High-elasticity water-resistant flexible waterborne polyurethane elastic film product

Abstract

The invention discloses a high-elasticity water-resistant flexible waterborne polyurethane elastic film product, and belongs to the field of waterborne polyurethane elastic film products. The waterborne polyurethane structure contains a strong supramolecular dynamic crosslinking unit and a polysiloxane unit, the strong supramolecular dynamic crosslinking unit has a metal-ligand effect and an optional multiple hydrogen bond effect, and the metal-ligand effect is preformed. In the polymerization process of the waterborne polyurethane, a preformed metal complex with a metal-ligand function serves as a weaving node, and the metal complex serves as a monomer and is cross-linked with a waterborne polyurethane chain segment. Due to the woven cross-linked interweaving structure, macromolecular chains connected to weaving nodes are spontaneously entangled. High polymer chain entanglement, reversibility of dynamic bonds and a cross-linked network endow the film with high strength, high elasticity, high flexibility and high density; meanwhile, the polysiloxane endows the film with water resistance and low viscosity. The waterborne polyurethane elastic film product prepared by adopting the structure is super-flexible, high in elasticity and good in water resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of waterborne polyurethane elastic film products, and in particular relates to a highly elastic, water-resistant and flexible waterborne polyurethane elastic film product. Background Art

[0002] Elastic film products such as condoms, medical gloves, organ bands, and finger cots are generally natural latex elastic film products. However, with the development of the times, the inherent defects of the elastic film of natural latex products have been gradually discovered. At the same time, the new viruses of the new era have put forward higher requirements for elastic film products such as condoms, medical gloves, and organ bands. The use and safety of these natural latex elastic film products cannot meet the requirements of modern people for such elastic film products. There are the following problems with latex elastic film products: 1. Allergy problems: dissolved protein, vulcanizer, antioxidant, accelerator; 2. Nitrosamine and toxicity problems. Especially for condoms, the thickness of latex condoms is more than 30 microns. A study in the United States shows that for every 10 microns decrease in condom thickness, the sensitivity of men will increase by 20%; in terms of virus blocking efficiency, the widely used latex condoms cannot prevent the spread of any sexually transmitted diseases.

[0003] Polyurethane materials are block polymers containing a large number of carbamate groups. They are usually polymerized by stepwise polymerization of diisocyanates or polyisocyanates with compounds containing two or more active hydrogens. In addition to the formation of carbamate groups, urea, biuret and other groups are also generated. This type of structure gives polyurethane good chemical stability, biocompatibility, resistance to corrosion by various acids, alkalis and organic solvents, and at the same time gives polyurethane high strength, good elasticity and excellent processing properties. This structure determines that polyurethane can be used to prepare ultra-thin elastic films. Currently, polyurethane films are used to make condoms, medical gloves, organ bands, and finger cots. The prepared films have good thermal conductivity, are non-toxic, and have high strength. At the same time, compared with latex elastic film products, it has good thermal conductivity, no allergic reactions, no special odor, and is not affected by various oily lubricants. In addition, polyurethane elastic film products can effectively filter HIV and prevent pregnancy. However, the elasticity of polyurethane elastic film products is not as good as natural latex, and the cost is high. At the same time, the prepared condoms are easy to fall off and break during use.

[0004] Moreover, the flexibility and elasticity of elastic film products currently on the market have not yet met the current needs of people. At the same time, the new era has put forward higher requirements for the high elasticity, water resistance and flexibility of water-based polyurethane elastic film products. At the same time, improving the flexibility, water resistance and high elasticity of polyurethane elastic film products is still a huge challenge.

[0005] The above problems are solved by preparing highly elastic, water-resistant and flexible waterborne polyurethane elastic film products. The current method for improving the high elasticity of polyurethane is to increase the covalent crosslinking degree of the material. For example, patent CN 108095882 A uses a crosslinking agent to increase the crosslinking degree of the material and improve the elasticity of the film. When the covalent crosslinking degree of the material is low, it is difficult to obtain a highly elastic polyurethane film; however, when the covalent crosslinking degree of the polyurethane film is high, the tensile modulus of the elastic film will be greatly increased, that is, the hardness of the material will be increased. For example, patent CN 108095882 B uses the addition of unsaturated diols and graphite to obtain highly elastic and soft waterborne polyurethane condoms, but the condoms obtained by this method contain a large amount of unsaturated bonds and graphite, and the obtained material has poor water resistance and high modulus.

[0006] At the same time, the dynamic bond cross-linking formed later is introduced: metal-coordination effect and multi-hydrogen bond effect, which will affect the dynamic bond cross-linking formed later due to the steric hindrance effect.

[0007] Therefore, it is necessary to prepare a new type of cross-linked waterborne polyurethane elastic film product and obtain a highly elastic, water-resistant and flexible waterborne polyurethane elastic film product.

[0008] Furthermore, there is no report that metal-ligand interaction is first formed and then introduced as a cross-linking agent together with polysiloxane into waterborne polyurethane elastic film products to simultaneously improve their flexibility, water resistance and high elasticity. Summary of the invention

[0009] In order to solve the problems existing in the above-mentioned prior art, the present invention prepares a highly elastic, water-resistant and flexible waterborne polyurethane elastic film product. Compared with traditional cross-linking agents and traditional dynamic bond modifications, a new approach is taken to introduce preformed metal-ligand effects. The waterborne polyurethane structure contains strong supramolecular dynamic cross-linking units, which contain metal-ligand effects and optional multiple hydrogen bonds and dynamic covalent bonds, and the metal-ligand effects are preformed. During the polymerization of waterborne polyurethane, the preformed metal complex containing metal-ligand effects is a braiding node, and the metal complex is cross-linked with the waterborne polyurethane chain segment as a monomer. Due to the interwoven structure of the braided cross-linking, the polymer chains connected at the braiding nodes are spontaneously entangled. At the same time, the polysiloxane and / or fluorine-containing units introduced into the structure of the waterborne polyurethane elastic film product give it water resistance and low surface viscosity. The strong supramolecular dynamic crosslinking units and polysiloxane and / or fluorine-containing units introduced in the scheme form a crosslinking network and polymer entanglement in the waterborne polyurethane, which endows the waterborne polyurethane elastic film product with high elasticity and water resistance, and the dynamic bonds contained in the waterborne polyurethane elastic film product with flexibility, and the introduced polysiloxane and / or fluorine-containing units reduce the self-adhesion caused by the supramolecular metal ligand effect and the optional dynamic covalent bonds and hydrogen bonds, thereby avoiding the self-adhesion of the waterborne polyurethane elastic film product. The waterborne polyurethane in the present invention contains polysiloxane and / or fluorine-containing units and strong supramolecular dynamic crosslinking units, and the prepared waterborne polyurethane film has a smooth surface, is flexible, water-resistant and highly elastic, and a waterborne polyurethane elastic film with excellent comprehensive performance is prepared.

[0010] The present invention is achieved through the following technical solutions:

[0011] The present invention prepares a highly elastic, water-resistant and flexible waterborne polyurethane elastic film product. The product is prepared by preparing an emulsion of a modified waterborne polyurethane polymer and by a film-forming process; wherein the modified waterborne polyurethane polymer structure contains a strong supramolecular dynamic crosslinking unit and a polysiloxane unit, and the strong supramolecular dynamic crosslinking unit is introduced at least by a polymerization reaction of a metal complex and a diisocyanate; the metal complex contains at least three reactive groups and is preformed by at least two ligand compounds and a metal ion;

[0012] The modified waterborne polyurethane polymer is prepared from the following raw materials in parts by weight:

[0013]

[0014] In the present invention, the ligand compound has the following general structure: R1-R3-M-R4-R2, wherein R1 and R2 are reactive groups independently selected from hydroxyl, amino, thiol and combinations thereof; R3 and R4 are absent or are carbon chain linking groups selected from C 1-24 Alkylene, substituted C1-24 Alkylene. Substituted C 1-24 The alkylene group contains heteroatoms or heteroatom-containing groups substituted with C 1-24 The hydrogen atoms of the alkylene group, wherein the heteroatoms include but are not limited to O, S, N, P, Si, F, Cl, Br, I, B.

[0015] One of the preferred groups of R3 and R4 is that R3 and R4 include C 3～6 Divalent cycloalkyl, substituted C 3～6 A1, A2, A3 are each independently selected from the group consisting of alkyl, cycloalkyl, phenyl, aralkyl, substituted alkyl, substituted cycloalkyl, substituted phenyl, substituted aralkyl, hybridized alkyl, hybridized cycloalkyl, hybridized phenyl, and hybridized aralkyl.

[0016] One of the preferred groups of R3 and R4 is C 1～24 Alkylene, more preferably C 1～12 Alkylene, more preferably C 1～9 Specifically, methylene, 1,2-ethylene, 1,3-propylene, 1,9-nonylene, -Ph-, and -CH2-Ph- are preferred.

[0017] M contains at least the following ligand structure:

[0018]

[0019] Indicates connection to polymer chains, cross-links, groups, atoms.

[0020] In the present invention, the metal complex contains at least three reactive groups and is preformed by at least two ligand compounds and a metal ion; preferably, the metal complex contains at least four reactive groups and is preformed by at least two ligand compounds and a metal ion.

[0021] Wherein, the metal ions of the metal complex are selected from one or more of the following: calcium ion, zinc ion, iron ion, cuprous ion, ferrous ion, cupric ion, and lanthanide metal ion; the metal ion is dissolved in an organic solvent in the form of a metal ion salt and then added to the coordination reaction, and the metal ion salt comprises calcium chloride, ferric chloride, ferrous chloride, cupric chloride, cuprous chloride, cerium chloride, europium chloride, zinc chloride, calcium nitrate, ferric nitrate, ferrous nitrate, cupric nitrate, cuprous nitrate, cerium nitrate, europium nitrate, zinc nitrate, calcium perchlorate, ferric perchlorate, ferrous perchlorate, cupric perchlorate, cuprous perchlorate, cerium perchlorate, europium perchlorate, zinc perchlorate, ferric sulfate, ferrous sulfate, cupric sulfate, cuprous sulfate, cerium sulfate, europium sulfate, and zinc sulfate; the organic solvent comprises acetone, acetonitrile, and tetrahydrofuran.

[0022] Wherein, the ligand compound comprises dimethylglyoxime,

[0023] Preformed metal complexes, in the process of waterborne polyurethane polymerization, the preformed metal complexes containing metal ligands are braided nodes, and the metal complexes are cross-linked with waterborne polyurethane segments as monomers. Due to the interwoven structure of the braided cross-linking, the polymer chains connected at the braided nodes are spontaneously entangled. The entanglement of the polymer chains gives the material high elasticity, while the dynamic metal-coordination effect and the cross-linking network give the material flexibility and density.

[0024] In the present invention, the polysiloxane unit is introduced by polymerization reaction of polysiloxane and isocyanate, wherein the polysiloxane is selected from at least one of hydroxyl-terminated polysiloxane, amino-terminated polysiloxane and mercapto-terminated polysiloxane. Hydroxyl-terminated polysiloxane, amino-terminated polysiloxane and mercapto-terminated polysiloxane have the following general structure: Wherein R5 and R6 are independently selected from hydroxyl, amino, and thiol, L1 and L2 are divalent linking groups independently selected from C 1-20 Alkylene, substituted C 1-20 Hydrocarbylene, J, Q are independently selected from methyl, long chain alkyl, phenyl, epoxy, trifluoropropyl, perfluoroalkyl oxasulfonylpropyl, CF3OCF(CF3)CF2OCF2(CH2)2-; substituted C 1-20 Alkylene refers to C 1-20 The group obtained by substituting the hydrogen atom of the hydrocarbon group includes, but is not limited to, 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, and fluorine-containing hydrocarbon group. The fluorine-containing hydrocarbon group is selected from one of trifluoropropyl, perfluoroalkyl oxasulfonylpropyl, fluorine ether, and fluorine ester; x and y are integers of 5 to 40; m, n, and o are integers of 1 to 30.

