Water-resistant flexible waterborne polyurethane film product based on multiple hydrogen bonds

Abstract

The invention discloses a water-resistant flexible waterborne polyurethane film product based on multiple hydrogen bonds. A multiple hydrogen bond unit and a polysiloxane unit are constructed in a waterborne polyurethane structure, and a waterproof flexible waterborne polyurethane film product is prepared through combination of the multiple hydrogen bond unit and the polysiloxane unit. The toughness of a waterborne polyurethane film product is improved based on the energy dissipation effect of multiple hydrogen bonds, meanwhile, the water resistance of the waterborne polyurethane film product is improved based on the hydrophobic characteristic and flexibility of polysiloxane, the modulus and surface viscosity of the film are reduced, and the film demolding effect is enhanced. According to the water-resistant flexible waterborne polyurethane film product based on the multiple hydrogen bonds, the thickness is smaller than 30 microns, the breaking force is larger than 20 N, the elongation at break is larger than 690%, the blasting volume is larger than 11 L, the blasting pressure is larger than 3 KPa, and after the waterborne polyurethane film product is soaked in hot water at the temperature of 50 + / -1 DEG C for 1 hour, the breaking force is larger than 18 N, the 100% tensile modulus is smaller than 1.0 MPa, and the toughness is larger than 32 MJ / m < 3 >.

Description

Technical Field

[0001] The invention belongs to the field of waterborne polyurethane film products, and in particular relates to a water-resistant and flexible waterborne polyurethane film product based on multiple hydrogen bonds. Background Art

[0002] Natural latex is soft, wear-resistant, elastic and cheap. It is the main raw material for film products on the market, such as condoms, medical gloves, finger cots, organ bags, etc. However, with the development of science and technology, the defects of traditional natural latex film products continue to emerge. Medical evidence shows that from the perspective of bacteria barrier, the soluble substances in the film are dissolved after molding, forming "holes", which cannot effectively isolate viruses with smaller diameters such as HIV and hepatitis B virus, resulting in the loss of its protective effect; and some water-soluble proteins in natural latex can cause latex allergic reactions, such as contact herpes zoster, dermatitis, rhinitis, conjunctivitis, asthma and anaphylactic shock. At the same time, natural latex has residual nitrosamines during the vulcanization process, which poses a risk of causing cancer.

[0003] Especially for condom film products, since it is the most widely used and simple tool for contraception and prevention of sexually transmitted diseases in the world, the safety of condoms has received more extensive attention. Existing condoms are mainly made of natural latex as raw materials. They have the characteristics of natural latex. When used as condom products, they have the inherent defects of natural latex. At the same time, the thickness of natural latex condoms is above 30um, and the user's physical examination is poor. When it is made below 30um, natural latex condoms have poor strength and are easy to break during use. Therefore, in the context of the new era, higher requirements are put forward for film products such as condoms.

[0004] Waterborne polyurethane material is a polymer material with alternating soft segment chains and hard segment chains and containing a large number of carbamate groups. Waterborne polyurethane film has good mechanical properties, good thermal conductivity, dense film structure, and good biocompatibility. Therefore, it has broad application prospects in the fields of film products such as condoms, medical gloves, finger cots, organ bags, etc.

[0005] At present, water-based polyurethane condom film products have been developed at home and abroad. Patent CN 112062983 A discloses a high-burst volume water-based polyurethane condom and its preparation method. The prepared condom has a burst volume greater than 12L, a burst pressure greater than 1.5kPa, and a 100% modulus less than or equal to 2.0MPa. Patent CN 113069269 A discloses a composite polyurethane condom, the prepared condom has a burst volume greater than 11L, a burst pressure greater than 5kPa, and a 100% modulus less than or equal to 1.9MPa. Although water-based polyurethane condoms have made great progress, compared with natural latex condoms, there is still a large gap in the flexibility of water-based polyurethane condoms. The 100% modulus of existing water-based polyurethane condoms is generally 1.5-2MPa, while the 100% modulus of natural latex is about 0.7MPa. At the same time, the State Food and Drug Administration issued a new standard for water-based polyurethane condoms, "YY / T 1850-2023 Technical Requirements and Test Methods for Polyurethane Condoms for Male Use", which will be implemented on January 15, 2024. Compared with the previous standard "HG / T 5456-2018 Polyurethane Condoms", the new standard has higher requirements for the mechanical properties of water-based polyurethane condoms, such as the tear force increased from 10N to 20N, and the burst pressure increased from 1.0KPa to 2.0KPa. At the same time, the new standard adds water resistance requirements, that is, after the water-based polyurethane condoms are immersed in hot water at (50±1)℃ for 1 hour, their tear force should be no less than 15N. Patent CN 107266645 A discloses a siloxane-modified aqueous polyurethane emulsion and a method for preparing aqueous polyurethane condoms. The prepared condoms have a burst volume greater than 6L, a burst pressure greater than 2.5kPa, and a 100% modulus less than 2.0MPa, but the maximum force is less than 20N, and no water resistance test is performed. Patent CN 111138614A discloses an aqueous polyurethane emulsion for low-modulus, high-strength, ultra-thin polyurethane condoms and a method for preparing the same. The prepared condoms have a thickness of less than 30um, a film elongation at break of not less than 1000%, a breaking strength of not less than 30MPa, a 100% modulus of not more than 1.8MPa, a condom burst pressure greater than 2.5kPa, a burst volume of not less than 6L, but the maximum force is less than 20N, and no water resistance test is performed.

[0006] Therefore, the high flexibility, low modulus, water resistance and other properties required by current film products such as gloves and condoms do not meet people's requirements for use. There is an urgent need to develop a low modulus, water-resistant, and highly flexible water-based polyurethane film product to meet people's requirements for film products in the new era. Summary of the invention

[0007] In view of the above background, the present invention provides a water-resistant and flexible waterborne polyurethane film product based on multiple hydrogen bonds.

[0008] The invention is designed from the molecular structure of waterborne polyurethane according to the relationship between the structure and performance of waterborne polyurethane, and develops a water-resistant and flexible waterborne polyurethane film product based on multiple hydrogen bonds. The product is characterized in that the product is obtained from an emulsion prepared from a waterborne polyurethane polymer through a film-forming process; the waterborne polyurethane polymer contains at least one multiple hydrogen bond unit and at least one polysiloxane unit in its structure, the multiple hydrogen bond unit is formed by a hydrogen bond monomer, and the at least one hydrogen bond monomer is formed by the reaction of a hydrogen bond monomer precursor compound and an isocyanate group during the preparation of the waterborne polyurethane polymer; the number of hydrogen bond teeth of the multiple hydrogen bond unit is not less than 3; and the polysiloxane unit is introduced through the polymerization reaction of polysiloxane and diisocyanate.

[0009] The waterborne polyurethane polymer is prepared from the following raw materials in parts by weight:

[0010] 3-10 parts of polysiloxane

[0011] Polymer polyol 40-70 parts

[0012] 2-15 parts of hydrogen bond monomer compound

[0013] 3-6 parts of hydrophilic chain extender

[0014] 10-30 parts of diisocyanate

[0015] Crosslinking agent 0.5-25 parts

[0016] 2-5 parts of salt-forming agent.

[0017] Wherein, the hydrogen bonding monomer has the following general structure:

[0018]

[0019] According to a preferred embodiment of the present invention, the hydrogen bonding monomer has at least one of the following general structures:

[0020]

[0021] Wherein, L1 is a divalent linking group, and the divalent linking group is selected from a carbon chain linking group or a linking group containing a dynamic bond, and the carbon chain linking group is C 1-24 Alkylene or substituted C 1-24Hydrocarbylene; wherein the linking group containing a dynamic bond is selected from a linking group containing a dynamic disulfide bond, a linking group containing a dynamic diselenide bond, a linking group containing a dynamic ketal bond, a linking group containing a dynamic acetal bond, a linking group containing a dynamic thioketal bond, a linking group containing a dynamic thioacetal bond, a linking group containing a dynamic imine bond, and a linking group containing a dynamic oxime bond; Indicates connection to polymer chains, cross-links, groups, atoms.

[0022] According to the general structure of the hydrogen bonding monomer, the hydrogen bonding monomer precursor compound of the hydrogen bonding monomer is selected from at least one of the following compounds:

[0023]

[0024] Wherein L6 is a divalent linking group, the divalent linking group is selected from a carbon chain linking group or a linking group containing a dynamic bond, the carbon chain linking group is C 1-24 Alkylene or substituted C 1-24 A alkylene group; wherein the linking group containing a dynamic bond is selected from a linking group containing a dynamic disulfide bond, a linking group containing a dynamic diselenide bond, a linking group containing a dynamic ketal bond, a linking group containing a dynamic acetal bond, a linking group containing a dynamic thioketal bond, a linking group containing a dynamic thioacetal bond, a linking group containing a dynamic imine bond, and a linking group containing a dynamic oxime bond.

[0025] According to an embodiment of the present invention, it also contains at least a second hydrogen bonding monomer, which is formed by the reaction of a hydrogen bonding monomer precursor compound and an isocyanate group during the preparation of the waterborne polyurethane polymer, or the hydrogen bonding monomer precursor compound is first prepared and then used as a polymerization monomer for the polymerization reaction of the waterborne polyurethane polymer, and the second hydrogen bonding monomer is in the polymer main chain and / or polymer chain side group or side chain or end group.

[0026] The second hydrogen bond monomer has one of the following general structures:

[0027]

[0028]

[0029] According to the general structure of the second hydrogen bonding monomer, the hydrogen bonding monomer precursor compounds of the second hydrogen bonding monomer can be listed as follows, but the present invention is not limited thereto:

[0030] According to an embodiment of the present invention, the structure of the polysiloxane is as follows: Wherein, R1 and R2 are each independently selected from one of hydroxyl, amino, and thiol; R3, R4, R5, R6, R7, and R8 are each independently selected from one of methyl, long-chain alkyl, phenyl, and epoxy hydrocarbon; L2 and L3 are divalent linking groups, each independently selected from C 1-24 Alkylene, substituted C 1-24 Hydrocarbylene, One of -OH2CH2C-OH2CH2CH2C-, -OH2CH2CH2C-OH2CH2CH2C-, -OH2CH2C-OH2CH2C-, wherein the carbon atom in -OH2CH2C-OH2CH2CH2C-, -OH2CH2CH2C-OH2CH2CH2C-, and -OH2CH2C-OH2CH2C- is connected to the silicon atom; wherein the substituted C 1-24 Alkylene refers to C 1-24 The hydrogen atom of the alkylene group is substituted, and the substituents include but are not limited to fluorine atoms, C 1-8 Perfluorocarbon chain, C 1-8 Non-perfluorocarbon chain, oxo (=O), thio (=S), amino (connected to the main chain carbon through a carbon-nitrogen double bond), oxygen heteroalkyl in the form of ether bond, thio heteroalkyl in the form of thioether bond, nitrogen heteroalkyl in the form of tertiary amino group; wherein m, is the number of repeating units, and m is an integer of 25-40. One of the preferred groups of L2 and L3 is At least one of; wherein i, x, y, z are the number of repeating units, and i, x, y, z are integers of 1-30. According to an embodiment of the present invention, the polysiloxane has a structure as shown below: Among them, R9, R 10 Each independently selected from one of hydroxyl, amino, and thiol, R f One selected from fluorine atoms and fluorine-containing side groups, wherein the fluorine-containing side groups are selected from C 1-8 Perfluorocarbon chain, C 1-8 One of the non-perfluorocarbon chains, L4 and L5 are divalent linking groups, each independently selected from C 1-24 Alkylene, substituted C 1-24 Hydrocarbylene, One of -OH2CH2C-OH2CH2CH2C-, -OH2CH2CH2C-OH2CH2CH2C-, -OH2CH2C-OH2CH2C-, wherein the carbon atom in -OH2CH2C-OH2CH2CH2C-, -OH2CH2CH2C-OH2CH2CH2C-, and -OH2CH2C-OH2CH2C- is connected to the silicon atom; wherein the substituted C 1-24 Alkylene refers to C 1-24The hydrogen atom of the alkylene group is substituted, and the substituents include but are not limited to fluorine atoms, C 1-8 Perfluorocarbon chain, C 1-8 Non-perfluorocarbon chain, oxo (=O), thio (=S), amino (connected to the main chain carbon through a carbon-nitrogen double bond), oxygen heteroalkyl in the form of ether bond, thio heteroalkyl in the form of thioether bond, and nitrogen heteroalkyl in the form of tertiary amino group; wherein n is the number of repeating units, and n is an integer of 25-40.

[0031] One of the preferred groups of L4 and L5 is

[0032] At least one of; wherein k, p, q, j is the number of repeating units, and k, p, q, j is an integer from 1 to 30.

[0033] One of the preferred groups of L2, L3, L4, and L5 is C 1-12 Alkylene, more preferably C 1-10 Alkylene, more preferably C 1-3 Specifically, one of 1,2-ethylene and 1,3-propylene is preferred.

[0034] According to an embodiment of the present invention, the polysiloxane is selected from a block copolymer of polysiloxane and a fluorinated polyether, wherein the block copolymer of polysiloxane and a fluorinated polyether is formed by polymerization of a polysiloxane segment and a fluorinated polyether segment through diisocyanate or a diisocyanate-terminated polymer; wherein the structure of the polysiloxane segment is as follows:

[0035]

[0036] The structure of the fluorinated polyether segment is shown below:

[0037]

[0038] Among them, R 17 , R 18 , R 25 , R 26 Each independently selected from one of hydroxyl, amino, and thiol, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24Each independently selected from a methyl group, a long-chain alkyl group, a phenyl group, an epoxy group, a fluorine atom, and a fluorine-containing side group, wherein the fluorine-containing side group is selected from C 1-8 Perfluorocarbon chain, C 1-8 One of the non-perfluorocarbon chains, L7, L8, L9, L 10 is a divalent linking group, each independently selected from C 1-24 Alkylene, substituted C 1-24 Hydrocarbylene,

[0039] -OH2CH2C-OH2CH2CH2C-, -OH2CH2CH2C-OH2CH2CH2C-, -OH2CH2C-OH2CH2C-; wherein the substituted C 1-24 Alkylene refers to C 1-24 The hydrogen atom of the alkylene group is substituted, and the substituents include but are not limited to fluorine atoms, C 1-8 Perfluorocarbon chain, C 1-8 Non-perfluorocarbon chain, oxo (=O), thio (=S), amino (connected to the main chain carbon through a carbon-nitrogen double bond), oxygen heteroalkyl in the form of ether bond, thio heteroalkyl in the form of thioether bond, nitrogen heteroalkyl in the form of tertiary amino group; wherein r, s, t, e, u, v, w are the number of repeating units, r, s, t are integers of 25-40, and e, u, v, w are integers of 1-30.

[0040] The isocyanate is selected from isophorone diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, hydrogenated phenylmethane diisocyanate, 1,3-phenylene diisocyanate, toluene 2,6-diisocyanate, L-lysine diisocyanate, toluene-2,4-diisocyanate, 1,5-naphthalene diisocyanate, cyclohexane-1,4-diisocyanate, trans-1,4-cyclohexyl diisocyanate, 4,4'-methylenebis(phenyl isocyanate) ), at least one of 1,4-diisocyanatobutane, 1,4-cyclohexanedimethyl diisocyanate, and 4,4-diisocyanate dicyclohexylmethane; wherein the isocyanate-terminated polymer is selected from isocyanate-terminated polytetrahydrofuran diol with an average number average molecular weight of 1000-2000Da, polycarbonate diol with an average number average molecular weight of 1000-2000Da, polycaprolactone diol with an average number average molecular weight of 1000-2000Da, Polybutadiene glycol with a weight of 1000-2000Da, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, butyl ethyl propanediol, diethyl pentanediol, 3-methyl-1,5-pentanediol, 1,3-butanediol, trimethyl pentanediol, 1,5-pentanediol, 1,2-pentanediol, hydroxy neopentyl alcohol At least one of esters, ethyl hexanediol, dodecanediol, 1,4-dihydroxymethylcyclohexane, cyclohexanediol, dodecanediol, spirodiol, hydroquinone dihydroxyethyl ether, resorcinol dihydroxyethyl ether, resorcinol bishydroxypropyl ether, resorcinol bishydroxypropyl ethyl ether, 4-hydroxyethyloxyethyl-1-hydroxyethylphenylene diether, 3-hydroxyethyloxyethyl-1-hydroxyethylphenylene diether, bisphenol A dihydroxyethyl ether, bisphenol A dihydroxypropyl ether, dimethylolpropionic acid, and dimethylolbutyric acid.

