polyurethane soft segments, the introduction of polyurethane hard segments, and the introduction of end groups. The soft segment of polyurethane is mainly introduced through perfluoropolyether, semifluoropolyether, perfluoropolyester, or the mixture of the above fluorine-containing compounds and ordinary polyether or polyester is introduced as a soft segment at the same time, and the process is relatively complicated; the hard segment of polyurethane Introduction such as patent CN 101157750A mainly through the introduction of short-chain fluorinated diols, and the reaction of short-chain fluorinated diols and polyisocyanate compounds to prepare fluorine-containing polyurethanes. Due to the large content of hard segments, fluorine-containing polyurethane elastomers are relatively brittle ; The introduction of end groups, such as patent CN 101979756A, is mainly simply capped with fluoroalkyl alcohols. The fluorine content of the polyurethane thus obtained is low, and the effects of high oil resistance, water resistance and antifouling cannot be achieved. The base fluorine content increases, the cost increases, and the fluorine utilization rate decreases, which is not conducive to environmental friendliness and does not meet the requirements for the development of green chemistry.

Silicone has both an inorganic structure (-Si-O-Si-) main chain and an organic group (CH ₃ , Ph, etc.) side chain. Because it has the characteristics of both organic and inorganic materials, and its structure has the advantages of bond angle, bond length and bond energy, organosilicon compounds have many unique properties, such as low surface tension, special flexibility and good flexibility. chemical stability. The invention introduces the excellent properties of silicone into fluorine-containing polyurethane through chemical reaction, which can not only reduce the cost while maintaining good water resistance, oil resistance and anti-fouling performance, but also be friendly to the environment, and at the same time improve the brittleness of fluorine-containing polyurethane The problem.

Contents of the invention

The purpose of the present invention is to provide a preparation method of silicon-fluorine-containing polyurethane water-repellent finishing agent to solve the problem of high cost and high brittleness caused by increasing the fluorine content of fluorine-containing polyurethane to improve water resistance, oil resistance and antifouling performance. technical problem.

In order to solve the above technical problems, the present invention provides a method for preparing a silicon-fluorine-containing polyurethane water-repellent finishing agent, which is characterized in that the specific steps are:

The first step: dissolving the isocyanate and fluorine-containing alcohol in the solvent, while stirring the reaction under the protection of nitrogen;

The second step: adding at least one of polyether diol and polyester diol and a catalyst to the reaction system of the first step, stirring and reacting with the remaining isocyanate in the reaction system of the first step to obtain a prepolymer R1;

The third step: dissolve the organosiloxane in the solvent, add the catalyst to obtain the organosiloxane solution, add it dropwise to the prepolymer R1 obtained in the second step, and mix it with the reaction system of the second step The remaining isocyanate is stirred and reacted to obtain prepolymer R2;

Step 4: Add diol or diamine as a chain extender to the prepolymer R2 obtained in the third step, stir and react with the remaining isocyanate in the reaction system of the third step, and finally add a small molecule alcohol to react with The remaining isocyanate in the system is stirred and reacted to be blocked, and then silicon-containing fluorine polyurethane can be obtained.

Preferably, the molar ratio of isocyanate to fluorine-containing alcohol in the first step is 2:1-5:1, the total mass fraction of solute is 10-15%, the stirring speed is 50-200rpm, and the reaction temperature is 40-100 °C, the reaction time is 1-4h.

Preferably, the isocyanate in the first step is 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI), toluene diisocyanate (TDI), One or two or more of diphenylmethane diisocyanate (MDI), liquefied MDI, TDI dimer and HDI dimer are mixed.

Preferably, the fluorine-containing alcohol in the first step is perfluoroalkylethanol, its general formula is F(C ₂ F ₄ ) _n C ₂ H ₄ OH, n is an integer between 2-16, or N - Ethyl perfluorooctane sulfonamide ethanol.

Preferably, the solvent in the first step is N, N-dimethylformamide, N, N-dimethylacetamide, ethyl acetate, N-methylpyrrolidone, tetrahydrofuran, toluene and butanone One or a mixture of two or more.