[0025] One of the preferred groups of L1 and L2 is L1 and L2 comprising At least one of, wherein A4, A5, A6 are substituents containing 1 to 10 carbon atoms, and are independent of each other, any two of which are the same or different from each other; l, m, n, o, p, q are integers of 1 to 30; A1, A2, A3 are independently selected from, including but not limited to: oxo (=O), thio (=S), amino (connected to the main chain carbon through a carbon-nitrogen double bond), ether-bonded oxygen heteroalkyl, thioether-bonded thio heteroalkyl, tertiary amino-type nitrogen heteroalkyl, fluorine-containing hydrocarbon. The fluorine-containing hydrocarbon is selected from trifluoropropyl, perfluoroalkyl oxasulfonylpropyl, fluorine ether, and fluorine ester.

[0026] One of the preferred groups of L1 and L2 is C 1～12 Alkylene, more preferably C 1～10 Alkylene, more preferably C 1～3 Specifically, 1,2-ethylene and 1,3-propylene are preferred.

[0027] The polysiloxane is preferably at least one of amino-terminated polydimethylsiloxane, hydroxy-terminated polydimethylsiloxane, amino-terminated polyether polysiloxane, hydroxy-terminated long-chain alkane polysiloxane, amino-terminated long-chain alkane polysiloxane, amino-terminated amide polysiloxane, hydroxy-terminated fluoroalkyl polysiloxane, polyether-modified polydimethylsiloxane, amino-terminated polymethylphenylsiloxane, and hydroxy-terminated polymethylphenylsiloxane.

[0028] As the soft segment of polyurethane, the siloxane on the main chain can reduce the strength and modulus of polyurethane, making water-based polyurethane condoms softer. At the same time, the added polysiloxane is enriched on the film surface through the migration effect of siloxane during the preparation of the film, giving the film surface stronger water resistance, skin affinity and demolding effect. The fluorine-containing chain extender introduces fluorine atoms into the water-based polyurethane system, further reducing the surface energy of the water-based polyurethane film, while giving the water-based polyurethane film high water resistance and high strength. Furthermore, polysiloxane and / or fluorine-containing units reduce the self-adhesion caused by the dynamic covalent bonds and supramolecular metal ligands / hydrogen bonds, avoiding the self-adhesion of water-based polyurethane elastic film products.

[0029] In the present invention, the diisocyanate is selected from one or more 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-cyclohexane dimethyl diisocyanate, and 4,4-diisocyanate dicyclohexylmethane. The polymer diol is selected from at least one of polyester diol, polyolefin diol, and polyether diol. The polyester diol is selected from polyhexamethylene carbonate diol, polycarbonate-1,6-hexanediol ester diol, polycaprolactone carbonate hexamethylene ester diol, polybutylene carbonate diol, polycyclohexanedimethanol carbonate-1,6-hexanediol ester diol, polycarbonate-1,5-pentanediol-1,6-hexanediol ester diol, polyethylene carbonate diol, polypropylene carbonate diol, polycarbonate-1,4-butanediol-1,6-hexanediol ester diol, polycaprolactone 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 -At least one of adipic acid polyester diol, neopentyl glycol-adipic acid polyester diol, 1,6-hexanediol-adipic acid polyester diol, dimerized lactic acid polyethylene glycol, polyethylene glycol-polylactic acid-hydroxyacetic acid copolymer, ethylene glycol-seed diol polyester diol, diethylene glycol-seed diol polyester diol, neopentyl glycol-seed diol polyester diol, poly-3-methyl-1,5-pentanediol adipic acid ester diol, poly-1,4-cyclohexanedicarboxylic acid-3-methyl-1,5-pentanediol ester diol, and polyester diols of bio-based small molecule diols-acids, whose average number average molecular weight is 2000 to 4000 Da. The polyolefin diol is selected from at least one of polybutadiene diol, polybutadiene-acrylonitrile copolymer diol, hydroxyl-terminated epoxidized polybutadiene diol, hydroxyl-terminated polyisoprene diol, hydroxyl-terminated hydrogenated polyisoprene diol, hydrogenated polybutadiene diol, polystyrene-allyl alcohol copolymer diol, and polystyrene-ethylene-butylene-styrene diol, and its average number average molecular weight is 2000-4000Da. The polyether diol is selected from at least one of polytetramethylene ether diol, polytrimethylene ether diol, polyethylene oxide diol, polytetramethylene ether diol-propylene oxide copolyether diol, polytetramethylene ether diol-ethylene oxide copolyether diol, polypropylene oxide diol, polyethylene oxide diol, polyethylene oxide propylene oxide copolyether diol, and fluorine-containing polyether diol, and its average number average molecular weight is 2000-4000Da.

[0030] The fluorinated polyether diol includes perfluoropolyether diol and fluorinated linear polyether diol synthesized from bisphenol AF, ethylene oxide and propylene oxide.

[0031] The polymer diol is preferably at least one of polytetramethylene glycol, perfluoropolyether glycol, polycarbonate glycol and polyolefin glycol. The waterborne polyurethane soft segment contains polytetramethylene glycol, polycarbonate, polyolefin and fluorine-containing polyether structures and has excellent water resistance.

[0032] In the present invention, the hydrophilic chain extender is selected from at least one of dimethylol propionic acid, dimethylol butyric acid, sodium ethylenediamine ethanesulfonate, sodium N,N-(2-hydroxyethyl)-2-aminoethanesulfonate, sodium 1,4-butanediol-2-sulfonate, and methyldiethanolamine. The trifunctional crosslinking agent is selected from at least one of triethanolamine, triisopropanolamine, trimethylolpropane, trimethylolethane, 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, trihydroxyethyl isocyanurate, melamine, benzene-1,2,3-triamine, diethylenetriamine, low molecular weight polyether triol, and castor oil. The post-chain extender is selected from at least one of 1,3-propylenediamine, 1,4-butylenediamine, 1,6-hexanediamine, isophoronediamine, ethylenediamine, diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, trimethylhexanediamine, 1,12-dodecanediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)ether, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, polyetheramine, and sodium ethylenediamine ethanesulfonate. The catalyst is selected from at least one of dibutyltin dilaurate, bismuth laurate, bismuth isooctanoate, bismuth neodecanoate, stannous octoate, potassium oleate, cobalt octoate, ferric chloride, and sodium o-phenylphenol. The salt-forming agent is selected from at least one of triethylamine, diethanolamine, potassium hydroxide, sodium hydroxide, and diisopropylethanolamine.

[0033] The present invention provides a method for preparing a highly elastic, water-resistant and flexible waterborne polyurethane elastic film product, comprising the following steps:

[0034] (1) Preparation of modified waterborne polyurethane polymer

[0035] ① To synthesize the metal complex, first add 2.8-5 parts by weight of the ligand compound, 0.2-0.5 parts by weight of the metal ion salt, and 35-50 parts by weight of the organic solvent, and heat to 50-55°C with stirring for 0.5-1h;

[0036] ② Synthesis of prepolymer: 3-4 parts by weight of polysiloxane, 4.5-5 parts by weight of hydrophilic chain extender and 60-70 parts by weight of polymer diol are added into a new reactor, heated to 100-120°C with stirring, vacuum dehydrated for 2-3 hours, cooled to 45-65°C, added with 38.1-55.5 parts by weight of metal complex solution and 1.4-1.5 parts by weight of trifunctional crosslinking agent, stirred for 0.3-0.6 hours, and then added with 2 9.6-31.4 parts by weight of diisocyanate, stirring and heating to 65-80°C for reaction for 0.5-1h, adding 0.06-0.07 parts by weight of catalyst, stirring and heating to 90-95°C for reaction for 1-1.5h, adding 30-60 parts by weight of organic solvent for reaction for 4-5h, then cooling to 20-30°C, adding 3.4-3.5 parts by weight of salt-forming agent, stirring for 0.5-2h to obtain a modified waterborne polyurethane polymer;

[0037] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer is transferred to an emulsifier, and 400 to 600 parts by weight of ice water are added to the prepolymer under high-speed stirring at 6500 to 10000 r / min. After emulsification, 0.7 to 1.7 parts by weight of a post-chain extender are added, and then the rotation speed is adjusted to 300 to 600 r / min, and stirring is continued for 5 to 7 hours; the obtained polyurethane emulsion is heated to 45 to 60° C., and the organic solvent is removed under a vacuum condition of -0.08 to -0.09 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products;

[0038] (3) Film formation

[0039] ① Glass mold cleaning: The glass mold is first cleaned with an alkaline detergent, then with an acidic detergent, and finally with neutral deionized water, and dried to 70°C;

[0040] ② Dip the mold release agent: immerse the glass mold at 70℃ in the mold release agent for 30s, then slowly take it out at a uniform speed and dry it at 70℃;

[0041] ③ Dipping in emulsion: immerse the 70°C glass mold with a release agent in polyurethane emulsion for 10 seconds, then slowly take it out at a uniform speed, dry it at 90°C for 10 seconds, immerse it in polyurethane emulsion for 10 seconds, then slowly take it out at a uniform speed, dry it at 90°C for 20 seconds, immerse it in polyurethane emulsion for 10 seconds, then slowly take it out at a uniform speed, and finally dry it at 80°C for 7 minutes;

[0042] ④ Curling and drying: The film obtained in step ③ is curled to a suitable position, and the mold after curling is dried at 90°C for 5 minutes;

[0043] ⑤Immersing in anti-adhesive agent, drying, and demoulding: After curling and drying, the mold is cooled to 30°C, immersed in anti-adhesive agent, dried at 90°C, and then demoulded to obtain a polyurethane elastic film product;

[0044] The organic solvent is selected from one or more of acetone, acetonitrile, tetrahydrofuran, ethyl acetate and n-propyl acetate.

[0045] In the present invention, the strong supramolecular dynamic crosslinking unit further comprises a strong hydrogen bonding unit. The strong hydrogen bonding unit is introduced by pre-forming a hydrogen bonding compound from a hydrogen bonding monomer compound and / or by forming a hydrogen bonding unit from a reactant that can generate a hydrogen bonding monomer when polymerizing the modified waterborne polyurethane polymer. The hydrogen bonding monomer is selected from at least one of the following structures:

[0046] Wherein R7 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 1-15 Alkylene or substituted C 1-15 The preferred number of carbon atoms is C 1-12 , that is, C 1-12 Alkylene or substituted C 1-12 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.

[0047] One of the preferred groups of R7 is that R7 includes phenylene and substituted phenylene. Substituted phenylene means that any hydrogen atom on the phenylene is replaced by a substituent; the substituent includes but is not limited to heteroatoms and groups containing heteroatoms. Specifically, -Ph-,

[0048] One of the preferred groups of R7 is C 1～12 Specifically, methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,11-undecylene, and 1,12-dodecylene are preferred.

[0049] One of the preferred groups of R7 is one of the following structures:

[0050] The hydrogen bonding monomer compound is selected from the following compounds:

[0051] The reactants capable of generating hydrogen bond monomers are selected from the following compounds: succinic acid hydrazide, adipic acid dihydrazide, isophthalic acid dihydrazide and dodecanedicarboxylic acid dihydrazide, sebacic acid dihydrazide, azelaic acid dihydrazide, maleic acid dihydrazide, oxalyl dihydrazide, phthalic acid dihydrazide, 2,5-dibutoxyterephthaloyl hydrazide, 2,5-bis(benzyloxy)terephthaloyl hydrazide, 3,3'-dithiobispropionic acid hydrazide,

[0052]

[0053] In the present invention, the strong supramolecular dynamic cross-linking unit contains both metal-coordination effect and strong hydrogen bonding effect, which further strengthens and toughens the waterborne polyurethane film.