[0041] Furthermore, the preferred polysiloxane has an average number average molecular weight of 2000-3000 Da.

[0042] According to an embodiment of the present invention, the diisocyanate is selected from at least one of isophorone diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, hydrogenated phenylmethane diisocyanate, 1,3-phenylene diisocyanate, toluene 2,6-diisocyanate, L-lysine diisocyanate, toluene-2,4-diisocyanate, 1,5-naphthalene diisocyanate, cyclohexane-1,4-diisocyanate, trans-1,4-cyclohexyl diisocyanate, 4,4'-methylenebis(phenyl isocyanate), 1,4-diisocyanatobutane, 1,4-cyclohexanedimethyl diisocyanate, and 4,4-diisocyanate dicyclohexylmethane.

[0043] One of the preferred groups of diisocyanates is at least one of isophorone diisocyanate, hexamethylene diisocyanate, and hydrogenated phenylmethane diisocyanate.

[0044] According to an embodiment of the present invention, the polymer polyol is selected from at least one of polyether diol, polyester diol and polyolefin diol.

[0045] The polyether diol is selected from at least one of polytetramethylene glycol, polytetramethylene glycol-propylene oxide copolymer glycol, polypropylene glycol glycol, polypropylene oxide glycol, polyethylene oxide glycol, polyethylene oxide propylene oxide copolyether glycol, and perfluoropolyether glycol, and has an average number average molecular weight of 1000-10000 Da.

[0046] The polyester diol is selected from at least one of polycarbonate diol, polycaprolactone diol, polylactic acid diol, polyethylene glycol-adipic acid polyester diol, poly-1,4-butylene glycol-adipic acid polyester diol, polyethylene glycol propylene glycol-adipic acid polyester diol, polyethylene glycol butylene glycol-adipic acid polyester diol, neopentyl glycol-adipic acid polyester diol, polyhexanediol adipate diol, polylactic acid-glycolic acid copolymer, and polyglycolic acid, and its average number average molecular weight is 1000-10000Da.

[0047] The polyolefin diol is selected from at least one of polybutadiene diol, polybutadiene-acrylonitrile copolymer diol, hydrogenated polybutadiene diol, and hydrogenated styrene-butadiene block copolymer diol, and has an average number average molecular weight of 1000-10000 Da.

[0048] One of the preferred groups of polymer polyols is at least one of polytetramethylene glycol, polycarbonate glycol, polycaprolactone glycol and polybutadiene glycol; further, the preferred polymer polyol has an average number average molecular weight of 2000-3000 Da.

[0049] According to an embodiment of the present invention, the cross-linking agent is selected from at least one of trimethylolpropane, triethanolamine, triethylenetriamine, 1,2,6-hexanetriol, 1,2,8-octantriol, 1,3,5-pentanetriol, 2-methyl-1,2,3-propanetriol, 2,4,6-trimethylbenzene-1,3,5-triol, melamine, benzene-1,2,3-triamine, modified castor oil, polyether triol, polyether tetraol, polyether hexol, and polyether octaol; wherein the modified castor oil has an average number average molecular weight of 500-1200Da and a functionality of 2.5-3.5; wherein the polyether triol, polyether tetraol, polyether hexol, and polyether octaol have an average number average molecular weight of 3000-10000Da.

[0050] One of the preferred groups of crosslinking agents is at least one of trimethylolpropane, triethanolamine, modified castor oil, and polyether triol; wherein the modified castor oil has an average number average molecular weight of 500-1200Da and a functionality of 2.5-3.5; wherein the polyether triol has an average number average molecular weight of 3000-5000Da.

[0051] According to an embodiment of the present invention, the hydrophilic chain extender is selected from at least one of dimethylolpropionic acid, dimethylolbutyric acid, sodium ethylenediamine ethanesulfonate, sodium N,N-(2-hydroxyethyl)-2-aminoethanesulfonate, sodium 1,4-butanediol-2-sulfonate, and methyldiethanolamine.

[0052] One of the preferred groups of hydrophilic chain extenders is at least one of dimethylol propionic acid and dimethylol butyric acid.

[0053] According to an embodiment of the present invention, the salt-forming agent is selected from at least one of triethylamine, diethanolamine, potassium hydroxide, sodium hydroxide and diisopropylethanolamine.

[0054] One of the preferred groups of salt-forming agents is triethylamine.

[0055] According to an embodiment of the present invention, the organic solvent used in the present invention is at least one of acetone and butanone.

[0056] According to an embodiment of the present invention, the method for preparing a water-resistant and flexible waterborne polyurethane film product based on multiple hydrogen bonds is characterized in that the method for preparing the waterborne polyurethane film product comprises the following steps:

[0057] ⑴ Preparation of waterborne polyurethane emulsion

[0058] ① Raw material pretreatment: firstly, the hydrogen bond monomer precursor compound, polysiloxane, polymer polyol, hydrophilic chain extender and cross-linking agent are dehydrated under vacuum conditions at 90-120°C;

[0059] ② Preparation of waterborne polyurethane polymer: add the polysiloxane and polymer polyol treated in step ① to a reaction kettle, then add diisocyanate, react at 80-95° C. for 2-4 hours, and then cool to 60-70° C.; add the crosslinking agent treated in step ①, react at 80-90° C. for 2-4 hours, and then cool to 60-70° C.; add the hydrophilic chain extender and organic solvent treated in step ①, react at 70-90° C. for 2-4 hours, and then cool to 50-60° C.; add the hydrogen bond monomer precursor compound and organic solvent treated in step ①, react at 50-70° C. for 2-4 hours, and then cool to 20-30° C.; add a salt-forming agent and an organic solvent, react at 20-30° C. for 0.5-1 hour to obtain a waterborne polyurethane polymer;

[0060] ③ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ③ into an emulsification tank, maintain the temperature of the emulsification tank at 0-10° C., pour 500-700 parts by weight of deionized water into the emulsification tank, and stir at a speed of 8000-12000 rpm for 20-60 minutes. After emulsification, stir at a speed of 200-500 rpm for 4-6 hours to obtain a waterborne polyurethane emulsion;

[0061] ④ Removing organic solvent: Transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 40-50° C., and remove the organic solvent under vacuum to obtain the aqueous polyurethane emulsion for the film product.

[0062] ⑵ Forming process of waterborne polyurethane film products

[0063] ①Mold cleaning: acid wash, alkali wash, deionize the glass mold, and dry it at 100-110℃;

[0064] ②Impregnation of release agent: Cool the glass mold to 70-80℃, impregnate the release agent, and dry at 100-110℃;

[0065] ③Immersing in water-based polyurethane emulsion: Cool the glass mold to 60-70℃, immerse in water-based polyurethane emulsion for the first time, 70-80℃, bake for 1-3 minutes, immerse in water-based polyurethane emulsion for the second time, 70-80℃, bake for 1-3 minutes, immerse in water-based polyurethane emulsion for the third time, 70-80℃, bake for 6-8 minutes, and dry at 100-110℃ for 10-20 minutes;

[0066] ④ Curling: curl the water-based polyurethane film;

[0067] ⑤Immerse in release agent: immerse the mold in the release agent and dry at 100-110℃ for 20-30 minutes;

[0068] ⑥ Demolding, electrical inspection, and packaging: Cool the mold to room temperature, demold, and after passing the electrical inspection, optionally add an anti-sticking agent / lubricant and package to obtain the finished waterborne polyurethane film product.

[0069] The anti-sticking agent is a water suspension formed by adding a water suspension of silicon dioxide into an aqueous polyurethane emulsion; the lubricant includes water-based, silicon-based and oil-based lubricants.

[0070] According to an embodiment of the present invention, the method for preparing a water-resistant and flexible waterborne polyurethane film product based on multiple hydrogen bonds is characterized in that the method for preparing the waterborne polyurethane film product comprises the following steps:

[0071] ⑴ Preparation of waterborne polyurethane emulsion

[0072] ① Raw material pretreatment: firstly, dehydrate the hydrogen bond monomer precursor compound, polysiloxane, polymer polyol, hydrophilic chain extender and cross-linking agent under vacuum conditions of 90-120°C;

[0073] ② Preparation of hydrogen-bonding monomer: Add the hydrogen-bonding monomer precursor compound treated in step ① and the organic solvent into the reaction kettle, then add diisocyanate, and react at 0-10° C. for 2-4 hours;

[0074] ③ Preparation of waterborne polyurethane polymer: add the polysiloxane and polymer polyol treated in step ① into a reaction kettle, react at 80-95° C. for 2-4 hours, and then cool to 60-70° C.; add the crosslinking agent treated in step ①, react at 80-90° C. for 2-4 hours, and then cool to 60-70° C.; add the hydrophilic chain extender and organic solvent treated in step ①, react at 70-90° C. for 2-4 hours, and then cool to 20-30° C.; add a salt-forming agent and an organic solvent, react at 20-30° C. for 0.5-1 hour, and obtain a waterborne polyurethane polymer;

[0075] ④ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ③ into an emulsification tank, maintain the temperature of the emulsification tank at 0-10°C, pour 500-700 parts by weight of deionized water into the emulsification tank, and stir at a speed of 8000-12000 rpm for 20-60 minutes, and stir at a speed of 200-500 rpm for 4-6 hours after emulsification to obtain a waterborne polyurethane emulsion;

[0076] ⑤ Removing organic solvent: The aqueous polyurethane emulsion prepared in step ③ is transferred to a desolventizing tank, heated to 40-50° C., and the organic solvent is removed under vacuum to obtain the aqueous polyurethane emulsion for the film product.

[0077] ⑵ Forming process of waterborne polyurethane film products

[0078] ①Mold cleaning: acid wash, alkali wash, deionize the glass mold, and dry it at 100-110℃;

[0079] ②Impregnation of release agent: Cool the glass mold to 70-80℃, impregnate the release agent, and dry at 100-110℃;

[0080] ③Immersing in water-based polyurethane emulsion: Cool the glass mold to 60-70℃, immerse in water-based polyurethane emulsion for the first time, 70-80℃, bake for 1-3 minutes, immerse in water-based polyurethane emulsion for the second time, 70-80℃, bake for 1-3 minutes, immerse in water-based polyurethane emulsion for the third time, 70-80℃, bake for 6-8 minutes, and dry at 100-110℃ for 10-20 minutes;

[0081] ④ Curling: curl the water-based polyurethane film;

[0082] ⑤Immerse in release agent: immerse the mold in the release agent and dry at 100-110℃ for 20-30 minutes;

[0083] ⑥ Demolding, electrical inspection, and packaging: Cool the mold to room temperature, demold, and after passing the electrical inspection, optionally add an anti-sticking agent / lubricant and package to obtain the finished waterborne polyurethane film product.

[0084] The anti-sticking agent is a water suspension formed by adding a water suspension of silicon dioxide into an aqueous polyurethane emulsion; the lubricant includes water-based, silicon-based and oil-based lubricants.

[0085] According to an embodiment of the present invention, the method for preparing a water-resistant and flexible waterborne polyurethane film product based on multiple hydrogen bonds is characterized in that the method for preparing the waterborne polyurethane film product comprises the following steps:

[0086] ⑴ Preparation of waterborne polyurethane emulsion

[0087] ① Raw material pretreatment: firstly, dehydrate the hydrogen bond monomer precursor compound, polysiloxane, polymer polyol, hydrophilic chain extender and cross-linking agent under vacuum conditions of 90-120°C;

[0088] ② Preparation of waterborne polyurethane polymer: add the polysiloxane and polymer polyol treated in step ① to a reaction kettle, then add diisocyanate, react at 80-95° C. for 2-4 hours, and then cool to 60-70° C.; add the crosslinking agent treated in step ①, react at 80-90° C. for 2-4 hours, and then cool to 60-70° C.; add the hydrophilic chain extender and organic solvent treated in step ①, react at 70-90° C. for 2-4 hours, and then cool to 50-60° C.; add the hydrogen bond monomer precursor compound, diisocyanate and organic solvent treated in step ①, react at 50-70° C. for 2-4 hours, and then cool to 20-30° C.; add a salt-forming agent and an organic solvent, react at 20-30° C. for 0.5-1 hour to obtain a waterborne polyurethane polymer;

[0089] ③ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ③ into an emulsification tank, maintain the temperature of the emulsification tank at 0-10° C., pour 500-700 parts by weight of deionized water into the emulsification tank, and stir at a speed of 8000-12000 rpm for 20-60 minutes. After emulsification, stir at a speed of 200-500 rpm for 4-6 hours to obtain a waterborne polyurethane emulsion;

[0090] ④ Removing organic solvent: Transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 40-50° C., and remove the organic solvent under vacuum to obtain the aqueous polyurethane emulsion for the film product.

[0091] ⑵ Forming process of waterborne polyurethane film products

[0092] ①Mold cleaning: acid wash, alkali wash, deionize the glass mold, and dry it at 100-110℃;

[0093] ②Impregnation of release agent: Cool the glass mold to 70-80℃, impregnate the release agent, and dry at 100-110℃;

[0094] ③Immersing in water-based polyurethane emulsion: Cool the glass mold to 60-70℃, immerse in water-based polyurethane emulsion for the first time, 70-80℃, bake for 1-3 minutes, immerse in water-based polyurethane emulsion for the second time, 70-80℃, bake for 1-3 minutes, immerse in water-based polyurethane emulsion for the third time, 70-80℃, bake for 6-8 minutes, and dry at 100-110℃ for 10-20 minutes;

[0095] ④ Curling: curl the water-based polyurethane film;

[0096] ⑤Immerse in release agent: immerse the mold in the release agent and dry at 100-110℃ for 20-30 minutes;

[0097] ⑥ Demolding, electrical inspection, and packaging: Cool the mold to room temperature, demold, and after passing the electrical inspection, optionally add an anti-sticking agent / lubricant and package to obtain the finished waterborne polyurethane film product.

[0098] The anti-sticking agent is a water suspension formed by adding a water suspension of silicon dioxide into an aqueous polyurethane emulsion; the lubricant includes water-based, silicon-based and oil-based lubricants.

[0099] Compared with the prior art, the present invention has the following advantages:

[0100] The waterborne polyurethane film product prepared by the present invention is easy to demould, not easy to adhere, and has the characteristics and advantages of excellent water resistance, flexibility and low modulus. The waterborne polyurethane in the present invention constructs multiple hydrogen bond units and polysiloxane and / or fluorine-containing units in its structure. A water-resistant and flexible waterborne polyurethane film product is prepared by combining multiple hydrogen bond units and polysiloxane and / or fluorine-containing units. The toughness of the waterborne polyurethane film product is improved based on the energy dissipation effect of multiple hydrogen bonds; at the same time, the water resistance of the waterborne polyurethane film product is improved based on the hydrophobic characteristics and flexibility of polysiloxane and / or fluorine-containing units, and the modulus of the waterborne polyurethane film product is reduced, the softness is improved, and the demoulding property of the waterborne polyurethane film product in the production process is improved, and the self-adhesion caused by the supramolecular hydrogen bonds and optional dynamic covalent bonds is further reduced. The performance of the waterborne polyurethane film product prepared by the present invention is better than the requirements of the new standard and has excellent comprehensive performance. The waterborne polyurethane film product prepared by the present invention has a thickness of less than 30 μm, a tearing force greater than 20 N, a tensile elongation greater than 690%, a bursting volume greater than 11 L, and a bursting pressure greater than 3 KPa. After the waterborne polyurethane film product is immersed in hot water at (50±1)° C. for 1 hour, its tearing force is greater than 18 N, its 100% tensile modulus is less than 1.0 MPa, and its toughness is greater than 32 MJ / m 3 The performance is better than the requirements of the new condom standard YY / T 1850-2023, and meets the new requirements for water-based polyurethane film products under the new standards and new era. In contrast, when the waterborne polyurethane film product only contains multiple hydrogen bond units without polysiloxane and / or fluorine-containing units, the prepared waterborne polyurethane film product is prone to adhesion and difficult demoulding. The 100% tensile modulus of the waterborne polyurethane film product is 2.0MPa, and its tear force is 11.2N after soaking in hot water at (50±1)°C for 1 hour. The water resistance does not meet the requirements of the new standard, and its 100% tensile modulus is relatively high, that is, the softness deviation; and when the waterborne polyurethane film product contains polysiloxane and / or fluorine-containing units without multiple hydrogen bond units, the tear force of the waterborne polyurethane film product is 12N, the bursting volume is 3L, the bursting pressure is greater than 1.1KPa, and the tear force of the waterborne polyurethane film product after soaking in hot water at (50±1)°C for 1 hour is 7.0N; as waterborne polyurethane film products, the performance of the two does not meet the requirements of the new condom standard.