Preferably, in the second step, the molar ratio of the isocyanate group contained in the isocyanate remaining in the reaction system of the first step to the hydroxyl group contained in at least one of the added polyether diol and polyester diol is 2:1-5:1, the mass of the catalyst added is 0-3% of the total mass of the reaction system in the first step, the stirring speed is 50-300rpm, the reaction temperature is 40-100°C, and the reaction time is 2-4h.

Preferably, the polyether diol in the second step is one or a mixture of two or more of polyoxypropylene glycol, polyethylene glycol and polytetrahydrofuran diol, and the polyester diol Polyethylene adipate diol, polybutylene adipate diol, polyneopentyl adipate diol, polydiethylene glycol adipate diol, One or more mixtures of polybutylene sebacate diol and polyneopentyl adipate diol.

Preferably, the catalyst in the second step is one or a mixture of two or more of a tertiary amine catalyst, an organotin catalyst and an organobismuth catalyst.

Preferably, in the third step, the molar ratio of the isocyanate group contained in the isocyanate remaining in the reaction system of the second step to the hydroxyl group or amino group contained in the added organosiloxane is 2:1-5:1. The mass fraction of organosiloxane in the oxane solution is 30-80%, the mass of the catalyst added is 0-3% of the total mass of the reaction system in the second step, the dropping speed is 15-30d/min, and the stirring speed is 100 -300rpm, the reaction temperature is 40-100°C, and the reaction time is 3-6h.

Preferably, the organosiloxane in the third step is a hydroxypropyl-terminated polysiloxane or an aminoalkyl-terminated polysiloxane.

Preferably, the solvent in the third step is one of N,N-dimethylformamide, N,N-dimethylacetamide, ethyl acetate, N-methylpyrrolidone, tetrahydrofuran, toluene and butanone a mixture of two or more.

Preferably, the catalyst in the third step is one or a mixture of two or more of a tertiary amine catalyst, an organotin catalyst and an organobismuth catalyst.

Preferably, in the fourth step, the molar ratio of the isocyanate group contained in the remaining isocyanate in the third step reaction system to the hydroxyl group of the diol or the amino group of the diamine added is 2:1-5:1, The temperature is 40-100°C, the stirring speed is 100-250rpm, the reaction time is 1-3h, and the end-capping reaction time is 0.5-2h after adding small molecule alcohol.

Preferably, the glycol in the fourth step is triethylene glycol, ethylene glycol, propylene glycol, 3-methylpropanediol, hexanediol, 1,4-butanediol, 3-methylpentanediol and One or a mixture of two or more neopentyl glycols.

Preferably, the diamine in the fourth step is one or both of ethylenediamine, hexamethylenediamine, cyclohexanediamine, isophoronediamine, dicyclohexylmethanediamine and toluenediamine a mixture of the above.

Preferably, the small molecule alcohol in the fourth step is one or a mixture of two or more of methanol, ethanol and isopropanol.

Preferably, the molar ratio of the small molecule alcohol added in the fourth step to the remaining isocyanate in the reaction system of the third step is 1:1.

Compared with prior art, advantage of the present invention is as follows:

(1) In the present invention, organosiloxane is added to the structure of fluorine-containing polyurethane in the form of terminal group introduction. Based on the excellent characteristics of organosiloxane with low surface tension, it solves the problem that cannot be solved by the simple preparation method of capping with fluoroalkyl alcohol. To ensure good oil resistance, water resistance and anti-fouling performance, while ensuring water repellency, the fluorine content inside the polyurethane is effectively controlled, thereby greatly reducing costs, and it is environmentally friendly and meets the requirements of green chemical development.

(2) The present invention introduces organosiloxane into fluorine-containing polyurethane. Based on the characteristics of organosiloxane's special flexibility and good chemical stability, the problem of high brittleness of fluorine-containing polyurethane is effectively improved.

(3) The preparation process of the present invention is simple, easy to operate, does not require special processing equipment, and the reaction conditions are mild and easy to control, and the preparation method is universal, and has broad application prospects in industrial production.