[0054] The present invention provides a method for preparing a highly elastic, water-resistant and flexible waterborne polyurethane elastic film product, which is characterized by comprising the following steps:

[0055] (1) Preparation of modified waterborne polyurethane polymer

[0056] ① To synthesize the metal complex, first add 2.8-10.7 parts by weight of the ligand compound, 0.2-0.6 parts by weight of the metal ion salt, and 30-50 parts by weight of the organic solvent, and heat to 40-55°C with stirring for 0.5-1h;

[0057] ② Synthesis of prepolymer: 3-5 parts by weight of polysiloxane, 3.5-5 parts by weight of hydrophilic chain extender and 50-70 parts by weight of polymer diol are added into a new reaction kettle, heated to 100-120°C with stirring, vacuum dehydrated for 2-3 hours, cooled to 45-65°C, added with 32.8-60.7 parts by weight of metal complex solution and 1-1.5 parts by weight of trifunctional crosslinking agent, stirred for 0.3-1 hour, then added with 22.4-34.9 parts by weight of diisocyanate, stirred and heated to 65-80°C for reaction for 0.5 ~1h, add 0.06~0.1 weight part of catalyst, stir and heat to 80~95℃ for reaction for 1~2h, add 30~60 weight parts of organic solvent for reaction for 3~5h, add 1.3~4.1 weight parts of reactant or hydrogen bond monomer compound that can generate hydrogen bond monomer, stir and cool to 50~65℃, add 50~80 weight parts of organic solvent for reaction for 3~5h, then cool to 20~30℃, add 1.4~4.9 weight parts of salt-forming agent, stir for 0.5~2h to obtain modified waterborne polyurethane polymer;

[0058] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer is transferred to an emulsifier, and 300 to 600 parts by weight of ice water are added to the prepolymer under high-speed stirring at 4000 to 10000 r / min. After emulsification, 0.3 to 15 parts by weight of a post-chain extender are added, and then the rotation speed is adjusted to 200 to 600 r / min, and stirring is continued for 5 to 7 hours; the obtained polyurethane emulsion is heated to 40 to 60° C., and the organic solvent is removed under a vacuum condition of -0.08 to -0.1 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products;

[0059] (3) Film formation

[0060] ① Glass mold cleaning: The glass mold is first cleaned with an alkaline detergent, then with an acidic detergent, and finally with neutral deionized water, and dried to 70°C;

[0061] ② Dip the mold release agent: immerse the glass mold at 70℃ in the mold release agent for 30s, then slowly take it out at a uniform speed and dry it at 70℃;

[0062] ③ Dipping in emulsion: immerse the 70℃ glass mold with release agent in polyurethane emulsion for 10s, then slowly take it out at a uniform speed, dry it at 90℃ for 10s, immerse it in polyurethane emulsion for 10s again, then slowly take it out at a uniform speed, dry it at 90℃ for 20s, immerse it in polyurethane emulsion for 10s again, then slowly take it out at a uniform speed, and finally bake it at 80℃ for 7min;

[0063] ④ Curling and drying: The film obtained in step ③ is curled to a suitable position, and the mold after curling is dried at 90°C for 5 minutes;

[0064] ⑤Immersing in anti-adhesive agent, drying, and demoulding: After curling and drying, the mold is cooled to 30°C, immersed in anti-adhesive agent, dried at 90°C, and then demoulded to obtain a polyurethane elastic film product;

[0065] The highly elastic, water-resistant and flexible waterborne polyurethane elastic film product is used for preparing condoms, organ bands, finger cots and medical gloves.

[0066] The organic solvent is selected from one or more of acetone, acetonitrile, tetrahydrofuran, ethyl acetate and n-propyl acetate.

[0067] The emulsion of the present invention is further enhanced by metal-coordination, wherein the metal-coordination is formed by coordination of carboxylic acid ligands and zinc ions, and coordinated in the waterborne polyurethane emulsion. The carboxylic acid ligand is introduced after the reaction of a carboxylic acid hydrophilic chain extender with isocyanate; the carboxylic acid hydrophilic chain extender includes dimethylol propionic acid and dimethylol butyric acid; the zinc ion is dissolved in water in the form of a zinc ion salt and then added to the coordination reaction, and the zinc ion salt is zinc acetate.

[0068] Accordingly, the present invention provides a method for preparing a highly elastic, water-resistant and flexible water-based polyurethane elastic film product, which is characterized by comprising the following steps:

[0069] (1) Preparation of modified waterborne polyurethane polymer

[0070] ① To synthesize the metal complex, first add 6.5 parts by weight of the ligand compound, 0.3 parts by weight of the metal ion salt, and 45 parts by weight of the organic solvent, and heat to 50°C with stirring for 0.8h;

[0071] ② Synthesis of prepolymer: 3 parts by weight of polysiloxane, 3.5 parts by weight of hydrophilic chain extender and 70 parts by weight of polymer diol are put into a new reactor, heated to 110°C with stirring, vacuum dehydrated for 2.5 hours, cooled to 55°C, 56.8 parts by weight of metal complex solution and 1.5 parts by weight of trifunctional crosslinking agent are put in, stirred for 0.5 hours, then 34.9 parts by weight of diisocyanate are put in, stirred and heated to 80°C for reaction for 0.5 hours, 0.1 parts by weight of catalyst are added, stirred and heated to 95°C for reaction for 1 hour, 30 parts by weight of organic solvent are put in for reaction for 5 hours, then cooled to 65°C, 2.2 parts by weight of reactant or hydrogen bond monomer compound capable of generating hydrogen bond monomer and 50 parts by weight of organic solvent are put in for reaction for 3 hours, then cooled to 20°C, 1.4 parts by weight of salt-forming agent are added, stirred for 2 hours to obtain a modified waterborne polyurethane polymer;

[0072] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer is transferred to an emulsifier, and 500 parts by weight of ice water is added to the prepolymer under high-speed stirring at 8000 r / min. After emulsification, 15 parts by weight of a post-chain extender is added, and then the speed is adjusted to 400 r / min and stirring is continued for 7 hours; 600 parts by weight of distilled water is added to dilute the emulsion, and then 1.5 parts by weight of zinc acetate is added and stirred for 2 hours. The obtained polyurethane emulsion is heated to 60° C. and the organic solvent is removed under a vacuum condition of -0.09 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products;

[0073] (3) Film formation

[0074] ① Glass mold cleaning: The glass mold is first cleaned with an alkaline detergent, then with an acidic detergent, and finally with neutral deionized water, and dried to 70°C;

[0075] ② Dip the mold release agent: immerse the glass mold at 70℃ in the mold release agent for 30s, then slowly take it out at a uniform speed and dry it at 70℃;

[0076] ③ Dipping in emulsion: immerse the 70°C glass mold with a release agent in polyurethane emulsion for 10 seconds, then slowly take it out at a uniform speed, dry it at 90°C for 10 seconds, immerse it in polyurethane emulsion for 10 seconds, then slowly take it out at a uniform speed, dry it at 90°C for 20 seconds, immerse it in polyurethane emulsion for 10 seconds, then slowly take it out at a uniform speed, and finally dry it at 80°C for 7 minutes;

[0077] ④ Curling and drying: The film obtained in step ③ is curled to a suitable position, and the mold after curling is dried at 90°C for 5 minutes;

[0078] ⑤Immersing in anti-adhesive agent, drying, and demoulding: After curling and drying, the mold is cooled to 30°C, immersed in anti-adhesive agent, dried at 90°C, and then demoulded to obtain a polyurethane elastic film product;

[0079] The organic solvent is selected from one or more of acetone, acetonitrile, tetrahydrofuran, ethyl acetate and n-propyl acetate.

[0080] The waterborne polyurethane contains polysiloxane and / or fluorine-containing units but does not contain strong supramolecular dynamic crosslinking units, and the prepared waterborne polyurethane film has low elongation at break, weak tensile strength and poor toughness; the waterborne polyurethane does not contain polysiloxane and / or fluorine-containing units but contains strong supramolecular dynamic crosslinking units, and the prepared waterborne polyurethane film has high surface viscosity and generally has a self-repairing function, and is difficult to be applied to waterborne polyurethane elastic film products; the waterborne polyurethane in the present invention contains polysiloxane and / or fluorine-containing units and strong supramolecular dynamic crosslinking units, and the prepared waterborne polyurethane film has a smooth surface, is flexible, water-resistant, highly elastic and has low viscosity, and a waterborne polyurethane elastic film with excellent comprehensive performance is prepared.

[0081] The present invention introduces the above-mentioned strong supramolecular dynamic cross-linking units and polysiloxane and / or fluorine-containing units to obtain water-resistant, high-elasticity and flexibility of the film. During the polymerization process of waterborne polyurethane, the preformed metal complex containing metal ligand action is a weaving node, and the metal complex is cross-linked with the waterborne polyurethane chain segment as a monomer. Due to the interwoven structure of the weaving cross-linking, the polymer chains connected at the weaving nodes are spontaneously entangled. In the present invention, the entanglement of the polymer chains gives the film high strength and high elasticity; the dynamic reversibility of the metal-ligand action and the multi-hydrogen bond action gives the film flexibility; the cross-linking network gives the film high strength, stability, high density and high elasticity; the dynamic covalent bond gives the film flexibility. Polysiloxane and / or fluorine-containing give the film water resistance and skin-softness, further reducing the self-adhesion caused by the supramolecular metal ligand action and the optional dynamic covalent bond and hydrogen bond dynamics. In the present invention, the strong supramolecular dynamic cross-linking structure and polysiloxane and / or fluorine-containing structure introduced into the waterborne polyurethane elastic film structure can maintain the low modulus of the film on the basis of enhancing the strength and elasticity of the film, and the prepared film can simultaneously obtain high elasticity, water resistance and flexibility. The highly elastic, water-resistant and flexible waterborne polyurethane elastic film product can be used to prepare condoms, and the highly elastic, water-resistant and flexible waterborne polyurethane elastic film product can be used to prepare organ bands, finger cots, and medical gloves.

[0082] Compared with the prior art, the present invention has the following beneficial effects:

[0083] (1) The present invention prepares a highly elastic, water-resistant and flexible waterborne polyurethane elastic film product, wherein the waterborne polyurethane elastic film structure contains a strong supramolecular dynamic crosslinking unit and a polysiloxane and / or a fluorine-containing unit, wherein the strong supramolecular dynamic crosslinking unit contains a metal-ligand effect and optional multiple hydrogen bonds and dynamic covalent bonds, and the metal ligand effect is preformed and then added to the waterborne polyurethane as a crosslinking agent to form a crosslinking network. During the polymerization of the waterborne polyurethane, the preformed metal complex containing the metal ligand effect is a braiding node, and the metal complex is crosslinked with the waterborne polyurethane chain segment as a monomer. Due to the interwoven structure of the braided crosslinking, the polymer chains connected at the braiding nodes are spontaneously entangled. The polymer entanglement, cross-linked network and dynamic bond hybridization in the waterborne polyurethane film structure give the material high elasticity, water resistance and flexibility; the polysiloxane added at the same time not only enriches on the film surface through the migration effect of siloxane during the preparation of the film, making the film surface more water-resistant, but also the polysiloxane and / or fluorine-containing units reduce the self-adhesion caused by the supramolecular metal ligand effect and the optional dynamic covalent bonds and hydrogen bonds, avoiding the self-adhesion of the waterborne polyurethane elastic film product. A highly elastic, water-resistant and flexible waterborne polyurethane elastic film product prepared using the above structure has good flexibility, high elasticity and water resistance. This solution solves the shortcomings of existing waterborne polyurethane elastic film products in terms of water resistance, flexibility and elasticity.

[0084] (2) The waterborne polyurethane contains polysiloxane and / or fluorine-containing units but does not contain strong supramolecular dynamic crosslinking units, and the prepared waterborne polyurethane film has low elongation at break, weak tensile strength and poor toughness; the waterborne polyurethane does not contain polysiloxane and / or fluorine-containing units but contains strong supramolecular dynamic crosslinking units, and the prepared waterborne polyurethane film has high surface viscosity and generally has self-healing function, which makes it difficult to be applied to waterborne polyurethane elastic film products; the waterborne polyurethane in the present invention contains polysiloxane and / or fluorine-containing units and strong supramolecular dynamic crosslinking units, and the prepared waterborne polyurethane film has a smooth surface, is flexible, water-resistant and highly elastic, and a waterborne polyurethane elastic film with excellent comprehensive performance is prepared.