[0101] The waterborne polyurethane film product of the present invention does not use catalysts such as organic tin in the waterborne polyurethane polymerization process, thereby avoiding the catalytic effect of the catalyst on the hydrolysis of the waterborne polyurethane and improving the water resistance of the waterborne polyurethane film product. BRIEF DESCRIPTION OF THE DRAWINGS

[0102] Figure 1(a) is a picture of a waterborne polyurethane film product; (b) is a picture of a waterborne polyurethane film product under transverse stretching; (c) is a picture of a waterborne polyurethane film product under longitudinal stretching; (d) is a TGA picture of a sample of a waterborne polyurethane film product in Example 1; (e) is a DSC picture of a sample of a waterborne polyurethane film product in Example 1; (f) is a particle size distribution picture of the waterborne polyurethane emulsion in Example 1, wherein the initial curve refers to the particle size distribution picture of the waterborne polyurethane emulsion just after production, and the 180d curve refers to the particle size distribution picture of the waterborne polyurethane emulsion tested after 180 days of production;

[0103] Figure 2 (a) is the stress-strain curve of the water-based polyurethane film product sample and the commercial water-based polyurethane condom sample of Example 1, wherein Okamoto 001 curve refers to the stress-strain curve of the water-based polyurethane condom of Okamoto brand model 001, Sagami 001 curve refers to the stress-strain curve of the water-based polyurethane condom of Sagami brand model 001, Durex 001 curve refers to the stress-strain curve of the water-based polyurethane condom of Durex brand model 001, and Jissbon 001 curve refers to the stress-strain curve of the water-based polyurethane condom of Jissbon brand model 001; (b) is the stress-strain curve of the water-based polyurethane film product of Example 2; (c) is the stress-strain curve of the water-based polyurethane film product of Example 3; (d) is the stress-strain curve of the water-based polyurethane film product of Example 4;

[0104] Figure 3 (a) is the stress-strain curve of the waterborne polyurethane film product of Example 5; (b) is the stress-strain curve of the waterborne polyurethane film product of Example 6; (c) is the stress-strain curve of the waterborne polyurethane film product of Example 7; (d) is the stress-strain curve of the waterborne polyurethane film product of Example 8;

[0105] Figure 4 (a) is the stress-strain curve of the waterborne polyurethane film product of Example 9; (b) is the stress-strain curve of the waterborne polyurethane film product of Example 10; (c) is the stress-strain curve of the waterborne polyurethane film product of Example 11; (d) is the stress-strain curve of the waterborne polyurethane film product of Example 12;

[0106] Figure 5 (a) is the stress-strain curve of the waterborne polyurethane film product of Example 13; (b) is the stress-strain curve of the waterborne polyurethane film product of Example 14;

[0107] Figure 6 : The stress-strain curve of the waterborne polyurethane film product of Example 15 is shown in FIG. DETAILED DESCRIPTION

[0108] In the present invention, the range of carbon atoms in a group is marked in the subscript position of C in the form of a subscript, indicating the number of carbon atoms in the group, for example, C 1-24 means "having 1 to 24 carbon atoms". "Substituted C 1-24 "Alkylenyl" refers to C 1-24 A group obtained by replacing the hydrogen atom of an alkylene group. 1-12 The alkylene group may be selected from any alkylene group having the number of carbon atoms in the range indicated by the subscript, that is, selected from C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , C 12 Any alkylene group.

[0109] In the present invention, unless otherwise specified, an integer range marked in interval form means that any integer can be selected from the range, and the range includes both endpoints. For example, the integer range 25-40 means any integer among 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, and 40.

[0110] In the present invention, the dynamic disulfide bond can be formed by the oxidative coupling reaction of the sulfhydryl group contained in the compound raw material, the bonding reaction of the sulfhydryl radical, or by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw material containing the disulfide bond. In the present invention, the dynamic diselenide bond can be formed by the oxidative coupling reaction of the selenol contained in the compound raw material, the bonding reaction of the selenium radical, or by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw material containing the dynamic selenide bond. In the present invention, the dynamic ketal bond, dynamic acetal bond, dynamic thioketal bond, dynamic thioacetal bond can be formed by the condensation reaction of the ketone group, aldehyde group and hydroxyl group contained in the compound raw material, or by the exchange reaction of the acetal dynamic covalent bond with alcohol, thiol, aldehyde, ketone, or by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw material containing the acetal dynamic covalent bond. In the present invention, the dynamic imine bond and dynamic oxime bond can be formed by condensation reaction between keto group, aldehyde group, acyl group and amino group, hydrazine group and hydrazide group contained in the compound raw material, or can be formed by polymerization / cross-linking reaction between reactive groups contained in the compound raw material containing dynamic covalent bonds based on carbon-nitrogen double bonds.

[0111] In the present invention, “substituted”, taking “substituted” “phenylene” as an example, means that any one or more hydrogen atoms at any position in the substituted “phenylene” can be substituted.

[0112] In the present invention, the "long-chain alkyl" has a molecular weight of 100-1000 Da and a structure of a long straight-chain alkyl, wherein the alkyl is a hydrocarbon group formed by a saturated hydrocarbon group losing a hydrogen atom.

[0113] In the present invention, "fluorinated hydrocarbon group" refers to trifluoropropyl or perfluoroalkyl oxasulfonyl propyl or

[0114] In the present invention, "epoxy hydrocarbon group" refers to

[0115] The "alkaline detergent" in the present invention is an aqueous solution with a pH value greater than 10.

[0116] The "acidic detergent" in the present invention refers to an aqueous solution with a pH value of less than 2 to which detergent is added.

[0117] The "release agent" in the present invention refers to an aqueous solution containing silicon dioxide.

[0118] The "anti-sticking agent" in the present invention is an aqueous suspension formed by adding an aqueous suspension of silicon dioxide into an aqueous polyurethane emulsion.

[0119] The "lubricant" in the present invention is water-based, silicone-based and oil-based lubricants. The water-based lubricant is mainly composed of water, glycerin and other ingredients, has a moist texture, is easily absorbed by the skin, is refreshing to use and easy to clean; the oil-based lubricant contains mineral oil, etc., has a greasy texture, is not easily absorbed by the skin, has strong durability, and can be used in water; the silicone-based lubricant contains medical silicone oil.

[0120] When Da is used to describe the molecular weight of a compound formula in the present invention, the value falls within the range of ±10% (including the endpoint) of the stated value for a single compound molecule.

[0121] The invention discloses a water-resistant and flexible waterborne polyurethane film product based on multiple hydrogen bonds, which is characterized in that the product is obtained from an emulsion prepared from a waterborne polyurethane polymer through a film-forming process; the waterborne polyurethane polymer contains at least one multiple hydrogen bond unit and at least one polysiloxane unit in its structure, the multiple hydrogen bond unit is formed by a hydrogen bond monomer, and the at least one hydrogen bond monomer is formed by the reaction of a hydrogen bond monomer precursor compound and an isocyanate group during the preparation of the waterborne polyurethane polymer; the number of hydrogen bond teeth of the multiple hydrogen bond unit is not less than 3; and the polysiloxane unit is introduced through the polymerization reaction of polysiloxane and diisocyanate.

[0122] The waterborne polyurethane polymer of the present invention is prepared from the following raw materials in parts by weight:

[0123] 3-10 parts of polysiloxane

[0124] Polymer polyol 40-70 parts

[0125] 2-15 parts of hydrogen bond monomer precursor compound

[0126] 3-6 parts of hydrophilic chain extender

[0127] 10-30 parts of diisocyanate

[0128] Crosslinking agent 0.5-25 parts

[0129] 2-5 parts of salt-forming agent.

[0130] The hydrogen bonding monomer of the present invention has the following general structure:

[0131]

[0132] According to a preferred embodiment of the present invention, the hydrogen bonding monomer has the following general structure:

[0133]

[0134] Wherein, L1 is a divalent linking group, and both ends are connected to the carbon atoms of the hydrazide group, and the divalent linking group can be a carbon chain linking group or a linking group containing a dynamic bond; wherein the carbon chain linking group is C 1-24 Alkylene or substituted C 1-24 Hydrocarbylene; wherein the linker containing a dynamic bond is selected from a linker containing a dynamic disulfide bond, a linker containing a dynamic diselenide bond, a linker containing a dynamic ketal bond, a linker containing a dynamic acetal bond, a linker containing a dynamic thioketal bond, a linker containing a dynamic thioacetal bond, a linker containing a dynamic imine bond, and a linker containing a dynamic oxime bond. Wherein, the linker containing a dynamic disulfide bond is selected from the following structures:

[0135]

[0136]

[0137] Wherein, the linker containing a dynamic diselenide bond is selected from the following structures:

[0138]

[0139] Wherein, the linking group containing a dynamic ketal bond, the linking group containing a dynamic acetal bond, the linking group containing a dynamic thioketal bond, and the linking group containing a dynamic thioacetal bond are selected from the following structures:

[0140]

[0141] Wherein, the linker containing a dynamic imine bond and the linker containing a dynamic oxime bond are selected from the following structures:

[0142]

[0143] Indicates connection to polymer chains, cross-links, groups, atoms.

[0144] One of the preferred groups of L1 is C 2-8 The alkylene group is preferably 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, or 1,8-octylene.

[0145] One of the preferred groups of L1 is one of phenylene and substituted phenylene; wherein the substituted phenylene is a phenylene in which any hydrogen atom is substituted by a substituent; wherein the substituent includes but is not limited to a heteroatom or a group containing a heteroatom; specifically,

[0146] One of the preferred options for L1:

[0147] Any one of.

[0148] According to the general structure of the hydrogen bonding monomer, the hydrogen bonding monomer precursor compound of the hydrogen bonding monomer is selected from at least one of the following compounds:

[0149] Wherein, L6 is a divalent linking group, and both ends are connected to the carbon atoms of the hydrazide group, and the divalent linking group can be a carbon chain linking group or a linking group containing a dynamic bond; wherein the carbon chain linking group is C 1-24 Alkylene or substituted C 1-24 Hydrocarbylene; wherein the linker containing a dynamic bond is selected from a linker containing a dynamic disulfide bond, a linker containing a dynamic diselenide bond, a linker containing a dynamic ketal bond, a linker containing a dynamic acetal bond, a linker containing a dynamic thioketal bond, a linker containing a dynamic thioacetal bond, a linker containing a dynamic imine bond, and a linker containing a dynamic oxime bond. Wherein, the linker containing a dynamic disulfide bond is selected from the following structures:

[0150]

[0151]

[0152] Wherein, the linker containing a dynamic diselenide bond is selected from the following structures:

[0153]

[0154] Wherein, the linking group containing a dynamic ketal bond, the linking group containing a dynamic acetal bond, the linking group containing a dynamic thioketal bond, and the linking group containing a dynamic thioacetal bond are selected from the following structures:

[0155]

[0156] Wherein, the linker containing a dynamic imine bond and the linker containing a dynamic oxime bond are selected from the following structures:

[0157]

[0158] Indicates connection to polymer chains, cross-links, groups, atoms.

[0159] One of the preferred groups of L6 is C 2-8 The alkylene group is preferably 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, or 1,8-octylene.

[0160] One of the preferred groups of L6 is one of phenylene and substituted phenylene; wherein the substituted phenylene is a phenylene in which any hydrogen atom is substituted by a substituent; wherein the substituent includes but is not limited to a heteroatom or a group containing a heteroatom; specifically,

[0161] One of the preferred options for L1:

[0162] Any one of.

[0163] According to the general structure of the hydrogen bonding monomer, the hydrogen bonding monomer precursor compounds of the hydrogen bonding monomer can be respectively listed as follows, but the present invention is not limited thereto.

[0164]

[0165]

[0166] 3,3'-Dithiobispropionyl hydrazide.

[0167] According to an embodiment of the present invention, it also contains at least a second hydrogen bonding monomer, which is formed by the reaction of a hydrogen bonding monomer precursor compound and an isocyanate group during the preparation of the waterborne polyurethane polymer, or the hydrogen bonding monomer precursor compound is first prepared and then used as a polymerization monomer for the polymerization reaction of the waterborne polyurethane polymer, and the second hydrogen bonding monomer is in the polymer main chain and / or polymer side chain, polymer side group, and polymer end group.

[0168] The second hydrogen bond monomer has one of the following general structures:

[0169]

[0170] According to the general structure of the second hydrogen bonding monomer, the hydrogen bonding monomer precursor compounds of the second hydrogen bonding monomer can be respectively listed as the following compounds, but the present invention is not limited thereto.

[0171]

[0172] According to an embodiment of the present invention, the number of hydrogen bond teeth of the multiple hydrogen bonds is the number of hydrogen bonds formed by the donor (D, that is, the hydrogen atom) and the acceptor (A, that is, the electronegative atom that accepts the hydrogen atom) of the hydrogen bonding group, and each DA combination is a tooth (as shown in the following formula, which lists the hydrogen bonding situations of tridentate, tetradentate, and hexadentate hydrogen bonding groups); since the more teeth the stronger the hydrogen bonding effect, the number of hydrogen bond teeth of the multiple hydrogen bonds described in the present invention usually exceeds that of the tridentate hydrogen bonds, and its effect is strong, which can effectively provide multiple hydrogen bond cross-linking effects.

[0173]

[0174] The hydrogen bonding conditions of the tridentate, tetradentate and hexadentate hydrogen bonding groups can be listed as follows, but the present invention is not limited thereto.

[0175]

[0176] According to an embodiment of the present invention, the water-resistant and flexible waterborne polyurethane film product based on multiple hydrogen bonds is characterized in that the waterborne polyurethane polymer is prepared from the following raw materials in parts by weight:

[0177] Polysiloxane 5-8 parts

[0178] Polymer polyol 45-60 parts

[0179] 2.5-6 parts of hydrogen bond monomer precursor compound

[0180] 4-6 parts of hydrophilic chain extender

[0181] 20-30 parts of diisocyanate

[0182] Crosslinking agent 0.6-18 parts

[0183] 2.5-3.5 parts of salt-forming agent.

[0184] The polysiloxane is selected, and its structure is shown below,

[0185]

[0186] Among them, R9, R 10 Each independently selected from one of hydroxyl, amino, and thiol, R fis selected from the group consisting of a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, an undecafluoropentyl group, a trifluoropropyl group, a perfluoroalkyl oxasulfonyl propyl group,

[0187] One of the groups, L4 and L5 are divalent linking groups, each independently selected from one of 1,2-ethylene and 1,3-propylene; wherein n is the number of repeating units; wherein the fluorinated polysiloxane has an average number average molecular weight of 2000-3000Da.