(4) The silicon-fluorine-containing polyurethane of the present invention can be used as fabric finishing agent, leather finishing agent, self-cleaning paint additive, etc., and has excellent water-repellent and oil-repellent finishing properties.

Detailed ways

Below in conjunction with embodiment, the present invention is further described in detail. The fluorine-containing alcohols used in the following examples were purchased from Harbin Xuejia Fluorosilicon Chemical Co., Ltd.; the organosiloxanes used in the examples were purchased from Shanghai Silicon Mountain Polymer Materials Co., Ltd.; Drugs and reagents were purchased from Shanghai Jingchun Reagent Co., Ltd.; cotton cloth and leather were provided by Jiangsu Baoze Polymer Co., Ltd.; the dynamic/static contact angle meter was SL200B from American Kono Industries; the vacuum drying oven was from Shanghai Qixin The DZF-6020 type of Scientific Instrument Co., Ltd.; the heating stirrer is the DF-101S type of Gongyi Yuhua Instrument Co., Ltd.

Example 1

(1) Dissolve 1 mol of diphenylmethane diisocyanate (MDI) and 0.3 mol of perfluoroalkylethanol (F(C ₂ F ₄ ) ₆ C ₂ H ₄ OH) in 150 g of N,N-dimethylformamide (DMF ) into the reaction kettle to fully dissolve, feed nitrogen, and stir the reaction at 40°C for 2 hours under the protection of nitrogen, with a stirring speed of 80rpm; the mole number of isocyanate groups contained in the remaining isocyanate in the reaction system is 1.7mol;

(2) Add 0.25mol polybutylene adipate diol (Mn=1000) and 1g dibutyltin dilaurate to the reaction kettle under the protection of nitrogen at 50°C and stir for 2h at a stirring speed of 100rpm to obtain the prepared Polymer R1; the number of moles of isocyanate groups contained in the remaining isocyanate in the reaction system is 1.2mol;

(3) 0.4mol terminal hydroxypropyl polysiloxane (HO-PDMS) (Mn=2000) was dissolved in tetrahydrofuran to obtain a solution with a mass fraction of 30%, and then 2g of dibutyltin dilaurate was added at 25d/ Add it dropwise to the prepolymer R1 at a speed of 1 min, stir and react for 6 hours at 65°C under the protection of nitrogen, and the stirring speed is 220rpm to obtain the prepolymer R2; the mole number of isocyanate groups contained in the remaining isocyanate in the reaction system is 0.4mol ;

(4) Add 0.18mol of triethylene glycol to the prepolymer R2, stir and react at 65°C for 1.2h under the protection of nitrogen, the stirring speed is 200rpm, finally add 0.04mol of methanol to capping, and continue to react for 1h under the same conditions, that is The prepared silicon-containing fluoropolyurethane can be obtained.

The properties of the prepared silicon-containing fluoropolyurethane were tested and characterized: the prepared silicon-containing fluoropolyurethane was diluted with N,N-dimethylformamide (DMF) to a mass fraction of 0.5%, and this dilution was applied to cotton cloth and On the leather surface, bake the cotton cloth and leather in an oven at 130°C for 3 minutes. The water contact angles measured with 5 μL droplets are 160° and 145° respectively, and the oil contact angles measured with 3 μL droplets are 155° and 145° respectively. , has excellent waterproof and oil-proof properties. The coated cotton and leather surfaces can be bent, folded and rolled freely without cracks, and have good flexibility.