[0085] (3) The highly elastic, water-resistant and flexible water-based polyurethane elastic film product of the present invention is used to prepare water-based polyurethane condoms. The prepared water-based polyurethane condoms are as thin as 20 μm or less, with an elongation at break of more than 550%, a tear force of more than 20 N, a 100% tensile modulus of less than 1.2 MPa, a Young's modulus of more than 15 MPa, and a tear force of more than 15 N after being soaked in 50°C hot water for one hour. The performance of the condoms prepared by the present invention can reach the latest condom industry standard YYT1850-2023. Moreover, after testing, the commercial water-based polyurethane condoms with a thickness of less than 20 microns, Sagami 001, can reach the latest condom industry standard YYT 1850-2023; the water-based polyurethane condoms Durex 001, Okamoto 001, and Jissbon 001 cannot reach the latest condom industry standard YYT 1850-2023. The 100% tensile modulus of Sagami 001 on the market is 2.0MPa, which means that the Sagami 001 condom is very hard, which affects the experience during use. The 100% tensile modulus of all formulations of the present invention is below 1.2MPa, and the 100% tensile modulus of Examples 7 and 14 is as low as 0.7-0.8MPa. At the same time, it has an ultra-thin thickness of 15-18 microns, a super-strong tear force of 28-30N, and an ultra-high Young's modulus of 26-30MPa. At the same time, the water resistance of the film was tested using the water resistance test standard in the condom industry standard YYT 1850-2023, and it was found that the film had 85% of the tear force of the original film, that is, it had good water resistance. This shows that the water-based polyurethane film prepared by the present invention is super flexible, highly elastic, and water-resistant. This shows that the highly elastic, water-resistant and flexible water-based polyurethane elastic film product prepared by the present invention can be used to prepare ultra-thin water-based polyurethane condoms. At the same time, the prepared condoms have good water resistance, flexibility and high elasticity, which solves the shortcomings of current water-based polyurethane condoms that are easy to fall off, easy to break and too hard, and at the same time meets the higher requirements for condoms in the new era.

[0086] (4) The highly elastic, water-resistant and flexible water-based polyurethane elastic film product prepared by the present invention has excellent comprehensive performance and meets the high requirements of the new era for medical gloves, organ bands and finger cots in terms of water resistance, flexibility and high elasticity.

[0087] These and other features and advantages of the present invention will become apparent with reference to the following description of the embodiments, examples and appended claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0088] Figure 1 The middle figure shows the stress-strain curve of the comparative sample 2 Sagami 001 condom sample;

[0089] Figure 2 The middle picture is a physical picture of the condom film prepared in Example 7;

[0090] Figure 3 a is a spectrum of the condom sample of Example 7 tested by differential scanning calorimeter; Figure 3 b is the infrared spectrum of the condom sample of Example 7; Figure 3 c is the thermogravimetric curve of Example 7; Figure 3 d is the particle size distribution diagram of the emulsion of Example 7;

[0091] Figure 4 a is the stress-strain curve of the condom sample in Example 1; Figure 4 b is the stress-strain curve of the condom sample of Example 3; Figure 4 c is the stress-strain curve of the condom sample of Example 16; Figure 4 d is the stress-strain curve of the condom sample of Example 17;

[0092] Figure 5 a is the stress-strain curve of the condom sample of Example 2; Figure 5 b is the stress-strain curve of the condom sample of Example 4; Figure 5 c is the stress-strain curve of the condom sample of Example 5; Figure 5 d is the stress-strain curve of the condom sample of Example 8;

[0093] Figure 6 a is the stress-strain curve of the condom sample of Example 9; Figure 6 b is the stress-strain curve of the condom sample of Example 10; Figure 6 c is the stress-strain curve of the condom sample of Example 11; Figure 6 d is the stress-strain curve of the condom sample of Example 12;

[0094] Figure 7 a is the stress-strain curve of the condom sample of Example 13; Figure 7 b is the stress-strain curve of the condom sample of Example 15;

[0095] Figure 8 a is the stress-strain curve of the condom sample of Example 6; Figure 8 b is the stress-strain curve of the condom sample of Example 7; Figure 8 c is the stress-strain curve of the condom sample of Example 14; Figure 8 d is the stress-strain curve of the condom sample in Example 18. DETAILED DESCRIPTION

[0096] Terminology

[0097] Most of the terms involved in the present invention have been disclosed in documents CN108530637A, CN 107266645 B, and CN109206550 B and various cited documents, and the term explanations and related structural examples are incorporated into the present invention as references, and will not be repeated here. If they are different from the description in the present invention, the present invention shall prevail. A brief summary is as follows.

[0098] For the sake of simplicity, the present invention also marks the number of carbon atoms in the group in the subscript form at the subscript position of C, indicating the number of carbon atoms in the group, for example, C 1-24 Means "having 1 to 24 carbon atoms", C 3-6 means "having 3 to 6 carbon atoms". "Substituted C 3-6 "Divalent cycloalkyl" refers to C 3-6 A group obtained by replacing the hydrogen atoms of a divalent cycloalkyl group. 1-24 "Substituted hydrocarbon group" means a group obtained by replacing the hydrogen atoms of the hydrocarbon group with 1 to 24 carbon atoms. For example, when a group can be selected from C 1-10 In the case of a hydrocarbon group, any hydrocarbon group having a carbon number in the range indicated by the subscript can be selected, that is, C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 Any hydrocarbon group.

[0099] 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, an integer range of 1 to 10 means any integer of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0100] For two or more objects in the present invention, when there are multiple levels of preference, it is not required that all of them are selected from the same level of preference groups. One can be preferred in a large range and the other in a small range, or one can be the largest range and the other can be any preferred situation, or they can be selected from the same level of preference. For example, "R8, R9, R 10 , R 11 , R12 The number of carbon atoms of each independently is preferably 1 to 20, more preferably 1 to 10", and may be all 1 to 20, or all 1 to 10, or some may be 1 to 20 and the others may be 1 to 10. Even if they are preferred at the same level or the same type, the structures of the two objects are not limited to be completely identical. For example, A and B are each independently selected from alkyl, cycloalkyl, aryl, and aralkyl. A may be methyl and B may be ethyl, or A may be butyl and B may be benzyl.

[0101] 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.

[0102] The divalent connecting group in the present invention, such as an alkylene group, an alkylene group, an arylene group, an amide bond, etc., can select any one of the two connecting ends when connecting other groups unless otherwise specified. For example, when an amide bond is used as the divalent connecting group between A-CH2CH2- and -CH2-B, it can be A-CH2CH2-C(=O)NH-CH2-B or A-CH2CH2-NHC(=O)-CH2-B.

[0103] In the present invention, a "substituent" may be a single atom (substituent atom) or an atomic group consisting of two or more atoms (substituent group).

[0104] In the present invention, "carbon chain linking group" refers to a linking group in which all the main chain atoms are carbon atoms, while the side chain part allows heteroatoms or heteroatom-containing groups to replace the hydrogen atoms of the main chain carbon. When the "main chain atom" is a heteroatom, it is also called a "main chain heteroatom", such as A-SCH2-B and AO-CH2-B are considered to contain main chain heteroatoms. Carbon chain linking groups can be divided into alkylene groups and carbon chain linking groups containing heteroatoms in the side groups; the carbon chain linking groups containing heteroatoms in the side groups include but are not limited to oxo (=O), thio (=S), amino (connected to the main chain carbon through a carbon-nitrogen double bond), oxygen heteroalkyl in the form of ether bonds, thio heteroalkyl in the form of thioether bonds, nitrogen heteroalkyl in the form of tertiary amino groups, etc.

[0105] The main chain of the "carbon chain linking group" in the present invention is composed entirely of carbon atoms, and the side groups of the carbon chain are allowed to contain heteroatoms. That is, it is connected by methylene or substituted methylene. The substituted methylene can be substituted by a monovalent substituent, two monovalent substituents or a divalent substituent (such as divalent oxygen, or forming a three-membered ring with a divalent methylene). The substituted methylene can be substituted by one hydrogen atom (such as -CH(CH3)-), or two hydrogen atoms can be substituted separately (such as -(CH3)C(OCH3)-), or two hydrogen atoms can be substituted at the same time (such as carbonyl, thiocarbonyl, -C(=NH)-, -C(=N + H2)-).

[0106] 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.

[0107] In the present invention, regarding alkenyl and alkene groups, in the present invention, unsaturated hydrocarbons lose hydrogen atoms to form such as alkenyl groups (also called alkenyl groups), alkynyl groups (also called alkynyl groups), dienyl groups, etc. Unsaturated hydrocarbons lose hydrogen atoms on unsaturated carbons to form hydrocarbon groups, such as 1-alkenyl, 1-alkynyl, 1-dienyl, etc., as examples, propenyl and propynyl; unsaturated hydrocarbons lose hydrogen atoms on saturated carbons to form hydrocarbon groups according to different unsaturated bonds, such as alkenyl-hydrocarbyl groups, alkynyl-hydrocarbyl groups, specifically allyl (2-propenyl) and propargyl (2-propynyl).

[0108] In the present invention, aromatic hydrocarbons lose a hydrogen atom to form aromatic hydrocarbon groups, and typically aromatic hydrocarbons lose a hydrogen atom on an aromatic ring to form aryl groups. Aromatic hydrocarbons lose hydrogen atoms on non-aromatic rings to form aryl-hydrocarbyl groups, such as aromatic hydrocarbons lose hydrogen atoms on non-aromatic rings to form aralkyl groups (aralkyl groups or arylalkyl groups). Aralkyl groups belong to the category of aryl-hydrocarbyl groups. For example, the most typical aryl group is phenyl, and the most typical aryl-hydrocarbyl and aralkyl groups are benzyl groups.

[0109] In the present invention, the "long-chain alkyl" has a molecular weight of 100 to 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.

[0110] In the present invention, "fluorine-containing hydrocarbon group" refers to trifluoropropyl or perfluoroalkyl oxasulfonylpropyl or CF3OCF(CF3)CF2OCF2(CH2)2-.

[0111] In the present invention, "epoxy hydrocarbon group" refers to

[0112] In the present invention, "braided cross-linking" refers to a cross-linked structure in which polymer chains are crossed with each other, formed by four or more polymer chains extending from each braiding point and connected to each other. During the stretching process of the "braided cross-linking" structure, crossed polymer chains form a polymer chain tangle, and the formed polymer chain tangle hinders the movement of the polymer chains, requiring higher external force for stretching.

[0113] In the present invention, "Ph" is a benzene ring.

[0114] The "post-chain extender" in the present invention refers to the chain extender added during the emulsification process of preparing the waterborne polyurethane.

[0115] In the present invention, "alkaline detergent" refers to 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] When Da is used to describe the molecular weight of a compound formula, for a single compound molecule, the value falls within the range of ±10% (including the endpoint) of the stated value.

[0120] In the present invention, the lanthanide metal ions are selected from cerium ions and europium ions.

[0121] In the present invention, "the range for selection includes but is not limited to" means that the structures within the range are optional, but not limited to the structures within the range shown, but not all structures within the range are applicable. The basic principle is to use the smooth implementation of the preparation method of the present invention as the screening standard.

[0122] In the present invention, in the structural formula In To indicate the connection with the polymer chain, cross-linked network chain or any other suitable group / atom in the general structure. In the structural formula, when the terminal group of the linker and its protected substituent are not ambiguous, it can be unmarked, such as the following phenylene structure

[0123] The heteroatoms in the present invention are not particularly limited, including but not limited to O, S, N, P, Si, F, Cl, Br, I, B, etc.

[0124] The present invention discloses a highly elastic, water-resistant and flexible waterborne polyurethane elastic film product, which belongs to the field of waterborne polyurethane elastic film products. The waterborne polyurethane structure contains a strong supramolecular dynamic crosslinking unit and a polysiloxane unit, wherein the strong supramolecular dynamic crosslinking unit contains a metal-ligand effect and an optional multiple hydrogen bond effect, and the metal ligand effect is preformed. During the polymerization of the waterborne polyurethane, the preformed metal complex containing the metal ligand effect is a weaving node, and the metal complex is crosslinked with the waterborne polyurethane chain segment as a monomer. Due to the interwoven structure of the weaving crosslinking, the polymer chains connected at the weaving nodes are spontaneously entangled. The entanglement of the polymer chains, the reversibility of the dynamic bonds and the crosslinking network give the film high strength, high elasticity, high flexibility and high density; at the same time, the polysiloxane gives the film water resistance. A highly elastic, water-resistant and flexible waterborne polyurethane elastic film product prepared by the above structure has good flexibility, high elasticity and water resistance.