[0188] The polysiloxane is selected from a block copolymer of polysiloxane and fluorine-containing polyether, wherein the block copolymer of polysiloxane and fluorine-containing polyether is formed by polymerization of polysiloxane segments and fluorine-containing polyether segments through diisocyanate or diisocyanate-terminated polymers; the block copolymer of polysiloxane and fluorine-containing polyether has a structure as shown below:

[0189] The structure of the fluorinated polyether chain segment is as follows:

[0190]

[0191] The structure of the fluorinated polyether chain is shown below:

[0192]

[0193] Among them, R 17 , R 18 , R 25 , R 26 Each independently selected from one of hydroxyl, amino, and thiol, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 Each is independently selected from a methyl group, a long-chain alkyl group, a phenyl group, and an epoxy group, R 19 , R 20 , R 21 , R 22 , R 23 , R 24 Each is independently selected from a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, an undecafluoropentyl group, a trifluoropropyl group, a perfluoroalkyl oxasulfonyl propyl group, One of L7, L8, L9, L 10is a divalent linking group, L7 and L8 are each independently selected from one of 1,2-ethylene, 1,3-propylene, OH2CH2C-OH2CH2CH2C-, -OH2CH2CH2C-OH2CH2CH2C-, and -OH2CH2C-OH2CH2C-, the carbon atoms in -OHCH2C-OH2CH2CH2C-, -OH2CH2CH2C-OH2CH2CH2C-, and -OH2CH2C-OH2CH2C- are connected to the silicon atom, and L9, L 10 Each independently selected from wherein r, s, t, e, u, v, and w are the numbers of repeating units; wherein the diisocyanate is selected from at least one of isophorone diisocyanate, hexamethylene diisocyanate, and hydrogenated phenylmethane diisocyanate; wherein the diisocyanate-terminated polymer is selected from isocyanate-terminated polytetrahydrofuran diol with an average number average molecular weight of 1000-2000Da, polycarbonate diol with an average number average molecular weight of 1000-2000Da, and polyisocyanate diol with an average number average molecular weight of 1000-2000Da. At least one of polycaprolactone diol with a molecular weight of 1000-2000Da, polybutadiene diol with an average number average molecular weight of 1000-2000Da, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, cyclohexanediol, dimethylolpropionic acid and dimethylolbutyric acid; wherein the polysiloxane has an average number average molecular weight of 2000-3000Da.

[0194] The structure of the polysiloxane is shown below:

[0195]

[0196] Wherein, R1 and R2 are each independently selected from one of hydroxyl, amino, and mercapto; R3, R4, R5, R6, R7, and R8 are each independently selected from one of methyl, long-chain alkyl, phenyl, and epoxy; L2 and L3 are divalent linking groups, each independently selected from one of 1,2-ethylene and 1,3-propylene; wherein m is the number of repeating units; wherein the non-fluorinated polysiloxane has an average number average molecular weight of 2000-3000Da.

[0197] The polymer polyol is selected from at least one of polytetramethylene glycol, polycarbonate glycol, polycaprolactone glycol and polybutadiene glycol; wherein the polymer polyol has an average number average molecular weight of 2000-3000 Da.

[0198] The hydrophilic chain extender is selected from at least one of dimethylol propionic acid and dimethylol butyric acid.

[0199] The diisocyanate is selected from at least one of isophorone diisocyanate, hexamethylene diisocyanate and hydrogenated phenylmethane diisocyanate.

[0200] The crosslinking agent is selected from at least one of trimethylolpropane, triethanolamine, modified castor oil and polyether triol; wherein the modified castor oil has an average number average molecular weight of 500-1200Da and a functionality of 2.5-3.5; wherein the polyether triol has an average number average molecular weight of 3000-5000Da.

[0201] The salt-forming agent is selected from triethylamine.

[0202] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described below in conjunction with specific embodiments. However, it should be pointed out that the specific material ratios, process conditions and results described in the embodiments of the present invention are only used to illustrate the present invention and cannot be used to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit and essence of the present invention should be included in the protection scope of the present invention.

[0203] Example 1

[0204] (1) Preparation of waterborne polyurethane emulsion:

[0205] ① Raw material pretreatment: first, the hydrogen bond monomer precursor compound 1 and dimethylol propionic acid of the following structure are respectively dehydrated at 90° C. and vacuum conditions below -0.09 MPa for 3 hours, and then cooled to 50° C. for standby use; the dihydroxy polysiloxane with an average number average molecular weight of 2000 Da, polytetrahydrofuran diol with an average number average molecular weight of 2000 Da, and modified castor oil with a trifunctionality average number average molecular weight of 579 Da are dehydrated at 115° C. and vacuum conditions below -0.09 MPa for 4 hours, and then cooled to 60° C. for standby use;

[0206] Hydrogen bond monomer precursor compound 1;

[0207] Bishydroxy polysiloxane with an average number average molecular weight of 2000Da;

[0208] ② Preparation of waterborne polyurethane polymer: 7.26 parts by weight of dihydroxy polysiloxane treated in step ①, 55.40 parts by weight of polytetrahydrofuran diol, and 23.68 parts by weight of isophorone diisocyanate were added to a reactor, reacted at 90°C for 3 hours, and then cooled to 60°C; 3.23 parts by weight of modified castor oil treated in step ① were added to a reactor, reacted at 90°C for 4 hours, and then cooled to 60°C; 4.56 parts by weight of dimethylol propionic acid treated in step ① and 30 parts by weight of acetone were added, reacted at 90°C for 3 hours, and then cooled to 50°C; 2.70 parts by weight of hydrogen bond monomer precursor compound 1 treated in step ① and 50 parts by weight of acetone were added, reacted at 60°C for 4 hours, and then cooled to 30°C; 3.11 parts by weight of triethylamine and 50 parts by weight of acetone were added, reacted at 30°C for 0.5 hours, and a waterborne polyurethane polymer was obtained;

[0209] ③ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ② into an emulsification tank, maintain the temperature of the emulsification tank at 0-10° C., pour 650 parts by weight of deionized water into the emulsification tank, and stir at a speed of 9000 rpm for 30 minutes. After emulsification, stir at a speed of 400 rpm for 4 hours to obtain a waterborne polyurethane emulsion;

[0210] ④ Removal of organic solvent: transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 45°C, and remove acetone under vacuum to obtain the aqueous polyurethane emulsion for the film product;

[0211] (2) Preparation of waterborne polyurethane film products

[0212] ①Mold cleaning: acid wash, alkali wash, deionize the glass mold, and dry it at 110℃;

[0213] ②Impregnation of release agent: Cool the glass mold to 75℃, impregnate the release agent, and dry at 110℃;

[0214] ③Immersing in water-based polyurethane emulsion: The glass mold is cooled to 60°C, immersed in water-based polyurethane emulsion for the first time, dried at 75°C for 1 minute, immersed in water-based polyurethane emulsion for the second time, dried at 75°C for 1 minute, immersed in water-based polyurethane emulsion for the third time, dried at 80°C for 7 minutes, and dried at 110°C for 20 minutes;

[0215] ④ Curling: Curl the waterborne polyurethane film to a suitable position;

[0216] ⑤Immerse in release agent: immerse the mold in the release agent and dry at 110℃ for 25 minutes;

[0217] ⑥ Demolding, electrical inspection, and packaging: Cool the mold to room temperature, demould, and after passing the electrical inspection, optionally add an anti-sticking agent / lubricant and package the finished waterborne polyurethane film product.

[0218] Example 2

[0219] (1) Preparation of waterborne polyurethane emulsion:

[0220] ① Raw material pretreatment: first, the hydrogen bond monomer precursor compound 2 and dimethylol propionic acid of the following structure are respectively dehydrated at 90° C. and vacuum conditions below -0.09 MPa for 3 hours, and then cooled to 50° C. for standby use; the dihydroxy polysiloxane with an average number average molecular weight of 2000Da and the polytetrahydrofuran diol with an average number average molecular weight of 2000Da of the following structure are dehydrated at 115° C. and vacuum conditions below -0.09 MPa for 4 hours, and then cooled to 60° C. for standby use;

[0221] Hydrogen bond monomer precursor compound 2;

[0222] Bishydroxy polysiloxane with an average number average molecular weight of 2000Da;

[0223] ② Preparation of waterborne polyurethane polymer: 7.44 parts by weight of dihydroxy polysiloxane treated in step ①, 56.75 parts by weight of polytetrahydrofuran diol, and 24.25 parts by weight of isophorone diisocyanate were added to a reactor, reacted at 90°C for 3 hours, and then cooled to 60°C; 0.83 parts by weight of triethanolamine was added to a reactor, reacted at 80°C for 2 hours, and then cooled to 60°C; 4.67 parts by weight of dimethylol propionic acid treated in step ① and 30 parts by weight of acetone were added, reacted at 90°C for 3 hours, and then cooled to 50°C; 2.82 parts by weight of hydrogen bond monomer precursor compound 2 treated in step ① and 50 parts by weight of acetone were added, reacted at 60°C for 4 hours, and then cooled to 30°C; 3.19 parts by weight of triethylamine and 50 parts by weight of acetone were added, reacted at 30°C for 0.5 hours, and a waterborne polyurethane polymer was obtained;

[0224] ③ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ② into an emulsification tank, maintain the temperature of the emulsification tank at 0-10° C., pour 635 parts by weight of deionized water into the emulsification tank, and stir at a speed of 9000 rpm for 30 minutes. After emulsification, stir at a speed of 400 rpm for 4 hours to obtain a waterborne polyurethane emulsion;

[0225] ④ Removal of organic solvent: transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 45°C, and remove acetone under vacuum to obtain the aqueous polyurethane emulsion for the film product;

[0226] (2) The preparation process of waterborne polyurethane film product is the same as that of Experimental Example 1.

[0227] Example 3

[0228] (1) Preparation of waterborne polyurethane emulsion:

[0229] ① Raw material pretreatment: first, the hydrogen bond monomer precursor compound 3, dimethylol propionic acid, and trimethylol propane of the following structure are respectively dehydrated at 90° C. and vacuum conditions below -0.09 MPa for 3 hours, and then cooled to 50° C. for standby use; the dihydroxy polysiloxane with an average number average molecular weight of 2500Da and the polytetrahydrofuran diol with an average number average molecular weight of 2000Da of the following structure are dehydrated at 115° C. and vacuum conditions below -0.09 MPa for 4 hours, and then cooled to 60° C. for standby use;

[0230] Hydrogen bond monomer precursor compound 3;

[0231] Bishydroxy polysiloxane with an average number average molecular weight of 2500Da;

[0232] ② Preparation of waterborne polyurethane polymer: 7.99 parts by weight of dihydroxy polysiloxane treated in step ①, 52.80 parts by weight of polytetrahydrofuran diol, and 26.08 parts by weight of isophorone diisocyanate were added to a reactor, reacted at 90°C for 3 hours, and then cooled to 60°C; 0.69 parts by weight of trimethylolpropane was added to a reactor, reacted at 90°C for 2 hours, and then cooled to 60°C; 4.35 parts by weight of dimethylolpropionic acid treated in step ① and 30 parts by weight of acetone were added, reacted at 90°C for 3 hours, and then cooled to 50°C; 5.07 parts by weight of hydrogen bond monomer precursor compound 3 treated in step ① and 50 parts by weight of acetone were added, reacted at 60°C for 4 hours, and then cooled to 30°C; 2.97 parts by weight of triethylamine and 50 parts by weight of acetone were added, reacted at 30°C for 0.5 hours, and a waterborne polyurethane polymer was obtained;

[0233] ③ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ② into an emulsification tank, maintain the temperature of the emulsification tank at 0-10° C., pour 682 parts by weight of deionized water into the emulsification tank, and stir at a speed of 9000 rpm for 30 minutes. After emulsification, stir at a speed of 400 rpm for 4 hours to obtain a waterborne polyurethane emulsion;

[0234] ④ Removal of organic solvent: transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 45°C, and remove acetone under vacuum to obtain the aqueous polyurethane emulsion for the film product;

[0235] (2) The preparation process of waterborne polyurethane film product is the same as that of Experimental Example 1.

[0236] Example 4

[0237] (1) Preparation of waterborne polyurethane emulsion:

[0238] ① Raw material pretreatment: first, the hydrogen bond monomer precursor compound 4, dimethylol propionic acid, and trimethylol propane of the following structure are dehydrated at 90°C and vacuum conditions below -0.09MPa for 3 hours, and then cooled to 50°C for standby use; the dihydroxy polysiloxane with an average number average molecular weight of 2500Da and the polycaprolactone diol with an average number average molecular weight of 2000Da of the following structure are dehydrated at 115°C and vacuum conditions below -0.09MPa for 4 hours, and then cooled to 60°C for standby use;

[0239] Hydrogen bond monomer precursor compound 4;

[0240] Bishydroxy polysiloxane with an average number average molecular weight of 2500Da;

[0241] ② Preparation of waterborne polyurethane polymer: 7.98 parts by weight of dihydroxy polysiloxane treated in step ①, 52.63 parts by weight of polycaprolactone diol, and 26.85 parts by weight of hydrogenated phenylmethane diisocyanate were added to a reactor, reacted at 90°C for 3 hours, and then cooled to 60°C; 0.69 parts by weight of trimethylolpropane was added to the reactor, reacted at 90°C for 2 hours, and then cooled to 60°C; 4.33 parts by weight of dimethylolpropionic acid treated in step ① and 30 parts by weight of acetone were added, reacted at 90°C for 3 hours, and then cooled to 50°C; 4.52 parts by weight of hydrogen bond monomer precursor compound 4 treated in step ① and 50 parts by weight of acetone were added, reacted at 60°C for 4 hours, and then cooled to 30°C; 2.96 parts by weight of triethylamine and 50 parts by weight of acetone were added, reacted at 30°C for 0.5 hours, and a waterborne polyurethane polymer was obtained;

[0242] ③ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ② into an emulsification tank, maintain the temperature of the emulsification tank at 0-10° C., pour 684 parts by weight of deionized water into the emulsification tank, and stir at a speed of 9000 rpm for 30 minutes. After emulsification, stir at a speed of 400 rpm for 4 hours to obtain a waterborne polyurethane emulsion;

[0243] ④ Removal of organic solvent: transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 45°C, and remove acetone under vacuum to obtain the aqueous polyurethane emulsion for the film product;

[0244] (2) The preparation process of waterborne polyurethane film product is the same as that of Experimental Example 1.

[0245] Example 5

[0246] (1) Preparation of waterborne polyurethane emulsion:

[0247] ① Raw material pretreatment: first, the hydrogen bond monomer precursor compound 5, dimethylolbutyric acid, and trimethylolpropane of the following structure are respectively dehydrated at 90° C. and vacuum conditions below -0.09 MPa for 3 hours, and then cooled to 50° C. for standby use; the dihydroxy polysiloxane with an average number average molecular weight of 2000 Da and the polytetrahydrofuran diol with an average number average molecular weight of 2000 Da of the following structure are dehydrated at 115° C. and vacuum conditions below -0.09 MPa for 4 hours, and then cooled to 60° C. for standby use;

[0248] Hydrogen bond monomer precursor compound 5;

[0249] Bishydroxy polysiloxane with an average number average molecular weight of 2000Da;

[0250] ② Preparation of waterborne polyurethane polymer: 7.23 parts by weight of dihydroxy polysiloxane treated in step ①, 55.16 parts by weight of polytetrahydrofuran diol, and 25.89 parts by weight of isophorone diisocyanate were added to a reactor, reacted at 90°C for 3 hours, and then cooled to 60°C; 0.73 parts by weight of trimethylolpropane was added to a reactor, reacted at 90°C for 2 hours, and then cooled to 60°C; 4.11 parts by weight of dimethylolbutyric acid treated in step ① and 30 parts by weight of acetone were added, reacted at 90°C for 3 hours, and then cooled to 50°C; 3.74 parts by weight of hydrogen bond monomer precursor compound 5 treated in step ① and 50 parts by weight of acetone were added, reacted at 60°C for 4 hours, and then cooled to 30°C; 3.10 parts by weight of triethylamine and 50 parts by weight of acetone were added, reacted at 30°C for 0.5 hours, and a waterborne polyurethane polymer was obtained;

[0251] ③ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ② into an emulsification tank, maintain the temperature of the emulsification tank at 0-10° C., pour 653 parts by weight of deionized water into the emulsification tank, and stir at a speed of 9000 rpm for 30 minutes. After emulsification, stir at a speed of 400 rpm for 4 hours to obtain a waterborne polyurethane emulsion;

[0252] ④ Removal of organic solvent: transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 45°C, and remove acetone under vacuum to obtain the aqueous polyurethane emulsion for the film product;

[0253] (2) The preparation process of waterborne polyurethane film product is the same as that of Experimental Example 1.