Example 2

(1) Dissolve 1 mol of toluene diisocyanate (TDI) and 0.35 mol of perfluoroalkylethanol (F(C ₂ F ₄ ) ₈ C ₂ H ₄ OH) in 100 g of N,N-dimethylacetamide (DMAc) and add Fully dissolve in the reaction kettle, feed nitrogen, stir and react at 80°C for 2 hours under the protection of nitrogen, and the stirring speed is 180rpm; the mole number of isocyanate groups contained in the remaining isocyanate in the reaction system is 1.65mol;

(2) Add 0.3 mol of polytetrahydrofuran diol (PTMG, Mn=1000), 0.8 g of N, N-dimethylcyclohexylamine in the reaction kettle under the protection of nitrogen at 80°C for 2 hours, and the stirring speed is 200 rpm to obtain Prepolymer R1; the number of moles of isocyanate groups contained in the remaining isocyanate in the reaction system is 1.05mol;

(3) Dissolve 0.35 mol terminal hydroxypropyl polysiloxane (HO-PDMS) (Mn=2000) in N-methylpyrrolidone to obtain a solution with a mass fraction of 80%, and then add 1 g of N, N-dimethyl Cyclohexylamine was added dropwise to the prepolymer R1 at a rate of 30d/min, stirred and reacted for 5h at 100°C under the protection of nitrogen, and the stirring speed was 220rpm to obtain the prepolymer R2; the remaining isocyanate contained in the reaction system The number of moles of isocyanate groups is 0.35mol;

(4) Add 0.15mol 1,4-butanediol to the prepolymer R2, stir and react at 100°C for 1.5h under the protection of nitrogen, and the stirring speed is 220rpm, finally add 0.05mol ethanol to capping, and continue the reaction under the same conditions for 0.5 h, the prepared silicon-containing fluoropolyurethane can be obtained.

The properties of the prepared silicon-containing fluoropolyurethane were tested and characterized: the prepared silicon-containing fluoropolyurethane was diluted with N,N-dimethylformamide (DMF) to a mass fraction of 0.5%, and this dilution was applied to cotton cloth and On the leather surface, bake the cotton cloth and leather in an oven at 130°C for 3 minutes. The water contact angles measured with 5 μL droplets are 158° and 146° respectively, and the oil contact angles measured with 3 μL droplets are 150° and 142° respectively. , has excellent waterproof and oil-proof properties. The coated cotton and leather surfaces can be bent, folded and rolled freely without cracks, and have good flexibility.

Example 3

(1) Dissolve 1 mol of 1,6-hexamethylene diisocyanate (HDI) and 0.4 mol of N-ethyl perfluorooctyl sulfonamide in ethanol in 100 g of ethyl acetate and add them to the reaction kettle to fully dissolve, and then pass in nitrogen gas, under the protection of nitrogen gas Stir the reaction at 50°C for 1 hour at a stirring speed of 100 rpm; the isocyanate group contained in the remaining isocyanate in the reaction system is 1.6 mol;

(2) Add 0.4mol polyoxypropylene diol (Mn=1000) and 0.5g triethylamine in the reaction kettle under the protection of nitrogen at 65°C and stir for 2h at a stirring speed of 120rpm to obtain the prepolymer R1; The isocyanate group contained in the remaining isocyanate in the system is 0.8mol;

(3) 0.25mol terminal hydroxypropyl polysiloxane (HO-PDMS) (Mn=2000) was dissolved in N-methylpyrrolidone to obtain a solution with a mass fraction of 50%, and then 0.5g triethylamine was added, Add it dropwise to prepolymer R1 at a speed of 20d/min, stir and react at 80°C under nitrogen protection for 6h, and the stirring speed is 180rpm to obtain prepolymer R2; the moles of isocyanate groups contained in the remaining isocyanate in the reaction system 0.3mol;

(4) Add 0.13mol of ethylene glycol to the prepolymer R2, stir and react at 80°C for 1h under nitrogen protection, the stirring speed is 220rpm, finally add 0.04mol of isopropanol to block, and continue to react for 0.5h under the same conditions, The prepared silicon-containing fluoropolyurethane can be obtained.

The properties of the prepared silicon-containing fluoropolyurethane were tested and characterized: the prepared silicon-containing fluoropolyurethane was diluted with N,N-dimethylformamide (DMF) to a mass fraction of 0.5%, and this dilution was applied to cotton cloth and On the leather surface, bake the cotton cloth and leather in an oven at 130°C for 3 minutes. The water contact angles measured with 5 μL droplets are 156° and 142° respectively, and the oil contact angles measured with 3 μL droplets are 152° and 140° respectively. , has excellent waterproof and oil-proof properties. The coated cotton and leather surfaces can be bent, folded and rolled freely without cracks, and have good flexibility.