[0125] The strong hydrogen bond unit contains no less than 4-tooth hydrogen bonds; the number of teeth is the number of hydrogen bonds formed by the donor (D, i.e., hydrogen atom) and the acceptor (A, i.e., electronegative atom that accepts hydrogen atom) of the hydrogen bond group, and each DA combination is one tooth (as shown in the following formula, which lists the hydrogen bond formation of the tetradentate hydrogen bond group); since the more teeth there are, the stronger the hydrogen bond effect is, usually exceeding the tetradentate hydrogen bond, and its effect is strong, the multiple hydrogen bond cross-linking structure of the present invention can effectively provide a strong hydrogen bond cross-linking effect;

[0126]

[0127] The present invention is achieved through the following technical solutions:

[0128] The present invention prepares a highly elastic, water-resistant and flexible waterborne polyurethane elastic film product. The product is prepared by preparing an emulsion of a modified waterborne polyurethane polymer and by a film-forming process; wherein the modified waterborne polyurethane polymer structure contains a strong supramolecular dynamic crosslinking unit and a polysiloxane unit, and the strong supramolecular dynamic crosslinking unit is introduced at least by a polymerization reaction of a metal complex and a diisocyanate; the metal complex contains at least three reactive groups and is preformed by at least two ligand compounds and a metal ion;

[0129] The modified waterborne polyurethane polymer is prepared from the following raw materials in parts by weight:

[0130]

[0131] According to an embodiment of the present invention, the ligand compound has a structure shown in the following general formula: R1-R3-M-R4-R2, wherein R1 and R2 are reactive groups independently selected from hydroxyl, amino, thiol and combinations thereof; R3 and R4 do not exist or are carbon chain linking groups in the ligand compound; wherein the carbon chain linking group connects the ligand reactive group and the reactive group, and the main chain is entirely composed of carbon atoms. R3 and R4 may be aliphatic or aromatic; may be hydrocarbon groups or contain heteroatoms, but heteroatoms may only exist in the side groups of the carbon chain. For example, R3 and R4 may contain –C(=O)–, –C(OX)–, –C(CH2OX)–, –C(=S)–, –C(=NX)–, wherein X is a hydrocarbon group; but may not contain –O–, –S–, –C(=S)–O–, –C(=O)–S–, –C(=O)–O–, –C(=O)–NH–, –NH–C(=O)–O–, etc.

[0132] R3 and R4 are preferably spaced 1 to 24 atoms apart, more preferably 1 to 12 atoms apart, more preferably 1 to 6 atoms apart, and most preferably 1, 2 or 3 atoms apart. For example, the atomic spacing of p-phenylene, i.e. 1,4-phenylene, is 4, the atomic spacing of m-phenylene is 3, the atomic spacing of o-phenylene is 2, and the atomic spacing of –CH2–, –CH(CH3)–, –C(CH3)2–, –CH(CH2Ph)2–, –C(CH2OX)– is 1, wherein X is a hydrocarbon group.

[0133] R3 and R4 are alkylene groups or side groups containing heteroatoms in carbon chain linking groups; preferably, the number of carbon atoms is C 1～24 , that is, C 1～24 Alkylene or C 1～24 The side group contains a carbon chain linking group containing heteroatoms. The structures of R3 and R4 are linear, branched or cyclic.

[0134] One of the preferred groups is that R3 and R4 include C 3～6 Divalent cycloalkyl, substituted C 3～6A1, A2, A3 are each independently selected from the group consisting of alkyl, cycloalkyl, phenyl, aralkyl, substituted alkyl, substituted cycloalkyl, substituted phenyl, substituted aralkyl, hybridized alkyl, hybridized cycloalkyl, hybridized phenyl, and hybridized aralkyl.

[0135] One of the preferred groups of R3 and R4 is C 1～24 Alkylene, more preferably C 1～12 Alkylene, more preferably C 1～9 Hydrocarbylene. Specifically, methylene, 1,2-ethylene, 1,3-propylene, 1,9-nonylene, -Ph-, -CH2-Ph- are preferred. Wherein, Ph is a benzene ring, and -Ph- can be at the para position, meta position, or ortho position.

[0136] M is a ligand group, which contains a coordination group or a coordination atom and reacts with the metal ion to form a coordination effect. M contains at least the following ligand structure:

[0137]

[0138] According to an embodiment of the present invention, the metal complex contains at least three reactive groups and is preformed by at least two ligand compounds and a metal ion; preferably, the metal complex contains at least four reactive groups and is preformed by at least two ligand compounds and a metal ion.

[0139] Wherein, the metal ions of the metal complex are selected from one or more of the following: calcium ion, zinc ion, iron ion, cuprous ion, ferrous ion, cupric ion, and lanthanide metal ion; the metal ion is dissolved in an organic solvent in the form of a metal ion salt and then added to the coordination reaction, and the metal ion salt comprises calcium chloride, ferric chloride, ferrous chloride, cupric chloride, cuprous chloride, cerium chloride, europium chloride, zinc chloride, calcium nitrate, ferric nitrate, ferrous nitrate, cupric nitrate, cuprous nitrate, cerium nitrate, europium nitrate, zinc nitrate, calcium perchlorate, ferric perchlorate, ferrous perchlorate, cupric perchlorate, cuprous perchlorate, cerium perchlorate, europium perchlorate, zinc perchlorate, ferric sulfate, ferrous sulfate, cupric sulfate, cuprous sulfate, cerium sulfate, europium sulfate, and zinc sulfate; the organic solvent comprises acetone, acetonitrile, and tetrahydrofuran.

[0140] Wherein, the ligand compound comprises dimethylglyoxime,

[0141]

[0142] According to an embodiment of the present invention, the polysiloxane unit is introduced by polymerization reaction of polysiloxane and isocyanate, wherein the polysiloxane is selected from at least one of hydroxyl-terminated polysiloxane, amino-terminated polysiloxane and mercapto-terminated polysiloxane. Hydroxyl-terminated polysiloxane, amino-terminated polysiloxane and mercapto-terminated polysiloxane have the following general structure: Wherein R5 and R6 are independently selected from hydroxyl, amino, and thiol, L1 and L2 are divalent linking groups independently selected from C 1-20 Alkylene, substituted C 1-20 Alkylidene, -(CH2)3O(CH2CH2O) m [CH[CH(CH3)CH2O] n CH(CH3)CH2-, -(CH2)3NH(CH2) o -; J, Q are independently selected from methyl, long chain alkyl, phenyl, epoxy hydrocarbon, trifluoropropyl, perfluoroalkyl oxasulfonyl propyl, CF3OCF(CF3)CF2OCF2(CH2)2-; substituted C 1-20 Alkylene refers to C 1-20 The group obtained by substituting the hydrogen atom of the hydrocarbon group includes, but is not limited to, 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, and fluorine-containing hydrocarbon group. The fluorine-containing hydrocarbon group is selected from one of trifluoropropyl, perfluoroalkyl oxasulfonylpropyl, fluorine ether, and fluorine ester; x and y are integers of 5 to 40; m, n, and o are integers of 1 to 30.

[0143] L1 and L2 are divalent linking groups in polysiloxane, connecting silicon atoms and hydroxyl groups or amino groups or mercapto groups. The main chain can be composed entirely of carbon atoms or contain heteroatoms. L1 and L2 can be aliphatic or aromatic; can be hydrocarbon groups or contain heteroatoms, and heteroatoms can exist on the main carbon chain. For example, L1 and L2 can contain –C(=O)–, –C(OX)–, –C(CH2OX)–, –C(CF2X)–, –C(=S)–, –C(=NX)–, where X is a hydrocarbon group; they can also contain –O–, –S–, –C(=S)–O–, –C(=O)–S–, –C(=O)–O–, –C(=O)–NH–, –NH–C(=O)–O–, etc.

[0144] L1 and L2 are preferably 1 to 20 atoms apart, more preferably 1 to 10 atoms apart, more preferably 1 to 6 atoms apart, and most preferably 1, 2 or 3 atoms apart. For example, the atomic spacing of p-phenylene, i.e. 1,4-phenylene, is 4, the atomic spacing of m-phenylene is 3, the atomic spacing of o-phenylene is 2, and the atomic spacing of –CH2–, –CH(CH3)–, –C(CH3)2–, –CH(CH2Ph)2–, –C(CH2OX)– is 1, wherein X is a hydrocarbon group.

[0145] One of the preferred groups of L1 and L2 is L1 and L2 comprising At least one of, wherein A4, A5, A6 are substituents containing 1 to 10 carbon atoms, and are independent of each other, any two of which are the same or different, l, m, n, o, p, q are integers of 1 to 30; A1, A2, A3 are independently selected from, including but not limited to: oxo (=O), thio (=S), amino (connected to the main chain carbon through a carbon-nitrogen double bond), ether-bonded oxygen heteroalkyl, thioether-bonded thio heteroalkyl, tertiary amino-based nitrogen heteroalkyl, fluorine-containing hydrocarbon. The fluorine-containing hydrocarbon is selected from trifluoropropyl, perfluoroalkyl oxasulfonylpropyl, fluorine ether, and fluorine ester.

[0146] One of the preferred groups of L1 and L2 is C 1～20 Alkylene, more preferably C 1～10 Alkylene, more preferably C 1～3 Specifically, 1,2-ethylene and 1,3-propylene are preferred.

[0147] According to an embodiment of the present invention, the diisocyanate is selected from one or more 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-cyclohexane dimethyl diisocyanate, and 4,4-diisocyanate dicyclohexylmethane. The polymer diol is selected from at least one of polyester diol, polyolefin diol, and polyether diol. The polyester diol is selected from polyhexamethylene carbonate diol, polycarbonate-1,6-hexanediol ester diol, polycaprolactone carbonate hexamethylene ester diol, polybutylene carbonate diol, polycyclohexanedimethanol carbonate-1,6-hexanediol ester diol, polycarbonate-1,5-pentanediol-1,6-hexanediol ester diol, polyethylene carbonate diol, polypropylene carbonate diol, polycarbonate-1,4-butanediol-1,6-hexanediol ester diol, polycaprolactone 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 -At least one of adipic acid polyester diol, neopentyl glycol-adipic acid polyester diol, 1,6-hexanediol-adipic acid polyester diol, dimerized lactic acid polyethylene glycol, polyethylene glycol-polylactic acid-hydroxyacetic acid copolymer, ethylene glycol-seed diol polyester diol, diethylene glycol-seed diol polyester diol, neopentyl glycol-seed diol polyester diol, poly-3-methyl-1,5-pentanediol adipic acid ester diol, poly-1,4-cyclohexanedicarboxylic acid-3-methyl-1,5-pentanediol ester diol, and polyester diols of bio-based small molecule diols-acids, whose average number average molecular weight is 2000 to 4000 Da. The polyolefin diol is selected from at least one of polybutadiene diol, polybutadiene-acrylonitrile copolymer diol, hydroxyl-terminated epoxidized polybutadiene diol, hydroxyl-terminated polyisoprene diol, hydroxyl-terminated hydrogenated polyisoprene diol, hydrogenated polybutadiene diol, polystyrene-allyl alcohol copolymer diol, and polystyrene-ethylene-butylene-styrene diol, and its average number average molecular weight is 2000-4000Da. The polyether diol is selected from at least one of polytetramethylene ether diol, polytrimethylene ether diol, polyethylene oxide diol, polytetramethylene ether diol-propylene oxide copolyether diol, polytetramethylene ether diol-ethylene oxide copolyether diol, polypropylene oxide diol, polyethylene oxide diol, polyethylene oxide propylene oxide copolyether diol, and fluorine-containing polyether diol, and its average number average molecular weight is 2000-4000Da.

[0148] The fluorinated polyether diol includes perfluoropolyether diol and fluorinated linear polyether diol synthesized from bisphenol AF, ethylene oxide and propylene oxide.