[0254] Example 6

[0255] (1) Preparation of waterborne polyurethane emulsion:

[0256] ① Raw material pretreatment: first, the hydrogen bond monomer precursor compound 6, dimethylolbutyric acid, and trimethylolpropane of the following structure are respectively dehydrated at 90° C. and vacuum conditions below -0.09 MPa for 3 hours, and then cooled to 50° C. for standby use; the dihydroxy polysiloxane with an average number average molecular weight of 2000 Da and the polytetrahydrofuran diol with an average number average molecular weight of 3000 Da of the following structure are dehydrated at 115° C. and vacuum conditions below -0.09 MPa for 4 hours, and then cooled to 60° C. for standby use;

[0257] Hydrogen bond monomer precursor compound 6;

[0258] Bishydroxy polysiloxane with an average number average molecular weight of 2000Da;

[0259] ② Preparation of waterborne polyurethane polymer: 7.99 parts by weight of dihydroxy polysiloxane treated in step ①, 59.92 parts by weight of polytetrahydrofuran diol, and 20.06 parts by weight of isophorone diisocyanate were added to a reactor, reacted at 90°C for 3 hours, and then cooled to 60°C; 0.60 parts by weight of trimethylolpropane was added to a reactor, reacted at 90°C for 2 hours, and then cooled to 60°C; 4.33 parts by weight of dimethylolbutyric acid treated in step ① and 30 parts by weight of acetone were added, reacted at 90°C for 3 hours, and then cooled to 50°C; 2.78 parts by weight of hydrogen bond monomer precursor compound 6 treated in step ① and 50 parts by weight of acetone were added, reacted at 60°C for 4 hours, and then cooled to 30°C; 3.26 parts by weight of triethylamine and 50 parts by weight of acetone were added, reacted at 30°C for 0.5 hours, and a waterborne polyurethane polymer was obtained;

[0260] ③ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ② into an emulsification tank, maintain the temperature of the emulsification tank at 0-10° C., pour 782 parts by weight of deionized water into the emulsification tank, and stir at a speed of 9000 rpm for 30 minutes. After emulsification, stir at a speed of 400 rpm for 4 hours to obtain a waterborne polyurethane emulsion;

[0261] ④ Removal of organic solvent: transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 45°C, and remove acetone under vacuum to obtain the aqueous polyurethane emulsion for the film product;

[0262] (2) The preparation process of waterborne polyurethane film product is the same as that of Experimental Example 1.

[0263] Example 7

[0264] (1) Preparation of waterborne polyurethane emulsion:

[0265] ① Raw material pretreatment: first, the hydrogen bond monomer precursor compound 7 and dimethylolbutyric acid of the following structure are respectively dehydrated at 90° C. and vacuum conditions below -0.09 MPa for 3 hours, and then cooled to 50° C. for standby use; the dihydroxy polysiloxane with an average number average molecular weight of 2000Da, polytetrahydrofuran diol with an average number average molecular weight of 2000Da, and polyether triol with an average number average molecular weight of 3000Da of the following structure are dehydrated at 115° C. and vacuum conditions below -0.09 MPa for 4 hours, and then cooled to 60° C. for standby use;

[0266] Hydrogen bond monomer precursor compound 7;

[0267] Bishydroxy polysiloxane with an average number average molecular weight of 2000Da;

[0268] ② Preparation of waterborne polyurethane polymer: 5.81 parts by weight of dihydroxy polysiloxane treated in step ①, 45.48 parts by weight of polytetrahydrofuran diol, and 23.13 parts by weight of isophorone diisocyanate were added to a reactor, reacted at 90°C for 3 hours, and then cooled to 60°C; 12.77 parts by weight of polyether triol were added to a reactor, reacted at 90°C for 3 hours, and then cooled to 60°C; 4.22 parts by weight of dimethylol butyric acid treated in step ① and 50 parts by weight of acetone were added, reacted at 90°C for 3 hours, and then cooled to 50°C; 5.36 parts by weight of hydrogen bond monomer precursor compound 7 treated in step ① and 50 parts by weight of acetone were added, reacted at 60°C for 4 hours, and then cooled to 30°C; 3.18 parts by weight of triethylamine and 50 parts by weight of acetone were added, reacted at 30°C for 0.5 hours, and a waterborne polyurethane polymer was obtained;

[0269] ③ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ② into an emulsification tank, maintain the temperature of the emulsification tank at 0-10° C., pour 823 parts by weight of deionized water into the emulsification tank, and stir at a speed of 9000 rpm for 30 minutes. After emulsification, stir at a speed of 400 rpm for 4 hours to obtain a waterborne polyurethane emulsion;

[0270] ④ Removal of organic solvent: transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 45°C, and remove acetone under vacuum to obtain the aqueous polyurethane emulsion for the film product;

[0271] (2) The preparation process of waterborne polyurethane film product is the same as that of Experimental Example 1.

[0272] Example 8

[0273] (1) Preparation of waterborne polyurethane emulsion:

[0274] ① Raw material pretreatment: first, the hydrogen bond monomer precursor compound 8 and dimethylolbutyric acid of the following structures were dehydrated at 90° C. and vacuum conditions below -0.09 MPa for 3 hours, and then cooled to 50° C. for standby use; the average number average molecular weight of 2000Da bisaminopolysiloxane, the average number average molecular weight of 2000Da polytetrahydrofuran diol, the average number average molecular weight of 2000Da polycarbonate diol, and the average number average molecular weight of 5000Da polyether triol of the following structures were dehydrated at 115° C. and vacuum conditions below -0.09 MPa for 4 hours, and then cooled to 60° C. for standby use;

[0275] Hydrogen bond monomer precursor compound 8;

[0276] Bisaminopolysiloxane with an average number average molecular weight of 2000Da;

[0277] ② Preparation of waterborne polyurethane polymer: 39.89 parts by weight of polytetrahydrofuran diol, 6.13 parts by weight of bisamino polysiloxane, 5.36 parts by weight of polycarbonate diol, and 20.02 parts by weight of isophorone diisocyanate treated in step ① are added to a reactor, reacted at 90°C for 3 hours, and then cooled to 60°C; 16.86 parts by weight of polyether triol are added to a reactor, reacted at 90°C for 4 hours, and then cooled to 60°C; 4.01 parts by weight of dimethylol butyric acid and 60 parts by weight of acetone treated in step ① are added, reacted at 90°C for 3 hours, and then cooled to 50°C; 4.69 parts by weight of hydrogen bond monomer precursor compound 7 and 50 parts by weight of acetone treated in step ① are added, reacted at 60°C for 4 hours, and then cooled to 30°C; 3.02 parts by weight of triethylamine and 50 parts by weight of acetone are added, reacted at 30°C for 0.5 hours, and a waterborne polyurethane polymer is obtained;

[0278] ③ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ② into an emulsification tank, maintain the temperature of the emulsification tank at 0-10° C., pour 1044 parts by weight of deionized water into the emulsification tank, and stir at a speed of 9000 rpm for 30 minutes. After emulsification, stir at a speed of 400 rpm for 4 hours to obtain a waterborne polyurethane emulsion;

[0279] ④ Removal of organic solvent: transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 45°C, and remove acetone under vacuum to obtain the aqueous polyurethane emulsion for the film product;

[0280] (2) The preparation process of waterborne polyurethane film product is the same as that of Experimental Example 1.

[0281] Example 9

[0282] (1) Preparation of waterborne polyurethane emulsion:

[0283] ① Raw material pretreatment: first, the hydrogen bond monomer precursor compound 2, the hydrogen bond monomer precursor compound 9, dimethylolbutyric acid, and trimethylolpropane of the following structure are respectively dehydrated at 90° C. and vacuum conditions below -0.09 MPa for 3 hours, and then cooled to 50° C. for standby use; the polytetrahydrofuran diol with an average number average molecular weight of 3000 Da, the dihydroxy polysiloxane with an average number average molecular weight of 2500 Da, and the polybutylene diol with an average number average molecular weight of 2000 Da are dehydrated at 115° C. and vacuum conditions below -0.09 MPa for 4 hours, and then cooled to 60° C. for standby use;

[0284] Hydrogen bond monomer precursor compound 2;

[0285] Hydrogen bond monomer precursor compound 9;

[0286] Bishydroxy polysiloxane with an average number average molecular weight of 2500Da;

[0287] ② Preparation of waterborne polyurethane polymer: 64.89 parts by weight of polytetramethylene glycol, 3.60 parts by weight of dihydroxy polysiloxane, 2.88 parts by weight of polybutylene glycol and 18.43 parts by weight of isophorone diisocyanate treated in step ① were added to a reaction kettle, reacted at 90°C for 3 hours, and then cooled to 60°C; 0.71 parts by weight of trimethylolpropane was added to a reaction kettle, reacted at 90°C for 4 hours, and then cooled to 60°C; 3. 22 parts by weight of dimethylolbutyric acid, 2.84 parts by weight of hydrogen bond monomer compound 9, and 80 parts by weight of acetone, react at 90° C. for 3 hours, and then cool to 50° C.; add 1.08 parts by weight of hydrogen bond monomer compound 2 treated in step ① and 50 parts by weight of acetone, react at 60° C. for 4 hours, and then cool to 30° C.; add 2.43 parts by weight of triethylamine and 50 parts by weight of acetone, react at 30° C. for 0.5 hour, to prepare a waterborne polyurethane polymer;

[0288] ③ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ② into an emulsification tank, maintain the temperature of the emulsification tank at 0-10° C., pour 833 parts by weight of deionized water into the emulsification tank, and stir at a speed of 9000 rpm for 30 minutes. After emulsification, stir at a speed of 400 rpm for 4 hours to obtain a waterborne polyurethane emulsion;

[0289] ④ Removal of organic solvent: transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 45°C, and remove acetone under vacuum to obtain the aqueous polyurethane emulsion for the film product;

[0290] (2) The preparation process of waterborne polyurethane film product is the same as that of Experimental Example 1.

[0291] Example 10

[0292] (1) Preparation of waterborne polyurethane emulsion:

[0293] ① Raw material pretreatment: first, the hydrogen bond monomer precursor compound 4, the hydrogen bond monomer precursor compound 10, and dimethylolbutyric acid of the following structures are respectively dehydrated at 90°C and vacuum conditions below -0.09MPa for 3 hours, and then cooled to 50°C for standby use; the polycaprolactone diol with an average number average molecular weight of 2000Da and the dihydroxy polysiloxane with an average number average molecular weight of 2500Da of the following structure are dehydrated at 115°C and vacuum conditions below -0.09MPa for 4 hours, and then cooled to 60°C for standby use;

[0294] Hydrogen bond monomer precursor compound 4;

[0295] Hydrogen bond monomer precursor compound 10;

[0296] Bishydroxy polysiloxane with an average number average molecular weight of 2500Da;

[0297] ② Preparation of hydrogen bonding monomer: 2.32 parts by weight of hydrogen bonding monomer precursor compound 10 treated in step ① and 30 parts by weight of acetone were added to a reaction kettle, and then 23.36 parts by weight of diisocyanate were added, and the mixture was reacted at 5° C. for 3 hours;

[0298] ③ Preparation of waterborne polyurethane polymer: 54.81 parts by weight of polycaprolactone diol and 9.14 parts by weight of dihydroxy polysiloxane treated in step ① are added to a reaction kettle, reacted at 90°C for 3 hours, and then cooled to 60°C; 0.80 parts by weight of triethanolamine are added to a reaction kettle, reacted at 80°C for 3 hours, and then cooled to 60°C; 4.08 parts by weight of dimethylolbutyric acid and 60 parts by weight of acetone treated in step ① are added, reacted at 90°C for 3 hours, and then cooled to 50°C; 2.36 parts by weight of hydrogen bond monomer compound 5 and 50 parts by weight of acetone treated in step ① are added, reacted at 60°C for 4 hours, and then cooled to 30°C; 3.08 parts by weight of triethylamine and 50 parts by weight of acetone are added, reacted at 30°C for 0.5 hours, and a waterborne polyurethane polymer is obtained;

[0299] ④ Emulsification of waterborne polyurethane polymer: Pour the waterborne polyurethane polymer prepared in step ② into an emulsification tank, maintain the temperature of the emulsification tank at 0-10° C., pour 657 parts by weight of deionized water into the emulsification tank, and stir at a speed of 9000 rpm for 30 minutes. After emulsification, stir at a speed of 400 rpm for 4 hours to obtain a waterborne polyurethane emulsion;

[0300] ⑤ Removing organic solvent: Transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 45°C, and remove acetone under vacuum to obtain the aqueous polyurethane emulsion for the film product;

[0301] (2) The preparation process of waterborne polyurethane film product is the same as that of Experimental Example 1.

[0302] Embodiment 11

[0303] (1) Preparation of waterborne polyurethane emulsion:

[0304] ① Raw material pretreatment: first, the hydrogen bond monomer precursor compound 11, the hydrogen bond monomer precursor compound 12, and dimethylolbutyric acid of the following structures are respectively dehydrated at 90° C. and vacuum conditions below -0.09 MPa for 3 hours, and then cooled to 50° C. for standby use; polytetrahydrofuran diol with an average number average molecular weight of 2000Da, polyhexanediol adipate diol with an average number average molecular weight of 2000Da, dihydroxy polysiloxane with an average number average molecular weight of 2500Da, and polyether triol with an average number average molecular weight of 3000Da are dehydrated at 115° C. and vacuum conditions below -0.09 MPa for 4 hours, and then cooled to 60° C. for standby use;

[0305] Hydrogen bond monomer precursor compound 11;

[0306] Hydrogen bond monomer precursor compound 12;

[0307] Bishydroxy polysiloxane with an average number average molecular weight of 2500Da;

[0308] ② Preparation of waterborne polyurethane polymer: 40.61 parts by weight of polytetramethylene glycol, 7.61 parts by weight of dihydroxy polysiloxane, 5.08 parts by weight of polyhexanediol adipate diol, and 22.57 parts by weight of isophorone diisocyanate treated in step ① were added to a reaction kettle, reacted at 90°C for 3 hours, and then cooled to 60°C; 13.40 parts by weight of polyether triol were added to a reaction kettle, reacted at 90°C for 4 hours, and then cooled to 60°C; 4.02 parts by weight of polyether triol treated in step ① were added to a reaction kettle, reacted at 90°C for 4 hours, and then cooled to 60°C; 1.97 parts by weight of hydrogen bonding monomer precursor compound 11 treated in step ①, 1.66 parts by weight of hydrogen bonding monomer precursor compound 12, and 50 parts by weight of acetone are added, and the mixture is reacted at 60° C. for 4 hours, and then the temperature is lowered to 30° C.; 3.03 parts by weight of triethylamine and 50 parts by weight of acetone are added, and the mixture is reacted at 30° C. for 0.5 hours to obtain a waterborne polyurethane polymer;

[0309] ③ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ② into an emulsification tank, maintain the temperature of the emulsification tank at 0-10° C., pour 788 parts by weight of deionized water into the emulsification tank, and stir at a speed of 9000 rpm for 30 minutes. After emulsification, stir at a speed of 400 rpm for 4 hours to obtain a waterborne polyurethane emulsion;

[0310] ④ Removal of organic solvent: transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 45°C, and remove acetone under vacuum to obtain the aqueous polyurethane emulsion for the film product;

[0311] (2) The preparation process of waterborne polyurethane film product is the same as that of Experimental Example 1.