Example 4

(1) Dissolve 1mol of isophorone diisocyanate (IPDI) and 0.3mol of N-ethyl perfluorooctane sulfonamide in ethanol in 80g of N, N-dimethylacetamide (DMAc) and add to the reaction kettle to fully dissolve, Introduce nitrogen, stir and react at 60°C for 2 hours under the protection of nitrogen, and the stirring speed is 80rpm; the mole number of isocyanate groups contained in the remaining isocyanate in the reaction system is 1.7mol;

(2) Add 0.2mol polyethylene glycol (Mn=1000) and 1g dibutyltin dilaurate to the reaction kettle under nitrogen protection at 65°C and stir for 2h at a stirring speed of 120rpm to obtain prepolymer R1; The number of moles of isocyanate groups contained in the remaining isocyanate in the system is 1.3mol;

(3) Dissolve 0.45mol of aminoalkyl-terminated polysiloxane (NH ₂ -PDMS) (Mn=2000) in N-methylpyrrolidone to obtain a solution with a mass fraction of 65%, and then add 0.5g of N,N- Dimethylcyclohexylamine was added dropwise to the prepolymer R1 at a speed of 30d/min, stirred and reacted for 5h at 75°C under the protection of nitrogen, and the stirring speed was 160rpm to obtain the prepolymer R2; the remaining isocyanate in the reaction system was The number of moles of isocyanate groups contained is 0.4mol;

(4) Add 0.18mol of ethylene glycol to the prepolymer R2, stir and react at 75°C for 1h under the protection of nitrogen, and the stirring speed is 200rpm, finally add 0.04mol of methanol for capping, and continue to react for 2h under the same conditions to obtain The prepared silicon-containing fluoropolyurethane.

The properties of the prepared silicon-containing fluoropolyurethane were tested and characterized: the prepared silicon-containing fluoropolyurethane was diluted with N,N-dimethylformamide (DMF) to a mass fraction of 0.5%, and this dilution was applied to cotton cloth and On the leather surface, bake the cotton cloth and leather in an oven at 130°C for 3 minutes. The water contact angles measured with 5 μL droplets are 157° and 143° respectively, and the oil contact angles measured with 3 μL droplets are 154° and 141° respectively. , has excellent waterproof and oil-proof properties. The coated cotton and leather surfaces can be bent, folded and rolled freely without cracks, and have good flexibility.

Example 5

(1) Dissolve 1mol of dicyclohexylmethane diisocyanate (HMDI) and 0.4mol of N-ethylperfluorooctyl sulfonamide ethanol in 200g of methyl ethyl ketone and add them to the reaction kettle to fully dissolve, feed nitrogen, and under the protection of nitrogen, Stir the reaction at 55°C for 1 hour, and the stirring speed is 120rpm; the mole number of isocyanate groups contained in the remaining isocyanate in the reaction system is 1.6mol;

(2) Add 0.35mol polytetrahydrofuran glycol (PTMG, Mn=1000) and 0.6g dibutyltin dilaurate to the reaction kettle under nitrogen protection at 65°C and stir for 1.5h at a stirring speed of 150rpm to obtain a prepolymer R1; the molar number of isocyanate groups contained in the remaining isocyanate in the reaction system is 0.9mol;

(3) Dissolve 0.25mol terminal hydroxypropyl polysiloxane (HO-PDMS) (Mn=2000) in N-methylpyrrolidone to obtain a solution with a mass fraction of 40%, and then add 0.8g of dilauric acid di Butyl tin was added dropwise to the prepolymer R1 at a speed of 15d/min, and stirred and reacted for 3 hours at 80°C under the protection of nitrogen at a stirring speed of 180rpm to obtain the prepolymer R2; the isocyanate group contained in the remaining isocyanate in the reaction system The number of moles is 0.4mol;

(4) Add 0.18mol propylene glycol to the prepolymer R2, stir and react at 80°C for 2h under the protection of nitrogen, and the stirring speed is 200rpm, finally add 0.04mol ethanol for capping, and continue to react for 0.5h under the same conditions to obtain the obtained Prepared silicon-containing fluoropolyurethane.