[0149] The polymer diol is preferably at least one of polytetramethylene glycol, perfluoropolyether glycol, polycarbonate glycol and polyolefin glycol. The waterborne polyurethane soft segment contains polytetramethylene glycol, polycarbonate, polyolefin and fluorine-containing polyether structures and has excellent water resistance.

[0150] According to an embodiment of the present invention, the hydrophilic chain extender is selected from at least one of dimethylol propionic acid, dimethylol butyric acid, sodium ethylenediamine ethanesulfonate, sodium N,N-(2-hydroxyethyl)-2-aminoethanesulfonate, sodium 1,4-butanediol-2-sulfonate, and methyldiethanolamine. The trifunctional crosslinking agent is selected from at least one of triethanolamine, triisopropanolamine, trimethylolpropane, trimethylolethane, 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, trihydroxyethyl isocyanurate, melamine, benzene-1,2,3-triamine, diethylenetriamine, low molecular weight polyether triol, and castor oil. The post-chain extender is selected from at least one of 1,3-propylenediamine, 1,4-butylenediamine, 1,6-hexanediamine, isophoronediamine, ethylenediamine, diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, trimethylhexanediamine, 1,12-dodecanediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)ether, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, polyetheramine, and sodium ethylenediamine ethanesulfonate. The catalyst is selected from at least one of dibutyltin dilaurate, bismuth laurate, bismuth isooctanoate, bismuth neodecanoate, stannous octoate, potassium oleate, cobalt octoate, ferric chloride, and sodium o-phenylphenol. The salt-forming agent is selected from at least one of triethylamine, diethanolamine, potassium hydroxide, sodium hydroxide, and diisopropylethanolamine.

[0151] According to an embodiment of the present invention, the strong supramolecular dynamic crosslinking unit further contains a strong hydrogen bonding unit. The strong hydrogen bonding unit is introduced by pre-forming a hydrogen bonding compound from a hydrogen bonding monomer compound and / or by forming a hydrogen bonding unit from a reactant that can generate a hydrogen bonding monomer when polymerizing the modified waterborne polyurethane polymer. The hydrogen bonding monomer is selected from at least one of the following structures:

[0152] Wherein R7 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 1-15 Alkylene or substituted C 1-15Hydrocarbylene; 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:

[0153]

[0154] Wherein, the linker containing a dynamic diselenide bond is selected from the following structures:

[0155]

[0156] 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:

[0157]

[0158]

[0159] Wherein, the linker containing a dynamic imine bond and the linker containing a dynamic oxime bond are selected from the following structures:

[0160]

[0161] One of the preferred groups of R7 is that R7 includes phenylene and substituted phenylene. Substituted phenylene means that any hydrogen atom on the phenylene is replaced by a substituent; the substituent includes but is not limited to heteroatoms and groups containing heteroatoms. Specifically, -Ph-,

[0162] One of the preferred groups of R7 is C 1～12 Specifically, methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, 1,10-decylene, 1,11-undecylene, and 1,12-dodecylene are preferred.

[0163] R7's preferred choice:

[0164] Any one of.

[0165] The hydrogen bonding monomer compound is selected from the following compounds:

[0166] The reactants capable of generating hydrogen bond monomers are selected from the following compounds: succinic acid hydrazide, adipic acid dihydrazide, isophthalic acid dihydrazide and dodecanedicarboxylic acid dihydrazide, sebacic acid dihydrazide, azelaic acid dihydrazide, maleic acid dihydrazide, oxalyl dihydrazide, phthalic acid dihydrazide, 2,5-dibutoxyterephthaloyl hydrazide, 2,5-bis(benzyloxy)terephthaloyl hydrazide, 3,3'-dithiobispropionic acid hydrazide,

[0167]

[0168] In the present invention, the strong supramolecular dynamic cross-linking unit contains both metal-coordination and strong hydrogen bonding, which can further enhance the toughening of the waterborne polyurethane film; the strong supramolecular dynamic cross-linking unit contains both metal-coordination, strong hydrogen bonding and dynamic covalent bonds, and the prepared waterborne polyurethane film has excellent flexibility, high elasticity and low modulus.

[0169] The emulsion prepared according to an embodiment of the present invention is further enhanced by metal-coordination, wherein the metal-coordination is formed by coordination of carboxylic acid ligands and zinc ions, and coordinated in the aqueous polyurethane emulsion. The carboxylic acid ligand is introduced after the reaction of a carboxylic acid hydrophilic chain extender with an isocyanate; the carboxylic acid hydrophilic chain extender comprises dimethylol propionic acid and dimethylol butyric acid; the zinc ion is dissolved in water in the form of a zinc ion salt and then added to the coordination reaction, and the zinc ion salt is zinc acetate.

[0170] The following is a further description of the preparation method of the highly elastic, water-resistant and flexible waterborne polyurethane elastic film product of the present invention in combination with some specific embodiments. The specific embodiments are for further illustrating the present invention in detail, but do not limit the protection scope of the present invention.

[0171] Example 1

[0172] (1) Preparation of modified waterborne polyurethane polymer

[0173] ① To synthesize the metal complex, first add 2.8kg dimethylglyoxime, 0.3kg zinc chloride, and 45kg acetone, stir and heat to 50℃ and react for 0.5h;

[0174] ② Synthesis of prepolymer: 3 kg of amino-terminated polydimethylsiloxane, 5 kg of DMBA and 70 kg of PTMG-2000 were put into a new reactor, heated to 120 ° C with stirring, vacuum dehydrated for 2 hours, cooled to 65 ° C, 48.1 kg of dimethylglyoxime and zinc ion complex solution and 1.5 kg of triethanolamine were added, stirred for 0.3 hours, and then 29.6 kg of IPDI was added, stirred and heated to 75 ° C for 0.8 hours, 0.06 kg of bismuth laurate was added, stirred and heated to 95 ° C for 1 hour, 30 kg of n-propyl acetate was added for 5 hours, and then cooled to 30 ° C, 3.4 kg of triethylamine was added, and stirred for 0.5 hours to obtain a modified waterborne polyurethane polymer;

[0175] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer was transferred to an emulsifier, and 600 kg of ice water was added to the modified waterborne polyurethane polymer under high-speed stirring at 10,000 r / min. After emulsification, 1.7 kg of IPDA was added, and then the speed was adjusted to 600 r / min and stirring was continued for 5 hours. The obtained polyurethane emulsion was heated to 60° C., and acetone was removed under a vacuum condition of -0.09 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products.

[0176] (3) Film formation

[0177] ① Glass mold cleaning: The glass mold is first cleaned with an alkaline detergent, then with an acidic detergent, and finally with neutral deionized water, and dried to 70°C;

[0178] ② Dip the mold release agent: immerse the glass mold at 70℃ in the mold release agent for 30s, then slowly take it out at a uniform speed and dry it at 70℃;

[0179] ③ Dipping in emulsion: immerse the 70°C glass mold with a release agent in polyurethane emulsion for 10 seconds, then slowly take it out at a uniform speed, dry it at 90°C for 10 seconds, immerse it in polyurethane emulsion for 10 seconds, then slowly take it out at a uniform speed, dry it at 90°C for 20 seconds, immerse it in polyurethane emulsion for 10 seconds, then slowly take it out at a uniform speed, and finally dry it at 80°C for 7 minutes;

[0180] ④ Curling and drying: The film obtained in step ③ is curled to a suitable position, and the mold after curling is dried at 90°C for 5 minutes;

[0181] ⑤Immersing in anti-adhesive agent, drying, and demoulding: After curling and drying, the mold is cooled to 30°C, immersed in anti-adhesive agent, dried at 90°C, and then demoulded to obtain a polyurethane elastic film product;

[0182] The structure of the amino-terminated polydimethylsiloxane is:

[0183] Example 2

[0184] (1) Preparation of modified waterborne polyurethane polymer

[0185] ① First, add 9.1 kg of synthetic metal complex 0.4kg copper chloride, 50kg acetonitrile, stir and heat to 55℃ for 0.8h;

[0186] ② Synthesis of prepolymer: 3 kg of hydroxyl-terminated polydimethylsiloxane, 5 kg of DMBA and 70 kg of PTMG-2000 were put into a new reactor, heated to 120 ° C with stirring, vacuum dehydration for 2 hours, cooled to 65 ° C, and 59.5 kg of The complex solution of copper ions and 1.4 kg of trimethylolpropane were stirred for reaction for 0.3 h, and then 22.4 kg of HDI was added, and the mixture was heated to 75°C with stirring for reaction for 0.8 h, and 0.1 kg of bismuth laurate was added, and the mixture was heated to 95°C with stirring for reaction for 1 h, and 30 kg of n-propyl acetate was added for reaction for 5 h, and the mixture was cooled to 50-65°C with stirring, and 1.5 kg of succinic acid hydrazide and 80 kg of acetone were added for reaction for 5 h, and then the mixture was cooled to 30°C, and 3.4 kg of triethylamine was added, and the mixture was stirred for 0.5 h to obtain a modified waterborne polyurethane polymer;

[0187] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer is transferred to an emulsifier, and 600 kg of ice water is added to the modified waterborne polyurethane polymer under high-speed stirring at 10,000 r / min. After emulsification, 0.6 kg of ethylenediamine is added, and then the speed is adjusted to 600 r / min and stirring is continued for 5 hours; the obtained polyurethane emulsion is heated to 60° C., and acetonitrile and acetone are removed under a vacuum condition of -0.09 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products;

[0188] (3) Film forming method is the same as in Example 1

[0189] The structure of the polydimethylsiloxane terminated with a hydroxyl group is:

[0190]

[0191] Example 3

[0192] (1) Preparation of modified waterborne polyurethane polymer

[0193] ① To synthesize the metal complex, first add 2.8kg dimethylglyoxime, 0.2kg zinc chloride, and 45kg acetone, stir and heat to 50℃ and react for 0.5h;

[0194] ② Synthesis of prepolymer: 3.5 kg of amino-terminated polyether polysiloxane, 5 kg of DMBA and 70 kg of polycarbonate diol-2000 were put into a new reactor, heated to 120 ° C with stirring, vacuum dehydrated for 2 hours, cooled to 65 ° C, 48 kg of dimethylglyoxime and zinc ion complex solution and 1.4 kg of trimethylolpropane were added, stirred and reacted for 0.3 hours, and then 29.6 kg of IPDI was added, stirred and heated to 75 ° C for reaction for 0.8 hours, 0.06 kg of bismuth laurate was added, stirred and heated to 95 ° C for reaction for 1 hour, 30 kg of ethyl acetate was added for reaction for 5 hours, and then cooled to 30 ° C, 3.5 kg of diethanolamine was added, and stirred for 0.5 hours to obtain a modified waterborne polyurethane polymer;

[0195] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer was transferred to an emulsifier, and 600 kg of ice water was added to the modified waterborne polyurethane polymer under high-speed stirring at 10,000 r / min. After emulsification, 1.7 kg of IPDA was added, and then the speed was adjusted to 600 r / min and stirring was continued for 5 hours. The obtained polyurethane emulsion was heated to 60° C., and acetone was removed under a vacuum condition of -0.09 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products.