[0312] Example 12

[0313] (1) Preparation of waterborne polyurethane emulsion:

[0314] ① Raw material pretreatment: first, the hydrogen bond monomer precursor compound 1 and dimethylol propionic acid of the following structure are respectively dehydrated at 90° C. and vacuum conditions below -0.09 MPa for 3 hours, and then cooled to 50° C. for standby use; the dihydroxy polysiloxane with an average number average molecular weight of 2000 Da, polytetrahydrofuran diol with an average number average molecular weight of 2000 Da, and modified castor oil with a trifunctionality average number average molecular weight of 579 Da are dehydrated at 115° C. and vacuum conditions below -0.09 MPa for 4 hours, and then cooled to 60° C. for standby use;

[0315] Hydrogen bond monomer precursor compound 1;

[0316] Bishydroxy polysiloxane with an average number average molecular weight of 2000Da;

[0317] ② Preparation of waterborne polyurethane polymer: 7.26 parts by weight of dihydroxy polysiloxane treated in step ①, 55.40 parts by weight of polytetrahydrofuran diol, and 12.54 parts by weight of isophorone diisocyanate were added to a reactor, reacted at 90° C. for 3 hours, and then cooled to 60° C.; 3.23 parts by weight of modified castor oil treated in step ① were added to a reactor, reacted at 90° C. for 4 hours, and then cooled to 60° C.; 4.56 parts by weight of diisocyanate treated in step ① were added to a reactor, reacted at 90° C. for 4 hours, and then cooled to 60° C. Hydroxymethylpropionic acid and 30 parts by weight of acetone are reacted at 90° C. for 3 hours, and then cooled to 50° C.; 2.70 parts by weight of the hydrogen bond monomer precursor compound 1 treated in step ①, 11.14 parts by weight of isophorone diisocyanate, and 50 parts by weight of acetone are added, and the mixture is reacted at 60° C. for 4 hours, and then cooled to 30° C.; 3.11 parts by weight of triethylamine and 50 parts by weight of acetone are added, and the mixture is reacted at 30° C. for 0.5 hours to obtain a waterborne polyurethane polymer;

[0318] ③ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ② into an emulsification tank, maintain the temperature of the emulsification tank at 0-10° C., pour 650 parts by weight of deionized water into the emulsification tank, and stir at a speed of 9000 rpm for 30 minutes. After emulsification, stir at a speed of 400 rpm for 4 hours to obtain a waterborne polyurethane emulsion;

[0319] ④ Removal of organic solvent: transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 45°C, and remove acetone under vacuum to obtain the aqueous polyurethane emulsion for the film product;

[0320] (2) The preparation process of waterborne polyurethane film product is the same as that of Experimental Example 1.

[0321] Embodiment 13

[0322] (1) Preparation of waterborne polyurethane emulsion:

[0323] ① Raw material pretreatment: first, the hydrogen bond monomer precursor compound 1 and dimethylol propionic acid of the following structure are respectively dehydrated at 90° C. and vacuum conditions below -0.09 MPa for 3 hours, and then cooled to 50° C. for standby use; the fluorinated dihydroxy polysiloxane with an average number average molecular weight of 2000 Da, polytetrahydrofuran diol with an average number average molecular weight of 2000 Da, and modified castor oil with a trifunctionality average number average molecular weight of 579 Da are dehydrated at 115° C. and vacuum conditions below -0.09 MPa for 4 hours, and then cooled to 60° C. for standby use;

[0324] Hydrogen bond monomer precursor compound 1;

[0325] Fluorinated dihydroxy polysiloxane with an average number average molecular weight of 2000Da;

[0326] ② Preparation of waterborne polyurethane polymer: 7.26 parts by weight of fluorine-containing dihydroxy polysiloxane treated in step ①, 55.40 parts by weight of polytetrahydrofuran diol, and 23.68 parts by weight of isophorone diisocyanate were added to a reactor, reacted at 90°C for 3 hours, and then cooled to 60°C; 3.23 parts by weight of modified castor oil treated in step ① were added to a reactor, reacted at 90°C for 4 hours, and then cooled to 60°C; 4.56 parts by weight of dimethylol propionic acid treated in step ① and 30 parts by weight of acetone were added, reacted at 90°C for 3 hours, and then cooled to 50°C; 2.70 parts by weight of hydrogen bond monomer precursor compound 1 treated in step ① and 50 parts by weight of acetone were added, reacted at 60°C for 4 hours, and then cooled to 30°C; 3.11 parts by weight of triethylamine and 50 parts by weight of acetone were added, reacted at 30°C for 0.5 hours, and a waterborne polyurethane polymer was obtained;

[0327] ③ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ② into an emulsification tank, maintain the temperature of the emulsification tank at 0-10° C., pour 650 parts by weight of deionized water into the emulsification tank, and stir at a speed of 9000 rpm for 30 minutes. After emulsification, stir at a speed of 400 rpm for 4 hours to obtain a waterborne polyurethane emulsion;

[0328] ④ Removal of organic solvent: transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 45°C, and remove acetone under vacuum to obtain the aqueous polyurethane emulsion for the film product;

[0329] (2) The preparation process of waterborne polyurethane film product is the same as that of Experimental Example 1.

[0330] Embodiment 14

[0331] (1) Preparation of waterborne polyurethane emulsion:

[0332] ① Raw material pretreatment: first, the hydrogen bond monomer precursor compound 1 and dimethylol propionic acid of the following structure are respectively dehydrated at 90° C. and vacuum conditions below -0.09 MPa for 3 hours, and then cooled to 50° C. for standby use; the block copolymer of polysiloxane and fluorine-containing polyether with an average number average molecular weight of 2000 Da, polytetrahydrofuran diol with an average number average molecular weight of 2000 Da, and modified castor oil with a trifunctionality average number average molecular weight of 579 Da are dehydrated at 115° C. and vacuum conditions below -0.09 MPa for 4 hours, and then cooled to 60° C. for standby use;

[0333] Hydrogen bond monomer precursor compound 1;

[0334]

[0335] , a block copolymer of polysiloxane with an average number average molecular weight of 2000Da and fluorinated polyether;

[0336] ② Preparation of waterborne polyurethane polymer: 7.26 parts by weight of the block copolymer of polysiloxane and fluorine-containing polyether treated in step ①, 55.40 parts by weight of polytetrahydrofuran diol, and 23.68 parts by weight of isophorone diisocyanate are added to a reactor, reacted at 90° C. for 3 hours, and then cooled to 60° C.; 3.23 parts by weight of modified castor oil treated in step ① are added to a reactor, reacted at 90° C. for 4 hours, and then cooled to 60° C.; 4.56 parts by weight of dimethylolpropionic acid treated in step ① and 30 parts by weight of acetone are added, reacted at 90° C. for 3 hours, and then cooled to 50° C.; 2.70 parts by weight of hydrogen bond monomer precursor compound 1 treated in step ① and 50 parts by weight of acetone are added, reacted at 60° C. for 4 hours, and then cooled to 30° C.; 3.11 parts by weight of triethylamine and 50 parts by weight of acetone are added, reacted at 30° C. for 0.5 hours to obtain a waterborne polyurethane polymer;

[0337] ③ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ② into an emulsification tank, maintain the temperature of the emulsification tank at 0-10° C., pour 650 parts by weight of deionized water into the emulsification tank, and stir at a speed of 9000 rpm for 30 minutes. After emulsification, stir at a speed of 400 rpm for 4 hours to obtain a waterborne polyurethane emulsion;

[0338] ④ Removal of organic solvent: transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 45°C, and remove acetone under vacuum to obtain the aqueous polyurethane emulsion for the film product;

[0339] (2) The preparation process of waterborne polyurethane film product is the same as that of Experimental Example 1.

[0340] Embodiment 15

[0341] (1) Preparation of waterborne polyurethane emulsion:

[0342] ① Raw material pretreatment: first, the hydrogen bond monomer precursor compound 13, dimethylol propionic acid, and trimethylol propane of the following structure are dehydrated at 90°C and vacuum conditions below -0.09MPa for 3 hours, and then cooled to 50°C for use; the dihydroxy polysiloxane with an average number average molecular weight of 2500Da and the polycaprolactone diol with an average number average molecular weight of 2000Da of the following structure are dehydrated at 115°C and vacuum conditions below -0.09MPa for 4 hours, and then cooled to 60°C for use;

[0343] Hydrogen bond monomer precursor compound 13;

[0344] Bishydroxy polysiloxane with an average number average molecular weight of 2500Da;

[0345] ② Preparation of waterborne polyurethane polymer: 7.98 parts by weight of dihydroxy polysiloxane treated in step ①, 52.63 parts by weight of polycaprolactone diol, and 26.85 parts by weight of hydrogenated phenylmethane diisocyanate were added to a reactor, reacted at 90°C for 3 hours, and then cooled to 60°C; 0.69 parts by weight of trimethylolpropane was added to the reactor, reacted at 90°C for 2 hours, and then cooled to 60°C; 4.33 parts by weight of dimethylolpropionic acid treated in step ① and 30 parts by weight of acetone were added, reacted at 90°C for 3 hours, and then cooled to 50°C; 5.32 parts by weight of hydrogen bond monomer precursor compound 13 treated in step ① and 50 parts by weight of acetone were added, reacted at 60°C for 4 hours, and then cooled to 30°C; 2.96 parts by weight of triethylamine and 50 parts by weight of acetone were added, reacted at 30°C for 0.5 hours, and a waterborne polyurethane polymer was obtained;

[0346] ③ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ② into an emulsification tank, maintain the temperature of the emulsification tank at 0-10° C., pour 684 parts by weight of deionized water into the emulsification tank, and stir at a speed of 9000 rpm for 30 minutes. After emulsification, stir at a speed of 400 rpm for 4 hours to obtain a waterborne polyurethane emulsion;

[0347] ④ Removal of organic solvent: transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 45°C, and remove acetone under vacuum to obtain the aqueous polyurethane emulsion for the film product;

[0348] (2) The preparation process of waterborne polyurethane film product is the same as that of Experimental Example 1.

[0349] Example 16

[0350] (1) Preparation of waterborne polyurethane emulsion:

[0351] ① Raw material pretreatment: first, the hydrogen bond monomer precursor compound 14, dimethylol propionic acid, and trimethylol propane of the following structure are dehydrated at 90° C. and vacuum conditions below -0.09 MPa for 3 hours, and then cooled to 50° C. for standby use; the dihydroxy polysiloxane with an average number average molecular weight of 2500 Da and the polytetrahydrofuran diol with an average number average molecular weight of 2000 Da of the following structure are dehydrated at 115° C. and vacuum conditions below -0.09 MPa for 4 hours, and then cooled to 60° C. for standby use;

[0352] Hydrogen bond monomer precursor compound 14;

[0353] Bishydroxy polysiloxane with an average number average molecular weight of 2500Da;

[0354] ② Preparation of waterborne polyurethane polymer: 7.99 parts by weight of dihydroxy polysiloxane treated in step ①, 52.80 parts by weight of polytetrahydrofuran diol, and 26.08 parts by weight of isophorone diisocyanate were added to a reactor, reacted at 90°C for 3 hours, and then cooled to 60°C; 0.69 parts by weight of trimethylolpropane was added to a reactor, reacted at 90°C for 2 hours, and then cooled to 60°C; 4.35 parts by weight of dimethylolpropionic acid treated in step ① and 30 parts by weight of acetone were added, reacted at 90°C for 3 hours, and then cooled to 50°C; 6.27 parts by weight of hydrogen bond monomer precursor compound 14 treated in step ① and 50 parts by weight of acetone were added, reacted at 60°C for 4 hours, and then cooled to 30°C; 2.97 parts by weight of triethylamine and 50 parts by weight of acetone were added, reacted at 30°C for 0.5 hours, and a waterborne polyurethane polymer was obtained;

[0355] ③ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ② into an emulsification tank, maintain the temperature of the emulsification tank at 0-10° C., pour 682 parts by weight of deionized water into the emulsification tank, and stir at a speed of 9000 rpm for 30 minutes. After emulsification, stir at a speed of 400 rpm for 4 hours to obtain a waterborne polyurethane emulsion;

[0356] ④ Removal of organic solvent: transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 45°C, and remove acetone under vacuum to obtain the aqueous polyurethane emulsion for the film product;

[0357] (2) The preparation process of waterborne polyurethane film product is the same as that of Experimental Example 1.

[0358] Comparative Example 1

[0359] Based on Example 1, 1,4-butanediol was used to replace the hydrogen bond monomer compound 1 in equal moles.

[0360] (1) Preparation of waterborne polyurethane emulsion:

[0361] ① Raw material pretreatment: first, 1,4-butanediol and dimethylol propionic acid are respectively dehydrated at 90°C and vacuum conditions below -0.09MPa for 3 hours, and then cooled to 50°C for standby use; the following structures of dihydroxy polysiloxane with an average molecular weight of 2000Da, polytetrahydrofuran diol with an average molecular weight of 2000Da, and modified castor oil with a trifunctionality average molecular weight of 579Da are dehydrated at 115°C and vacuum conditions below -0.09MPa for 4 hours, and then cooled to 60°C for standby use;

[0362] Bishydroxy polysiloxane with an average number average molecular weight of 2000Da;

[0363] ② Preparation of waterborne polyurethane polymer: 7.34 parts by weight of dihydroxy polysiloxane treated in step ①, 55.98 parts by weight of polytetrahydrofuran diol, and 23.92 parts by weight of isophorone diisocyanate were added to a reactor, reacted at 90°C for 3 hours, and then cooled to 60°C; 3.27 parts by weight of modified castor oil treated in step ① were added to a reactor, reacted at 90°C for 4 hours, and then cooled to 60°C; 4.61 parts by weight of dimethylol propionic acid treated in step ① and 30 parts by weight of acetone were added, reacted at 90°C for 3 hours, and then cooled to 50°C; 1.68 parts by weight of 1,4-butanediol treated in step ① and 50 parts by weight of acetone were added, reacted at 60°C for 4 hours, and then cooled to 30°C; 3.15 parts by weight of triethylamine and 50 parts by weight of acetone were added, reacted at 30°C for 0.5 hours, and a waterborne polyurethane polymer was obtained;

[0364] ③ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ② into an emulsification tank, maintain the temperature of the emulsification tank at 0-10° C., pour 644 parts by weight of deionized water into the emulsification tank, and stir at a speed of 9000 rpm for 30 minutes. After emulsification, stir at a speed of 400 rpm for 4 hours to obtain a waterborne polyurethane emulsion;

[0365] ④ Removal of organic solvent: transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 45°C, and remove acetone under vacuum to obtain the aqueous polyurethane emulsion for the film product;

[0366] (2) The preparation process of waterborne polyurethane film product is the same as that of Experimental Example 1.

[0367] Comparative Example 2

[0368] Based on Example 1, the average number average molecular weight 2000Da polytetrahydrofuran diol is used to replace the average number average molecular weight 2000Da dihydroxy polysiloxane by an equal mole.

[0369] (1) Preparation of waterborne polyurethane emulsion:

[0370] ① Raw material pretreatment: first, the hydrogen bond monomer compound 1 and dimethylol propionic acid of the following structures are respectively dehydrated at 90° C. and vacuum conditions below -0.09 MPa for 3 hours, and then cooled to 50° C. for standby use; polytetrahydrofuran diol with an average number average molecular weight of 2000 Da and modified castor oil with a trifunctional average number average molecular weight of 579 Da are dehydrated at 115° C. and vacuum conditions below -0.09 MPa for 4 hours, and then cooled to 60° C. for standby use;

[0371] Hydrogen bond monomer compound 1;

[0372] ② Preparation of waterborne polyurethane polymer: 62.67 parts by weight of polytetrahydrofuran diol and 23.68 parts by weight of isophorone diisocyanate treated in step ① are added to a reactor, reacted at 90° C. for 3 hours, and then cooled to 60° C.; 3.23 parts by weight of modified castor oil treated in step ① are added to a reactor, reacted at 90° C. for 4 hours, and then cooled to 60° C.; 4.56 parts by weight of dimethylolpropionic acid and 30 parts by weight of acetone treated in step ① are added, reacted at 90° C. for 3 hours, and then cooled to 50° C.; 2.70 parts by weight of hydrogen bond monomer compound 1 and 50 parts by weight of acetone treated in step ① are added, reacted at 60° C. for 4 hours, and then cooled to 30° C.; 3.11 parts by weight of triethylamine and 50 parts by weight of acetone are added, reacted at 30° C. for 0.5 hours, to obtain a waterborne polyurethane polymer;

[0373] ③ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ② into an emulsification tank, maintain the temperature of the emulsification tank at 0-10° C., pour 650 parts by weight of deionized water into the emulsification tank, and stir at a speed of 9000 rpm for 30 minutes. After emulsification, stir at a speed of 400 rpm for 4 hours to obtain a waterborne polyurethane emulsion;

[0374] ④ Removal of organic solvent: transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 45°C, and remove acetone under vacuum to obtain the aqueous polyurethane emulsion for the film product;

[0375] (2) The preparation process of waterborne polyurethane film product is the same as that of Experimental Example 1.