The properties of the prepared silicon-containing fluoropolyurethane were tested and characterized: the prepared silicon-containing fluoropolyurethane was diluted with N,N-dimethylformamide (DMF) to a mass fraction of 0.5%, and this dilution was applied to cotton cloth and On the leather surface, bake the cotton cloth and leather in an oven at 130°C for 3 minutes. The water contact angles measured with 5 μL droplets are 156° and 142° respectively, and the oil contact angles measured with 3 μL droplets are 152° and 140° respectively. , has excellent waterproof and oil-proof properties. The coated cotton and leather surfaces can be bent, folded and rolled freely without cracks, and have good flexibility.

Claims (17)

1. the preparation method of a siliceous fluoride polyurethane water repellent finishing agent is characterized in that, concrete steps are:

The first step: isocyanic ester and fluorine-containing alcohol are dissolved in the solvent, simultaneously stirring reaction under nitrogen protection;

Second step: at least a and catalyzer in polyether Glycols and the polyester diol is joined in the reaction system of the first step,, obtain performed polymer R1 with remaining isocyanic ester stirring reaction in the reaction system of the first step;

The 3rd step: organo-siloxane is dissolved in the solvent, adds catalyzer, obtain organo-siloxane solution, join with the mode that drips among the performed polymer R1 of the second step gained,, obtain performed polymer R2 with remaining isocyanic ester stirring reaction in the reaction system in second step;

The 4th step: join divalent alcohol or diamine among the performed polymer R2 of the 3rd step gained as chainextender; With the 3rd the step reaction system in remaining isocyanic ester stirring reaction; Add remaining isocyanic ester stirring reaction end-blocking in small molecular alcohol and the reaction system at last, can obtain siliceous fluoride polyurethane.

2. the preparation method of siliceous fluoride polyurethane water repellent finishing agent as claimed in claim 1; It is characterized in that; The isocyanic ester in the said the first step and the mol ratio of fluorine-containing alcohol are 2: 1-5: 1, and solute total mass mark is 10-15%, stirring velocity is 50-200rpm; Temperature of reaction is 40-100 ℃, and the reaction times is 1-4h.

3. the preparation method of siliceous fluoride polyurethane water repellent finishing agent as claimed in claim 1; It is characterized in that; Isocyanic ester in the said the first step is one or more the mixture in hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, liquefied mdi, TDI dimer and the HDI dimer.

4. the preparation method of siliceous fluoride polyurethane water repellent finishing agent as claimed in claim 1 is characterized in that, the fluorine-containing alcohol in the said the first step is a perfluoroalkyl ethanol, and its general formula is F (C ₂F ₄) _nC ₂H ₄OH, n are the integer between the 2-16, or N-ethyl perfluorinated octyl sulfuryl amine ethanol.

5. the preparation method of siliceous fluoride polyurethane water repellent finishing agent as claimed in claim 1; It is characterized in that; Solvent in the said the first step is N; The mixture of one or more in dinethylformamide, DMAC N,N, ETHYLE ACETATE, N-Methyl pyrrolidone, THF, toluene and the butanone.

6. the preparation method of siliceous fluoride polyurethane water repellent finishing agent as claimed in claim 1; It is characterized in that in said second step, the mol ratio of at least a contained hydroxyl in the NCO that the remaining isocyanic ester of the reaction system of the first step is contained and the polyether Glycols of adding and the polyester diol is 2: 1-5: 1; The quality of the catalyzer that adds is the 0-3% of the reaction system total mass of the first step; Stirring velocity is 50-300rpm, and temperature of reaction is 40-100 ℃, and the reaction times is 2-4h.