[0196] (3) Film forming method is the same as in Example 1

[0197] The structure of the amino-terminated polyether polysiloxane is:

[0198] Example 4

[0199] (1) Preparation of modified waterborne polyurethane polymer

[0200] ① First, add 4.6 kg of synthetic metal complex 0.4kg copper chloride, 30kg acetone, stir and heat to 40℃ for 1h;

[0201] ② Synthesis of prepolymer: 3 kg of amino-terminated long-chain alkane polysiloxane, 5 kg of DMPA and 70 kg of polybutadiene glycol-2000 were put into a new reactor, stirred and heated to 110 ° C, vacuum dehydrated for 2.6 hours, cooled to 45 ° C, and 55 kg of The complex solution of copper ions and 1.4 kg of trimethylolpropane were stirred for reaction for 0.9 h, and then 22.4 kg of HDI was added, and the temperature was raised to 75°C for reaction for 0.8 h, and 0.1 kg of dibutyltin dilaurate was added, and the temperature was raised to 95°C for reaction for 1 h, and 30 kg of n-propyl acetate was added for reaction for 5 h, and the temperature was lowered to 50-65°C with stirring, and 1.9 kg of isophthalic acid dihydrazide hydrazide and 80 kg of acetone were added for reaction for 5 h, and then the temperature was lowered to 30°C, and 1.9 kg of potassium hydroxide was added, and the mixture was stirred for 0.5 h to obtain a modified waterborne polyurethane polymer;

[0202] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer is transferred to an emulsifier, and 600 kg of ice water is added to the modified waterborne polyurethane polymer under high-speed stirring at 10,000 r / min. After emulsification, 15 kg of polyetheramine is added, and then the speed is adjusted to 600 r / min and stirring is continued for 5 hours; the obtained polyurethane emulsion is heated to 60° C., and acetone is removed under a vacuum condition of -0.09 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products;

[0203] (3) Film forming method is the same as in Example 1

[0204] The structure of the long-chain alkane polysiloxane terminated with an amino hydrocarbon group is:

[0205] Example 5

[0206] (1) Preparation of modified waterborne polyurethane polymer

[0207] ① First, add 10.7 kg of synthetic metal complex 0.6kg copper chloride, 50kg acetone, stir and heat to 55℃ for 0.7h;

[0208] ② Synthesis of prepolymer: 4 kg of amino-terminated amide polysiloxane, 5 kg of DMPA and 70 kg of polybutadiene-acrylonitrile copolymer-2000 were put into a new reactor, stirred and heated to 120 ° C, vacuum dehydrated for 2 hours, cooled to 65 ° C, and 61.3 kg of The complex solution of copper ions and 1 kg of diethylenetriamine were stirred for reaction for 0.5 h, then 31.8 kg of IPDI was added, the temperature was raised to 80°C for reaction for 0.5 h, 0.1 kg of dibutyltin dilaurate was added, the temperature was raised to 80°C for reaction for 2 h, 50 kg of n-propyl acetate was added for reaction for 4 h, the temperature was lowered to 65°C with stirring, 2.6 kg of dodecanedicarboxylic acid dihydrazide and 50 kg of acetone were added for reaction for 3 h, then the temperature was lowered to 30°C, 1.9 kg of potassium hydroxide was added, and the mixture was stirred for 0.5 h to obtain a modified waterborne polyurethane polymer;

[0209] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer is transferred to an emulsifier, and 300 kg of ice water is added to the modified waterborne polyurethane polymer under high-speed stirring at 4000 r / min. After emulsification, 1.2 kg of 1,6-hexanediamine is added, and then the speed is adjusted to 200 r / min, and stirring is continued for 7 hours; the obtained polyurethane emulsion is heated to 60° C., and acetone is removed under a vacuum condition of -0.09 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products;

[0210] (3) Film forming method is the same as in Example 1

[0211] The structure of the amide polysiloxane terminated with an amino hydrocarbon group is:

[0212] Example 6

[0213] (1) Preparation of modified waterborne polyurethane polymer

[0214] ① First, add 6.5 kg of synthetic metal complex 0.3kg ferric chloride, 45kg acetone, stir and heat to 50℃ for 0.8h;

[0215] ② Synthesis of prepolymer: 0.5 kg of perfluoropolyether diol, 3 kg of amino-terminated alkyl-capped amide polysiloxane, 3.5 kg of DMPA and 70 kg of polybutadiene diol-2000 were put into a new reactor, stirred and heated to 110 ° C, vacuum dehydrated for 2.5 hours, cooled to 55 ° C, and 56.8 kg of The complex solution of iron ions and 1.5 kg of trimethylolpropane were stirred for reaction for 0.5 h, then 34.9 kg of hydrogenated phenylmethane diisocyanate was added, the temperature was raised to 80 ° C with stirring for reaction for 0.5 h, 0.1 kg of bismuth neodecanoate was added, the temperature was raised to 95 ° C with stirring for reaction for 1 h, 30 kg of n-propyl acetate was added for reaction for 5 h, the temperature was lowered to 65 ° C with stirring, 2.2 kg of azelaic acid dihydrazide and 50 kg of acetone were added for reaction for 3 h, then the temperature was lowered to 20 ° C, 1.4 kg of sodium hydroxide was added, and the mixture was stirred for 2 h to obtain a modified waterborne polyurethane polymer;

[0216] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer is transferred to an emulsifier, and 500 kg of ice water is added to the modified waterborne polyurethane polymer under high-speed stirring at 8000 r / min. After emulsification, 15 kg of polyetheramine is added, and then the speed is adjusted to 400 r / min, and stirring is continued for 7 hours; the obtained polyurethane emulsion is heated to 40° C., and acetone is removed under a vacuum condition of -0.09 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products;

[0217] (3) Film forming method is the same as in Example 1

[0218] The structure of the amide polysiloxane terminated with an amino hydrocarbon group is: The structure of perfluoropolyether diol is: HO(CH2CH2O)3CH2CF2O(CF2CF2O) 10 (CF2O)5CF2CH2(OCH2CH2)3OH.

[0219] Example 7

[0220] (1) Preparation of modified waterborne polyurethane polymer

[0221] ① First, add 6.4 kg of synthetic metal complex 0.3kg cuprous chloride, 50kg acetonitrile, stir and heat to 50℃ for 0.6h;

[0222] ② Synthesis of prepolymer: 3.5 kg of amino-terminated fluoroalkyl polysiloxane, 4.5 kg of DMPA and 70 kg of polybutadiene glycol-2000 were put into a new reactor, heated to 115 ° C with stirring, vacuum dehydration for 2.3 hours, cooled to 45 ° C, and 56.7 kg of The complex solution of cuprous ions and 1.5 kg of triethanolamine were stirred for 0.3 h, and then 34.9 kg of hydrogenated phenylmethane diisocyanate was added, and the temperature was raised to 75 ° C and reacted for 0.8 h. 0.1 kg of bismuth isooctanoate was added, and the temperature was raised to 85 ° C and reacted for 2 h. 40 kg of n-propyl acetate was added and reacted for 3.5 h. After stirring and cooling to 50 ° C, 2.5 kg of The mixture was reacted with 80 kg of acetonitrile for 5 h, then cooled to 30 °C, 4.9 kg of diisopropylethanolamine was added, and stirred for 0.5 h to obtain a modified waterborne polyurethane polymer;

[0223] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer is transferred to an emulsifier, and 300 kg of ice water is added to the modified waterborne polyurethane polymer under high-speed stirring at 7000 r / min. After emulsification, 0.9 kg of 1,4-butanediamine is added, and then the speed is adjusted to 600 r / min and stirring is continued for 5 hours; the obtained polyurethane emulsion is heated to 60° C., and acetonitrile is removed under a vacuum condition of -0.08 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products;

[0224] (3) Film forming method is the same as in Example 1

[0225] The structure of the amino-terminated fluoroalkyl polysiloxane is:

[0226] Example 8

[0227] (1) Preparation of modified waterborne polyurethane polymer

[0228] ① First, add 5.7 kg of synthetic metal complex 0.3kg calcium chloride, 50kg acetone, stir and heat to 45℃ for 0.7h;

[0229] ② Synthesis of prepolymer: 3 kg of hydroxyl-terminated polyether-modified polydimethylsiloxane, 4.5 kg of DMPA and 70 kg of polycarbonate diol-2000 were put into a new reactor, heated to 120 ° C with stirring, vacuum dehydration for 3 hours, cooled to 45 ° C, and 56 kg of The complex solution of calcium ions and 1.5 kg of triethanolamine were stirred for reaction for 0.8 h, then 29.6 kg of IPDI was added, the temperature was raised to 75°C for reaction for 0.8 h, 0.07 kg of dibutyltin dilaurate was added, the temperature was raised to 85°C for reaction for 2 h, 30 kg of n-propyl acetate was added for reaction for 5 h, the temperature was lowered to 50°C with stirring, 2 kg of phthalic acid dihydrazide and 70 kg of acetone were added for reaction for 4 h, then the temperature was lowered to 30°C, 4.9 kg of diisopropylethanolamine was added, and the mixture was stirred for 0.5 h to obtain a modified waterborne polyurethane polymer;

[0230] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer is transferred to an emulsifier, and 600 kg of ice water is added to the modified waterborne polyurethane polymer under high-speed stirring at 4000 r / min. After emulsification, 0.7 kg of 1,3-propylenediamine is added, and then the speed is adjusted to 200 r / min and stirring is continued for 5 hours; the obtained polyurethane emulsion is heated to 50° C., and acetone is removed under a vacuum condition of -0.09 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products;

[0231] (3) Film forming method is the same as in Example 1

[0232] The structure of the hydroxyl-terminated polyether-modified polydimethylsiloxane is:

[0233] Example 9

[0234] (1) Preparation of modified waterborne polyurethane polymer

[0235] ① First, add 4.6 kg of synthetic metal complex 0.3kg ferrous chloride, 50kg tetrahydrofuran, stir and heat to 50℃ for 0.5h;

[0236] ② Synthesis of prepolymer: 4.5 kg of hydroxyl-terminated polyether-modified polydimethylsiloxane, 5 kg of DMBA and 70 kg of polycaprolactone diol-2000 were put into a new reactor, stirred and heated to 120 ° C, vacuum dehydrated for 2 hours, cooled to 65 ° C, and 54.9 kg of The complex solution of ferrous ions and 1.5 kg of triethanolamine were stirred for reaction for 0.3 h, then 29.6 kg of IPDI was added, the temperature was raised to 80°C for reaction for 0.5 h, 0.07 kg of dibutyltin dilaurate was added, the temperature was raised to 85°C for reaction for 2 h, 40 kg of n-propyl acetate was added for reaction for 3.5 h, the temperature was lowered to 50°C with stirring, 3.4 kg of 2,5-dibutoxyterephthaloylhydrazide and 80 kg of tetrahydrofuran were added for reaction for 5 h, then the temperature was lowered to 25°C, 4.9 kg of diisopropylethanolamine was added, and the mixture was stirred for 1.5 h to obtain a modified waterborne polyurethane polymer;

[0237] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer was transferred to an emulsifier, and 400 kg of ice water was added to the modified waterborne polyurethane polymer under high-speed stirring at 6000 r / min. After emulsification, 1.7 kg of IPDA was added, and then the speed was adjusted to 300 r / min and stirring was continued for 7 hours. The obtained polyurethane emulsion was heated to 50° C. and tetrahydrofuran was removed under a vacuum condition of -0.1 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products.