[0376] Comparative Example 3

[0377] Okamoto 001 condoms are available on the market.

[0378] Comparative Example 4

[0379] Sagami 001 condoms are available on the market.

[0380] Comparative Example 5

[0381] Durex 001 condoms are available on the market.

[0382] Comparative Example 6

[0383] Durex 001 condoms are available on the market.

[0384] The prepared waterborne polyurethane film product and commercially available products were subjected to performance tests in accordance with YY / T 1850-2023, including thickness, tear force, elongation at break, water resistance, burst volume, burst pressure, 100% tensile modulus, and toughness. The test data are shown in the following table:

[0385]

[0386]

[0387] From the data in the table, we can see that for commercial samples, the maximum force and water resistance of Okamoto 001, Durex 001 and Jissbon 001 do not meet the requirements of the new standard. Only the tearing force, elongation at break, bursting pressure, bursting volume and water resistance of Sagami 001 meet the requirements of the new standard. However, the 100% tensile modulus of Sagami 001 is 1.6MPa, which is too high.

[0388] Comparative Example 1 does not add hydrogen-bonding monomer compound 1, and its structure does not contain multiple hydrogen-bonding units. Its tear force and elongation at break are significantly reduced compared with Example 1, and its bursting pressure, bursting volume, and water resistance do not meet the requirements of the new standard. Comparative Example 2 contains hydrogen-bonding monomer compound 1, and its structure contains multiple hydrogen-bonding units, but no polysiloxane units. Its tear force, elongation at break, bursting pressure, and bursting volume can meet the requirements of the new standard, but its water resistance does not meet the requirements of the new standard, and its 100% tensile modulus is relatively high, at 2.0 MPa. Examples 1-15, their tear force, elongation at break, bursting pressure, bursting volume, and water resistance meet the requirements of the new standard, and their 100% tensile modulus is between 0.6-0.9 MPa, and their softness is better than that of commercial samples. Examples 1-15 are based on the combined effects of multiple hydrogen bond units and polysiloxane units. On the one hand, the multiple hydrogen bond units play a role in energy dissipation, achieving the effect of strengthening and toughening. At the same time, the addition of polysiloxane units reduces the 100% tensile modulus of the waterborne polyurethane and significantly improves the water resistance of the waterborne polyurethane.

[0389] Examples 1-8, 15, and 16 use separate dihydrazide hydrogen-bonding monomer precursor compounds. The main difference between Examples 1-8 is the different number of carbon atoms of the alkylene groups between the dihydrazides, namely, 1,2-ethylene, 1,4-butylene, 1,6-hexylene, 1,8-octylene, no alkylene group, methylene, 1,9-nonylene, and 1,14-dodecylene are given as examples, corresponding to Examples 1-8, respectively. From the experimental data, it can be seen that when the dihydrazides are 1,2-ethylene, 1,4-butylene, 1,6-hexylene, and 1,8-octylene, the comprehensive performance is better. In Examples 15 and 16, the dihydrazides are connected by a linker containing a dynamic disulfide bond and a linker containing a dynamic disulfide acetal bond, and the dihydrazide structures are respectively From the analysis of the relationship between structure and performance, the alkylene group between the dihydrazides has better performance within a certain range. When the number of carbon atoms of the alkylene group between the dihydrazides is less than 2, the multiple hydrogen bonds formed are too strong, which is not conducive to the energy dissipation of the stretching process. When the number of carbon atoms of the alkylene group between the dihydrazides is greater than 8, due to the long distance between the hydrazides, the hydrogen bonds formed are relatively independent, which reduces the energy dissipation effect in the stretching process. The linking group between the dihydrazides contains a dynamic bond, which is beneficial to the energy dissipation of the stretching process. In the present invention, when the number of carbon atoms of the alkylene group between the dihydrazides is 2-8 or the linking group between the dihydrazides contains a dynamic bond, the dihydrazide hydrogen bond monomer precursor compound can better reflect the strengthening and toughening effect of multiple hydrogen bonds.

[0390] The performance of the mixed chain extender of the dihydrazide hydrogen-bonding monomer precursor compound and the second hydrogen-bonding monomer precursor compound in Examples 9-11 is slightly weaker than that of the dihydrazide hydrogen-bonding monomer precursor compound alone. Since the dihydrazide hydrogen-bonding monomer can form a maximum of six hydrogen bonds, its hydrogen bonding effect is stronger than that of the second hydrogen-bonding monomer, that is, its strengthening and toughening effect is better than that of the second hydrogen-bonding monomer.

[0391] Compared with Example 1, Example 12 changes the process, that is, in the experimental process of Example 12, the amount of diisocyanate and polyol added is added according to the molar ratio of isocyanate group to polyol of 1.8, and then the cross-linking agent, hydrophilic chain extender, and hydrogen bond monomer precursor compound are added to react respectively, and the remaining diisocyanate is added to react together during the hydrogen bond monomer precursor compound reaction stage. The breaking force of the sample of Example 12 is 27.7N, the elongation at break is 790%, the burst volume is 16L, and the burst pressure is greater than 4.0KPa. After the waterborne polyurethane film product is soaked in hot water at (50±1)℃ for 1 hour, its breaking force is 24.9N, the 100% tensile modulus is 0.7MPa, and the toughness is 59.2MJ / m 3 The breaking force of the sample in Example 1 is 25.4N, the elongation at break is 766%, the bursting volume is 14L, and the bursting pressure is 3.7KPa. After the waterborne polyurethane film product is immersed in hot water at (50±1)℃ for 1 hour, its breaking force is 22.4N, the 100% tensile modulus is 0.6MPa, and the toughness is 42.1MJ / m 3 . The performance of the waterborne polyurethane safety sample of Example 12 is significantly better than that of the waterborne polyurethane safety sample of Example 1. Example 12 increases the soft segment chain by adjusting the molar ratio of the isocyanate group to the polyol in the early stage, and at the same time, the remaining diisocyanate is added during the reaction of the hydrogen bond monomer precursor compound to construct multiple hydrogen bond units with longer chain segments. This method promotes phase separation, makes the soft segment softer, strengthens the hydrogen bonding effect between the hard segments, improves the elongation at break, and is beneficial to the dissipation of energy and improves toughness.

[0392] Compared with Example 1, Example 13 uses fluorinated bishydroxy polysiloxane with an average number average molecular weight of 2000Da to replace the bishydroxy polysiloxane with an average number average molecular weight of 2000Da in Example 1. Compared with Example 1, Example 14 uses a block copolymer of polysiloxane with an average number average molecular weight of 2000Da and fluorinated polyether to replace the bishydroxy polysiloxane with an average number average molecular weight of 2000Da in Example 1. The tear force of the sample of Example 13 is 31.7N, the elongation at break is 800%, the burst volume is 17L, and the burst pressure is 4.1KPa. After the waterborne polyurethane film product is immersed in hot water at (50±1)℃ for 1 hour, its tear force is 28.8N, the 100% tensile modulus is 0.9MPa, and the toughness is 69.6MJ / m 3 The breaking force of the sample of Example 14 is 32.9N, the elongation at break is 824%, the burst volume is 17L, the burst pressure is 4.2KPa, and the breaking force of the waterborne polyurethane film product is 29.6N, the 100% tensile modulus is 0.9MPa, and the toughness is 72.3MJ / m after being soaked in hot water at (50±1)℃ for 1 hour. 3 . The performance of the waterborne polyurethane film products in Example 13 and Example 14 is significantly better than that of the waterborne polyurethane safety sample in Example 1. The fluorinated dihydroxy polysiloxane and the block copolymers of polysiloxane and fluorinated polyether in Example 13 and Example 14 have added fluorine components compared to dihydroxy polysiloxane. Fluorinated polymers have very low surface energy, which helps to reduce defects and crack propagation on the surface of the material. At the same time, due to the strong electronegativity of fluorine atoms, the interface properties inside the material can be improved, the intermolecular forces can be enhanced, and the energy dissipation capacity and toughness can be improved.

[0393] From the particle size distribution diagram of the aqueous polyurethane emulsion in Example 1 of the present invention, it can be seen that after the aqueous polyurethane emulsion is placed for 180 days after production, its particle size distribution diagram is similar to the particle size distribution diagram when it is just produced, indicating that the prepared aqueous polyurethane emulsion has good storage stability. From the DSC diagram of the aqueous polyurethane film product sample in Example 1, it can be seen that its glass transition temperature is about 30°C. From the TGA diagram of the aqueous polyurethane film product sample in Example 1, it can be seen that its initial thermal decomposition temperature is 220°C, indicating that it has good heat resistance.

[0394] The present invention constructs multiple hydrogen bond units and polysiloxane units in the waterborne polyurethane structure, and prepares a water-resistant and flexible waterborne polyurethane film product by combining the multiple hydrogen bond units and the polysiloxane units. The present invention improves the toughness of the waterborne polyurethane film product based on the energy dissipation effect of multiple hydrogen bonds. At the same time, based on the hydrophobic characteristics and flexibility of polysiloxane, the water resistance of the waterborne polyurethane film product is improved, the modulus of the waterborne polyurethane film product is reduced, and the demoulding property of the waterborne polyurethane film product in the production process is improved. The water-resistant and flexible waterborne polyurethane film product based on multiple hydrogen bonds disclosed by the present invention has a thickness of less than 30um, a tear force of more than 20N, an elongation at break of more than 690%, a burst volume of more than 11L, and a burst pressure of more than 3KPa. After the waterborne polyurethane film product is soaked in hot water at (50±1)℃ for 1 hour, its tear force is greater than 18N, the 100% tensile modulus is less than 1.0MPa, and the toughness is greater than 32MJ / m 3 The waterborne polyurethane film product disclosed in the present invention has excellent water resistance and flexibility, and also has the characteristics of low modulus, and meets the new requirements for waterborne polyurethane film products under the new standards and the new era.

[0395] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A water-resistant and flexible waterborne polyurethane film product based on multiple hydrogen bonds, characterized in that: The emulsion is prepared from a waterborne polyurethane polymer and obtained through a film-forming process; the waterborne polyurethane polymer contains at least one multiple hydrogen bond unit and at least one polysiloxane unit in its structure, the multiple hydrogen bond unit is formed by a hydrogen bond monomer, and the at least one hydrogen bond monomer is formed by the reaction of a hydrogen bond monomer precursor compound and an isocyanate group during the preparation of the waterborne polyurethane polymer; the number of hydrogen bond teeth of the multiple hydrogen bond unit is not less than 3; the polysiloxane unit is introduced by a polymerization reaction of polysiloxane and diisocyanate; The waterborne polyurethane polymer is prepared from the following raw materials in parts by weight: 3-10 parts of polysiloxane Polymer polyol 40-70 parts 2-15 parts of hydrogen bond monomer precursor compound 3-6 parts of hydrophilic chain extender 10-30 parts of diisocyanate Crosslinking agent 0.5-25 parts 2-5 parts of salt-forming agent; Wherein, the hydrogen bonding monomer has the following general structure:

2. The water-resistant and flexible waterborne polyurethane film product based on multiple hydrogen bonds according to claim 1, characterized in that: The hydrogen bonding monomer has at least one of the following general structures: Wherein, L1 is a divalent linking group, and the divalent linking group is selected from a carbon chain linking group or a linking group containing a dynamic bond; the carbon chain linking group is selected from C 1-24 Alkylidene, substituted C 1-24 The linking group containing a dynamic bond is selected from a linking group containing a dynamic disulfide bond, a linking group containing a dynamic diselenide bond, a linking group containing a dynamic ketal bond, a linking group containing a dynamic acetal bond, a linking group containing a dynamic thioketal bond, a linking group containing a dynamic thioacetal bond, a linking group containing a dynamic imine bond, and a linking group containing a dynamic oxime bond.

3. The water-resistant and flexible waterborne polyurethane film product based on multiple hydrogen bonds according to claim 1, characterized in that: The structure of the polysiloxane is shown below: Wherein, R1 and R2 are each independently selected from one of hydroxyl, amino, and thiol; R3, R4, R5, R6, R7, and R8 are each independently selected from one of methyl, long-chain alkyl, phenyl, and epoxy hydrocarbon; L2 and L3 are divalent linking groups, each independently selected from C 1-24 Alkylene, substituted C 1-24 Hydrocarbylene, One of -OH2CH2C-OH2CH2CH2C-, -OH2CH2CH2C-OH2CH2CH2C-, and -OH2CH2C-OH2CH2C-; wherein the carbon atoms of -OH2CH2C-OH2CH2CH2C-, -OH2CH2CH2C-OH2CH2CH2C-, and -OH2CH2C-OH2CH2C- are connected to silicon atoms; wherein m, x, y, and z are the number of repeating units, m is an integer of 25-40, and x, y, and z are integers of 1-30.

4. The water-resistant and flexible waterborne polyurethane film product based on multiple hydrogen bonds according to claim 1, characterized in that: The structure of the polysiloxane is shown below: Among them, R9, R 10 Each independently selected from one of hydroxyl, amino, and thiol, R f One selected from fluorine atoms and fluorine-containing side groups, wherein the fluorine-containing side groups are selected from C 1-8 Perfluorocarbon chain, C 1-8 One of the non-perfluorocarbon chains, L4 and L5 are divalent linking groups, each independently selected from C 1-24 Alkylene, substituted C 1-24 Hydrocarbylene, One of -OH2CH2C-OH2CH2CH2C-, -OH2CH2CH2C-OH2CH2CH2C-, and -OH2CH2C-OH2CH2C-; wherein the carbon atoms of -OH2CH2C-OH2CH2CH2C-, -OH2CH2CH2C-OH2CH2CH2C-, and -OH2CH2C-OH2CH2C- are connected to silicon atoms; wherein n, p, q, and j are the number of repeating units, n is an integer of 25-40, and p, q, and j are integers of 1-30.

5. The water-resistant and flexible waterborne polyurethane film product based on multiple hydrogen bonds according to claim 1, characterized in that: The polysiloxane is selected from a block copolymer of polysiloxane and fluorinated polyether, wherein the block copolymer of polysiloxane and fluorinated polyether is formed by polymerization of a polysiloxane segment and a fluorinated polyether segment through diisocyanate or a diisocyanate-terminated polymer; wherein the structure of the polysiloxane segment is as follows: The structure of the fluorinated polyether segment is shown below: Among them, R 17 , R 18 , R 25 , R 26 Each independently selected from one of hydroxyl, amino, and thiol, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 Each independently selected from a methyl group, a long-chain alkyl group, a phenyl group, an epoxy group, a fluorine atom, and a fluorine-containing side group, wherein the fluorine-containing side group is selected from C 1-8 Perfluorocarbon chain, C 1-8 One of the non-perfluorocarbon chains, L7, L8, L9, L 10 is a divalent linking group, each independently selected from C 1-24 Alkylene, substituted C 1-24 Hydrocarbylene, -OH2CH2C-OH2CH2CH2C-, -OH2CH2CH2C-OH2CH2CH2C-, -OH2CH2C-OH2CH2C-; wherein r, s, t, e, u, v, w are the number of repeating units, r, s, t are integers of 25-40, and e, u, v, w are integers of 1-30; The diisocyanate is selected from isophorone diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, hydrogenated phenylmethane diisocyanate, 1,3-phenylene diisocyanate, toluene 2,6-diisocyanate, L-lysine diisocyanate, toluene-2,4-diisocyanate, 1,5-naphthalene diisocyanate, cyclohexane-1,4-diisocyanate, trans-1,4-cyclohexyl diisocyanate, 4,4'-methylenebis(phenyl isocyanate) ), at least one of 1,4-diisocyanatobutane, 1,4-cyclohexanedimethyl diisocyanate, and 4,4-diisocyanate dicyclohexylmethane; wherein the diisocyanate-terminated polymer is selected from diisocyanate-terminated polytetrahydrofuran diol with an average number average molecular weight of 1000-2000Da, polycarbonate diol with an average number average molecular weight of 1000-2000Da, polycaprolactone diol with an average number average molecular weight of 1000-2000Da, Polybutadiene glycol with molecular weight of 1000-2000Da, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, butyl ethyl propanediol, diethyl pentanediol, 3-methyl-1,5-pentanediol, 1,3-butanediol, trimethyl pentanediol, 1,5-pentanediol, 1,2-pentanediol, hydroxy neopentyl alcohol At least one of esters, ethyl hexanediol, dodecanediol, 1,4-dihydroxymethylcyclohexane, cyclohexanediol, dodecanediol, spirodiol, hydroquinone dihydroxyethyl ether, resorcinol dihydroxyethyl ether, resorcinol bishydroxypropyl ether, resorcinol bishydroxypropyl ethyl ether, 4-hydroxyethyloxyethyl-1-hydroxyethylphenylene diether, 3-hydroxyethyloxyethyl-1-hydroxyethylphenylene diether, bisphenol A dihydroxyethyl ether, bisphenol A dihydroxypropyl ether, dimethylolpropionic acid, and dimethylolbutyric acid.