7. the preparation method of siliceous fluoride polyurethane water repellent finishing agent as claimed in claim 1; It is characterized in that; Polyether Glycols in said second step is one or more the mixture in polyoxytrimethylene divalent alcohol, polyoxyethylene glycol and the polytetrahydrofuran diol, and described polyester diol is polyethylene glycol adipate divalent alcohol, poly adipate succinic acid ester divalent alcohol, polyneopentyl glycol adipate divalent alcohol, gather one or more the mixture in diethylene glycol adipate divalent alcohol, polydiethylene glycol sebacate divalent alcohol and the polyneopentyl glycol adipate divalent alcohol.

8. the preparation method of siliceous fluoride polyurethane water repellent finishing agent as claimed in claim 1 is characterized in that, the catalyzer in said second step is one or more a mixture of tertiary amine catalyst, organotin catalysts and organic bismuth catalyst.

9. the preparation method of siliceous fluoride polyurethane water repellent finishing agent as claimed in claim 1; It is characterized in that in said the 3rd step, the NCO that the remaining isocyanic ester of the second step reaction system is contained and the hydroxyl that organo-siloxane contained or the amino mol ratio of adding are 2: 1-5: 1; The massfraction of organo-siloxane is 30-80% in the organo-siloxane solution; The quality of the catalyzer that adds is the 0-3% of the reaction system total mass in second step, and rate of addition is 15-30d/min, and stirring velocity is 100-300rpm; Temperature of reaction is 40-100 ℃, and the reaction times is 3-6h.

10. the preparation method of siliceous fluoride polyurethane water repellent finishing agent as claimed in claim 1 is characterized in that, the organo-siloxane in said the 3rd step is end hydroxypropyl ZGK 5 or end aminoalkylpolysiloxanes.

11. the preparation method of siliceous fluoride polyurethane water repellent finishing agent as claimed in claim 1; It is characterized in that; Solvent in said the 3rd step is N; The mixture of one or more of dinethylformamide, DMAC N,N, ETHYLE ACETATE, N-Methyl pyrrolidone, THF, toluene and butanone.

12. the preparation method of siliceous fluoride polyurethane water repellent finishing agent as claimed in claim 1 is characterized in that, the catalyzer in said the 3rd step is one or more a mixture of tertiary amine catalyst, organotin catalysts and organic bismuth catalyst.

13. the preparation method of siliceous fluoride polyurethane water repellent finishing agent as claimed in claim 1; It is characterized in that in said the 4th step, the mol ratio of the hydroxyl of the NCO that remaining isocyanic ester contained in the three-step reaction system and the divalent alcohol of adding or the amino of diamine is 2: 1-5: 1; Temperature is 40-100 ℃; Stirring velocity is 100-250rpm, and the reaction times is 1-3h, and the end capping time is 0.5-2h later on to add small molecular alcohol.

14. the preparation method of siliceous fluoride polyurethane water repellent finishing agent as claimed in claim 1; It is characterized in that; Divalent alcohol in said the 4th step is triethylene glycol, terepthaloyl moietie, Ucar 35,3-methyl propanediol, pinakon, 1, the mixture of one or more of 4-butyleneglycol, 3-methyl pentanediol and NSC 6366.

15. the preparation method of siliceous fluoride polyurethane water repellent finishing agent as claimed in claim 1; It is characterized in that the diamine in said the 4th step is one or more a mixture of quadrol, hexanediamine, cyclohexanediamine, isophorone diamine, dicyclohexyl methyl hydride diamines and tolylene diamine.

16. the preparation method of siliceous fluoride polyurethane water repellent finishing agent as claimed in claim 1 is characterized in that, the small molecular alcohol in said the 4th step is one or more a mixture of methyl alcohol, ethanol and Virahol.

17. the preparation method of siliceous fluoride polyurethane water repellent finishing agent as claimed in claim 1 is characterized in that, the mol ratio of remaining isocyanic ester is 1: 1 in small molecular alcohol that adds in said the 4th step and the three-step reaction system.