6. The water-resistant and flexible waterborne polyurethane film product based on multiple hydrogen bonds according to claim 1, characterized in that: The waterborne polyurethane polymer further comprises at least a second hydrogen-bonding monomer in its structure, which is formed by the reaction of a hydrogen-bonding monomer precursor compound and an isocyanate group during the preparation of the waterborne polyurethane polymer, or by first preparing a hydrogen-bonding monomer precursor compound and then using it as a polymerization monomer for the polymerization reaction of the waterborne polyurethane polymer, wherein the second hydrogen-bonding monomer is in the polymer main chain and / or polymer chain side group or side chain or end group.

7. The water-resistant and flexible waterborne polyurethane film product based on multiple hydrogen bonds according to claim 6, characterized in that: The second hydrogen bonding monomer has one of the following structures:

8. The water-resistant and flexible waterborne polyurethane film product based on multiple hydrogen bonds according to claim 6, characterized in that: The hydrogen-bonding monomer precursor compound of the second hydrogen-bonding monomer is selected from at least one of the following compounds:

9. The water-resistant and flexible waterborne polyurethane film product based on multiple hydrogen bonds according to claim 1, characterized in that: The waterborne polyurethane polymer is prepared from the following raw materials in parts by weight: Polysiloxane 5-8 parts Polymer polyol 45-60 parts 2.5-6 parts of hydrogen bond monomer precursor compound 4-6 parts of hydrophilic chain extender 20-30 parts of diisocyanate Crosslinking agent 0.6-18 parts 2.5-3.5 parts of salt-forming agent; Wherein, the polysiloxane has the following structure: Among them, R9, R 10 Each independently selected from one of hydroxyl, amino, and thiol, R f is selected from the group consisting of a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, an undecafluoropentyl group, a trifluoropropyl group, a perfluoroalkyl oxasulfonyl propyl group, L4 and L5 are divalent linking groups, each independently selected from one of 1,2-ethylene, 1,3-propylene, -OH2CH2C-OH2CH2CH2C-, -OH2CH2CH2C-OH2CH2CH2C-, -OH2CH2C-OH2CH2C-; one of the carbon atoms of -OH2CH2C-OH2CH2CH2C-, -OH2CH2CH2C-OH2CH2CH2C-, and -OH2CH2C-OH2CH2C- connected to the silicon atom; wherein n is the number of repeating units; wherein the fluorinated polysiloxane has an average number average molecular weight of 2000-3000Da; Wherein, the polysiloxane is selected from a block copolymer of polysiloxane and a fluorinated polyether, and the block copolymer of polysiloxane and a fluorinated polyether is polymerized by a polysiloxane segment and a fluorinated polyether segment through a diisocyanate or a diisocyanate-terminated polymer; wherein the structure of the polysiloxane segment is as follows: The structure of the fluorinated polyether segment is shown below: Among them, R 17 , R 18 , R 25 , R 26 Each independently selected from one of hydroxyl, amino, and thiol, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 Each is independently selected from a methyl group, a long-chain alkyl group, a phenyl group, and an epoxy group, R 19 , R 20 , R 21 , R 22 , R 23 , R 24 Each is independently selected from a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, an undecafluoropentyl group, a trifluoropropyl group, a perfluoroalkyl oxasulfonyl propyl group, One of L7, L8, L9, L 10 is a divalent linking group, L7 and L8 are each independently selected from one of 1,2-ethylene, 1,3-propylene, -OH2CH2C-OH2CH2CH2C-, -OH2CH2CH2C-OH2CH2CH2C-, and -OH2CH2C-OH2CH2C-; wherein the carbon atoms of -OH2CH2C-OH2CH2CH2C-, -OH2CH2CH2C-OH2CH2CH2C-, and -OH2CH2C-OH2CH2C- are connected to the silicon atom, and L9, L 10 Each independently selected from wherein r, s, t, e, u, v, and w are the numbers of repeating units; wherein the diisocyanate is selected from at least one of isophorone diisocyanate, hexamethylene diisocyanate, and hydrogenated phenylmethane diisocyanate; wherein the diisocyanate-terminated polymer is selected from isocyanate-terminated polytetrahydrofuran diol with an average number average molecular weight of 1000-2000Da, polycarbonate diol with an average number average molecular weight of 1000-2000Da, and polyisocyanate diol with an average number average molecular weight of 1000-2000Da. At least one of polycaprolactone diol with a molecular weight of 1000-2000Da, polybutadiene diol with an average number average molecular weight of 1000-2000Da, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, cyclohexanediol, dimethylol propionic acid, and dimethylol butyric acid; wherein the polysiloxane has an average number average molecular weight of 2000-3000Da; Wherein, the polysiloxane has the following structure: Wherein, R1 and R2 are each independently selected from one of hydroxyl, amino and thiol; R3, R4, R5, R6, R7 and R8 are each independently selected from one of methyl, long-chain alkyl, phenyl and epoxy hydrocarbon; L2 and L3 are divalent linking groups, each independently selected from one of 1,2-ethylene, 1,3-propylene, -OH2CH2C-OH2CH2CH2C-, -OH2CH2CH2C-OH2CH2CH2C-, -OH2CH2C-OH2CH2C-, and the carbon atoms in -OH2CH2C-OH2CH2CH2C-, O-H2CH2CH2C-OH2CH2CH2C-, and -OH2CH2C-OH2CH2C- are connected to silicon atoms; wherein m is the number of repeating units; wherein the polysiloxane has an average number average molecular weight of 2000-3000Da; Wherein, the polymer polyol is selected from at least one of polytetramethylene glycol, polycarbonate glycol, polycaprolactone glycol, and polybutadiene glycol; wherein, the polymer polyol has an average number average molecular weight of 2000-3000Da; Wherein, the hydrophilic chain extender is selected from at least one of dimethylol propionic acid and dimethylol butyric acid; Wherein, the diisocyanate is selected from at least one of isophorone diisocyanate, hexamethylene diisocyanate, and hydrogenated phenylmethane diisocyanate; Wherein, the crosslinking agent is selected from at least one of trimethylolpropane, triethanolamine, modified castor oil, and polyether triol; wherein, the modified castor oil has an average number average molecular weight of 500-1200Da and a functionality of 2.5-3.5; wherein, the polyether triol has an average number average molecular weight of 3000-5000Da; Wherein, the salt-forming agent is selected from triethylamine.

10. A method for preparing a water-resistant and flexible waterborne polyurethane film product based on multiple hydrogen bonds according to any one of claims 1 to 9, characterized in that: The preparation method of the waterborne polyurethane film product comprises the following steps: (1) Preparation of waterborne polyurethane emulsion ① Raw material pretreatment: firstly, the hydrogen bond monomer precursor compound, polysiloxane, polymer polyol, hydrophilic chain extender and cross-linking agent are dehydrated under vacuum conditions at 90-120°C; ② Preparation of waterborne polyurethane polymer: add the polysiloxane and polymer polyol treated in step ① to a reaction kettle, then add diisocyanate, react at 80-95° C. for 2-4 hours, and then cool to 60-70° C.; add the crosslinking agent treated in step ①, react at 80-90° C. for 2-4 hours, and then cool to 60-70° C.; add the hydrophilic chain extender and organic solvent treated in step ①, react at 70-90° C. for 2-4 hours, and then cool to 50-60° C.; add the hydrogen bond monomer precursor compound and organic solvent treated in step ①, react at 50-70° C. for 2-4 hours, and then cool to 20-30° C.; add a salt-forming agent and an organic solvent, react at 20-30° C. for 0.5-1 hour to obtain a waterborne polyurethane polymer; ③ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ③ into an emulsification tank, maintain the temperature of the emulsification tank at 0-10° C., pour 500-700 parts by weight of deionized water into the emulsification tank, and stir at a speed of 8000-12000 rpm for 20-60 minutes. After emulsification, stir at a speed of 200-500 rpm for 4-6 hours to obtain a waterborne polyurethane emulsion; ④ Removal of organic solvent: transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 40-50°C, and remove the organic solvent under vacuum to obtain the aqueous polyurethane emulsion for the film product; ⑵ Forming process of waterborne polyurethane film products ①Mold cleaning: acid wash, alkali wash, deionize the glass mold, and dry it at 100-110℃; ②Impregnation of release agent: Cool the glass mold to 70-80℃, impregnate the release agent, and dry at 100-110℃; ③Immersing in water-based polyurethane emulsion: Cool the glass mold to 60-70℃, immerse in water-based polyurethane emulsion for the first time, 70-80℃, bake for 1-3 minutes, immerse in water-based polyurethane emulsion for the second time, 70-80℃, bake for 1-3 minutes, immerse in water-based polyurethane emulsion for the third time, 70-80℃, bake for 6-8 minutes, and dry at 100-110℃ for 10-20 minutes; ④ Curling: curl the water-based polyurethane film; ⑤Immerse in release agent: immerse the mold in the release agent and dry at 100-110℃ for 20-30 minutes; ⑥ Demolding, electrical inspection, and packaging: Cool the mold to room temperature, demold, and after passing the electrical inspection, optionally add an anti-sticking agent / lubricant and package to obtain the finished waterborne polyurethane film product.

11. A method for preparing a water-resistant and flexible waterborne polyurethane film product based on multiple hydrogen bonds according to any one of claims 1 to 9, characterized in that: The preparation method of the waterborne polyurethane film product comprises the following steps: ⑴ Preparation of waterborne polyurethane emulsion ① Raw material pretreatment: firstly, the hydrogen bond monomer precursor compound, polysiloxane, polymer polyol, hydrophilic chain extender and cross-linking agent are dehydrated under vacuum conditions at 90-120°C; ② Preparation of hydrogen-bonding monomer: Add the hydrogen-bonding monomer precursor compound treated in step ① and the organic solvent into the reaction kettle, then add diisocyanate, and react at 0-10° C. for 2-4 hours; ③ Preparation of waterborne polyurethane polymer: add the polysiloxane and polymer polyol treated in step ① into a reaction kettle, react at 80-95° C. for 2-4 hours, and then cool to 60-70° C.; add the crosslinking agent treated in step ①, react at 80-90° C. for 2-4 hours, and then cool to 60-70° C.; add the hydrophilic chain extender and organic solvent treated in step ①, react at 70-90° C. for 2-4 hours, and then cool to 20-30° C.; add a salt-forming agent and an organic solvent, react at 20-30° C. for 0.5-1 hour, and obtain a waterborne polyurethane polymer; ④ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ③ into an emulsification tank, maintain the temperature of the emulsification tank at 0-10°C, pour 500-700 parts by weight of deionized water into the emulsification tank, and stir at a speed of 8000-12000 rpm for 20-60 minutes, and stir at a speed of 200-500 rpm for 4-6 hours after emulsification to obtain a waterborne polyurethane emulsion; ⑤ Removal of organic solvent: transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 40-50°C, and remove the organic solvent under vacuum to obtain the aqueous polyurethane emulsion for the film product; ⑵ Forming process of waterborne polyurethane film products ①Mold cleaning: acid wash, alkali wash, deionize the glass mold, and dry it at 100-110℃; ②Impregnation of release agent: Cool the glass mold to 70-80℃, impregnate the release agent, and dry at 100-110℃; ③Immersing in water-based polyurethane emulsion: Cool the glass mold to 60-70℃, immerse in water-based polyurethane emulsion for the first time, 70-80℃, bake for 1-3 minutes, immerse in water-based polyurethane emulsion for the second time, 70-80℃, bake for 1-3 minutes, immerse in water-based polyurethane emulsion for the third time, 70-80℃, bake for 6-8 minutes, and dry at 100-110℃ for 10-20 minutes; ④ Curling: curl the water-based polyurethane film; ⑤Immerse in release agent: immerse the mold in the release agent and dry at 100-110℃ for 20-30 minutes; ⑥ Demolding, electrical inspection, and packaging: Cool the mold to room temperature, demould, and after passing the electrical inspection, optionally add an anti-sticking agent / lubricant and package to obtain the finished waterborne polyurethane film product.

12. A method for preparing a water-resistant and flexible waterborne polyurethane film product based on multiple hydrogen bonds according to any one of claims 1 to 9, characterized in that: The preparation method of the waterborne polyurethane film product comprises the following steps: ⑴ Preparation of waterborne polyurethane emulsion ① Raw material pretreatment: firstly, the hydrogen bond monomer precursor compound, polysiloxane, polymer polyol, hydrophilic chain extender and cross-linking agent are dehydrated under vacuum conditions at 90-120°C; ② Preparation of waterborne polyurethane polymer: add the polysiloxane and polymer polyol treated in step ① to a reaction kettle, then add diisocyanate, react at 80-95° C. for 2-4 hours, and then cool to 60-70° C.; add the crosslinking agent treated in step ①, react at 80-90° C. for 2-4 hours, and then cool to 60-70° C.; add the hydrophilic chain extender and organic solvent treated in step ①, react at 70-90° C. for 2-4 hours, and then cool to 50-60° C.; add the hydrogen bond monomer precursor compound, diisocyanate and organic solvent treated in step ①, react at 50-70° C. for 2-4 hours, and then cool to 20-30° C.; add a salt-forming agent and an organic solvent, react at 20-30° C. for 0.5-1 hour to obtain a waterborne polyurethane polymer; ③ Emulsification of waterborne polyurethane polymer: pour the waterborne polyurethane polymer of step ③ into an emulsification tank, maintain the temperature of the emulsification tank at 0-10° C., pour 500-700 parts by weight of deionized water into the emulsification tank, and stir at a speed of 8000-12000 rpm for 20-60 minutes. After emulsification, stir at a speed of 200-500 rpm for 4-6 hours to obtain a waterborne polyurethane emulsion; ④ Removal of organic solvent: transfer the aqueous polyurethane emulsion prepared in step ③ to a desolventizing tank, heat it to 40-50°C, and remove the organic solvent under vacuum to obtain the aqueous polyurethane emulsion for the film product; ⑵ Forming process of waterborne polyurethane film products ①Mold cleaning: acid wash, alkali wash, deionize the glass mold, and dry it at 100-110℃; ②Impregnation of release agent: Cool the glass mold to 70-80℃, impregnate the release agent, and dry at 100-110℃; ③Immersing in water-based polyurethane emulsion: Cool the glass mold to 60-70℃, immerse in water-based polyurethane emulsion for the first time, 70-80℃, bake for 1-3 minutes, immerse in water-based polyurethane emulsion for the second time, 70-80℃, bake for 1-3 minutes, immerse in water-based polyurethane emulsion for the third time, 70-80℃, bake for 6-8 minutes, and dry at 100-110℃ for 10-20 minutes; ④ Curling: curl the water-based polyurethane film; ⑤Immerse in release agent: immerse the mold in the release agent and dry at 100-110℃ for 20-30 minutes; ⑥ Demolding, electrical inspection, and packaging: Cool the mold to room temperature, demould, and after passing the electrical inspection, optionally add an anti-sticking agent / lubricant and package to obtain the finished waterborne polyurethane film product.

13. The use of a water-resistant and flexible waterborne polyurethane film product based on multiple hydrogen bonds according to claim 1, characterized in that: Used for preparing condoms, gloves, and organ bags.

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