[0238] (3) Film forming method is the same as in Example 1

[0239] The structure of the hydroxyl-terminated polyether-modified polydimethylsiloxane is:

[0240] Example 10

[0241] (1) Preparation of modified waterborne polyurethane polymer

[0242] ① First, add 4.6 kg of synthetic metal complex 0.5kg cerium chloride, 50kg acetone, stir and heat to 50℃ for 0.5h;

[0243] ② Synthesis of prepolymer: 5 kg of hydroxyl-terminated polyether-modified polydimethylsiloxane, 4.5 kg of DMPA and 70 kg of polypropylene glycol-2000 were put into a new reactor, heated to 100 ° C with stirring, vacuum dehydration for 3 hours, cooled to 55 ° C, and 55.1 kg of The complex solution of cerium ions and 1.5 kg of triethanolamine were stirred for reaction for 0.4 h, then 29.6 kg of IPDI was added, the temperature was raised to 65 ° C with stirring for reaction for 1 h, 0.07 kg of dibutyltin dilaurate was added, the temperature was heated to 90 ° C with stirring for reaction for 1.5 h, 60 kg of ethyl acetate was added for reaction for 3 h, the temperature was lowered to 50 ° C with stirring, 4.1 kg of 2,5-bis(benzyloxy)terephthaloylhydrazide and 60 kg of acetone were added for reaction for 3.5 h, then the temperature was lowered to 20 ° C, 3.4 kg of triethylamine was added, and the mixture was stirred for 2 h to obtain a modified waterborne polyurethane polymer;

[0244] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer is transferred to an emulsifier, and 400 kg of ice water is added to the modified waterborne polyurethane polymer under high-speed stirring at 6500 r / min. After emulsification, 0.7 kg of 1,3-propylenediamine is added, and then the speed is adjusted to 300 r / min, and stirring is continued for 7 hours; the obtained polyurethane emulsion is heated to 45° C., and acetone is removed under a vacuum condition of -0.09 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products;

[0245] (3) Film forming method is the same as in Example 1

[0246] The structure of the hydroxyl-terminated polyether-modified polydimethylsiloxane is:

[0247] Embodiment 11

[0248] (1) Preparation of modified waterborne polyurethane polymer

[0249] ① First, add 4.3 kg of synthetic metal complex 0.6kg europium chloride, 50kg acetone, stir and heat to 50℃ for 0.5h;

[0250] ② Synthesis of prepolymer: 3kg of end-polyether modified polydimethylsiloxane, 4kg of DMPA and 50kg of PTMG-2000 were put into a new reactor, heated to 115℃ with stirring, vacuum dehydration for 3h, cooled to 55℃, and 54.9kg of The complex solution of europium ion and 1kg triethanolamine were stirred for 0.3h, then 25.6kg IPDI was added, stirred and heated to 65℃ for 1h, 0.07kg dibutyltin dilaurate was added, stirred and heated to 95℃ for 1h, 40kg n-propyl acetate was added for 3.5h, stirred and cooled to 50℃, and 1.7kg The mixture was reacted with 60 kg of acetone for 3.5 h, then cooled to 25°C, 3.4 kg of triethylamine was added, and stirred for 1.5 h to obtain a modified waterborne polyurethane polymer;

[0251] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer is transferred to an emulsifier, and 600 kg of ice water is added to the modified waterborne polyurethane polymer under high-speed stirring at 10,000 r / min. After emulsification, 0.3 kg of 1,3-propylenediamine is added, and then the speed is adjusted to 600 r / min and stirring is continued for 5 hours; the obtained polyurethane emulsion is heated to 60° C., and acetone is removed under a vacuum condition of -0.08 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products;

[0252] (3) Film forming method is the same as in Example 1

[0253] The structure of the terminal polyether-modified polydimethylsiloxane is:

[0254] Example 12

[0255] (1) Preparation of modified waterborne polyurethane polymer

[0256] ① First add 5kg of synthetic metal complex 0.35kg zinc nitrate and 35kg acetone, stir and heat to 55℃ for 1h;

[0257] ② Synthesis of prepolymer: 4 kg of hydroxyl-terminated polyether-modified polydimethylsiloxane, 4.5 kg of DMPA and 60 kg of polycaprolactone diol-3000 were put into a new reactor, stirred and heated to 120 ° C, vacuum dehydrated for 3 hours, cooled to 45 ° C, and 55.4 kg of The complex solution of zinc ion and 1.5kg triethanolamine were stirred for 0.5h, then 31.4kg IPDI was added, stirred and heated to 80℃ for 0.5h, 0.07kg dibutyltin dilaurate was added, stirred and heated to 95℃ for 1h, 50kg n-propyl acetate was added for 4h, stirred and cooled to 50℃, and 1.4kg The mixture was reacted with 60 kg of acetone for 3.5 h, then cooled to 25°C, 3.4 kg of triethylamine was added, and stirred for 1.5 h to obtain a modified waterborne polyurethane polymer;

[0258] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer is transferred to an emulsifier, and 600 kg of ice water is added to the modified waterborne polyurethane polymer under high-speed stirring at 10,000 r / min. After emulsification, 1 kg of 1,3-propylenediamine is added, and then the speed is adjusted to 600 r / min and stirring is continued for 5 hours; the obtained polyurethane emulsion is heated to 60° C., and acetone is removed under a vacuum condition of -0.09 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products;

[0259] (3) Film forming method is the same as in Example 1

[0260] The structure of the hydroxyl-terminated polyether-modified polydimethylsiloxane is:

[0261] Example 13

[0262] (1) Preparation of modified waterborne polyurethane polymer

[0263] ① First, add 5.3 kg of synthetic metal complex 0.3kg copper chloride, 48kg acetone, stir and heat to 50℃ for 0.9h;

[0264] ② Synthesis of prepolymer: 3 kg of hydroxyl-terminated polyether-modified polydimethylsiloxane, 5 kg of DMPA and 70 kg of polycarbonate diol-4000 were put into a new reactor, heated to 110 ° C with stirring, vacuum dehydration for 3 hours, cooled to 45 ° C, and 53.6 kg of The complex solution of copper ions and 1 kg of triethanolamine were stirred for 1 hour, and then 31.4 kg of IPDI was added, and the temperature was raised to 65 ° C for 1 hour. 0.07 kg of dibutyltin dilaurate was added, and the temperature was raised to 85 ° C for 2 hours. 30 kg of n-propyl acetate was added for 5 hours, and the temperature was lowered to 50 ° C. 4.0 kg of The mixture was reacted with 70 kg of acetone for 4 h, then cooled to 20°C, 3.4 kg of triethylamine was added, and stirred for 2 h to obtain a modified waterborne polyurethane polymer;

[0265] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer is transferred to an emulsifier, and 600 kg of ice water is added to the modified waterborne polyurethane polymer under high-speed stirring at 4000 r / min. After emulsification, 1.8 kg of 1,3-propylenediamine is added, and then the speed is adjusted to 600 r / min and stirring is continued for 5 hours; the obtained polyurethane emulsion is heated to 60° C., and acetone is removed under a vacuum condition of -0.09 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products;

[0266] (3) Film forming method is the same as in Example 1

[0267] The structure of the hydroxyl-terminated polyether-modified polydimethylsiloxane is:

[0268] Embodiment 14

[0269] (1) Preparation of modified waterborne polyurethane polymer

[0270] ① First, add 6.5 kg of synthetic metal complex 0.3kg ferric chloride, 50kg acetone, stir and heat to 50℃ for 0.5h;

[0271] ② Synthesis of prepolymer: 3 kg of fluoro-modified polydimethylsiloxane terminated with hydroxyl group, 4.5 kg of DMPA and 60 kg of PTMG-3000 were put into a new reactor, heated to 115 °C with stirring, vacuum dehydration for 3 hours, cooled to 45 °C, and 56.8 kg of The complex solution of iron ions and 1.5 kg of triethanolamine were stirred for 0.6 h, then 25.4 kg of IPDI was added, stirred and heated to 75 °C for 0.8 h, 0.07 kg of dibutyltin dilaurate was added, stirred and heated to 80 °C for 2 h, 60 kg of n-propyl acetate was added for 3 h, stirred and cooled to 50 °C, and 2.3 kg of The mixture was reacted with 80 kg of acetone for 5 h, then cooled to 20 °C, 3.4 kg of triethylamine was added, and stirred for 2 h to obtain a modified waterborne polyurethane polymer;

[0272] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer is transferred to an emulsifier, and 600 kg of ice water is added to the modified waterborne polyurethane polymer under high-speed stirring at 10,000 r / min. After emulsification, 0.7 kg of 1,3-propylenediamine is added, and then the speed is adjusted to 400 r / min and stirring is continued for 5 hours; the obtained polyurethane emulsion is heated to 60° C., and acetone is removed under a vacuum condition of -0.09 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products;

[0273] (3) Film forming method is the same as in Example 1

[0274] The structure of the fluorine-modified polydimethylsiloxane terminated with a hydroxyl group is:

[0275] Embodiment 15

[0276] (1) Preparation of modified waterborne polyurethane polymer

[0277] ① First, add 5.3 kg of synthetic metal complex 0.2kg calcium chloride, 45kg acetone, stir and heat to 50℃ for 0.6h;

[0278] ② Synthesis of prepolymer: 5 kg of hydroxyl-terminated polymethylphenylsiloxane, 4.5 kg of DMPA and 70 kg of polypropylene glycol-2000 were put into a new reactor, heated to 120 ° C with stirring, vacuum dehydration for 3 hours, cooled to 65 ° C, and 50.5 kg of The complex solution of calcium ions and 1.5 kg of triethanolamine were stirred for reaction for 0.5 h, then 31.4 kg of IPDI was added, the temperature was raised to 80°C for reaction for 0.5 h, 0.07 kg of dibutyltin dilaurate was added, the temperature was raised to 95°C for reaction for 1 h, 30 kg of n-propyl acetate was added for reaction for 5 h, the temperature was lowered to 50°C with stirring, 1.7 kg of adipic acid dihydrazide and 70 kg of acetone were added for reaction for 4 h, then the temperature was lowered to 30°C, 3.4 kg of triethylamine was added, and the reaction was stirred for 0.5 h to obtain a modified waterborne polyurethane polymer;

[0279] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer is transferred to an emulsifier, and 600 kg of ice water is added to the modified waterborne polyurethane polymer under high-speed stirring at 10,000 r / min. After emulsification, 0.7 kg of 1,3-propylenediamine is added, and then the speed is adjusted to 200 r / min, and stirring is continued for 7 hours; the obtained polyurethane emulsion is heated to 60° C., and acetone is removed under a vacuum condition of -0.1 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products;

[0280] (3) Film forming method is the same as in Example 1

[0281] The structure of the hydroxyl-terminated polymethylphenylsiloxane is:

[0282] Example 16

[0283] (1) Preparation of modified waterborne polyurethane polymer

[0284] ① First, add 4.6 kg of synthetic metal complex 0.5kg cerium chloride, 50kg acetone, stir and heat to 50℃ for 0.5h;

[0285] ② Synthesis of prepolymer: 0.6 kg of perfluoropolyether diol, 3 kg of long-chain alkane polysiloxane terminated with hydroxyl group, 4.5 kg of DMPA and 69.4 kg of PTMG-2000 were put into a new reactor, heated to 100 °C with stirring, vacuum dehydrated for 3 hours, cooled to 55 °C, and 55.1 kg of The complex solution of cerium ions and 1.5 kg of triethanolamine were stirred for reaction for 0.4 h, and then 29.6 kg of IPDI was added, and the temperature was raised to 80°C for reaction for 0.5 h, and 0.07 kg of dibutyltin dilaurate was added, and the temperature was raised to 90°C for reaction for 1.5 h, and 60 kg of ethyl acetate was added for reaction for 5 h, and then the temperature was lowered to 20°C, and 3.4 kg of triethylamine was added, and the mixture was stirred for 2 h to obtain a modified waterborne polyurethane polymer;

[0286] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer is transferred to an emulsifier, and 400 kg of ice water is added to the modified waterborne polyurethane polymer under high-speed stirring at 6500 r / min. After emulsification, 0.7 kg of 1,3-propylenediamine is added, and then the speed is adjusted to 300 r / min, and stirring is continued for 7 hours; the obtained polyurethane emulsion is heated to 45° C., and acetone is removed under a vacuum condition of -0.09 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products;

[0287] (3) Film forming method is the same as in Example 1

[0288] The structure of the long-chain alkane polysiloxane terminated with a terminal hydroxyl group is: The structure of perfluoropolyether diol is: HO(CH2CH2O)3CH2CF2O(CF2CF2O) 10 (CF2O)5CF2CH2(OCH2CH2)3OH.

[0289] Embodiment 17

[0290] (1) Preparation of modified waterborne polyurethane polymer

[0291] ① First add 5kg of synthetic metal complex 0.38kg zinc sulfate and 35kg acetone, stir and heat to 55℃ for 1h;

[0292] ② Synthesis of prepolymer: 1 kg of perfluoropolyether diol, 4 kg of long-chain alkane polysiloxane terminated with hydroxyl group, 4.5 kg of DMPA and 60 kg of PTMG-3000 were put into a new reactor, heated to 120 °C with stirring, vacuum dehydrated for 3 hours, cooled to 45 °C, and 55.4 kg of The complex solution of zinc ion and 1.5 kg of triethanolamine were stirred for reaction for 0.6 h, then 31.4 kg of IPDI was added, the temperature was raised to 65°C for reaction for 1 h, 0.07 kg of dibutyltin dilaurate was added, the temperature was raised to 95°C for reaction for 1 h, 50 kg of n-propyl acetate was added for reaction for 4 h, then the temperature was lowered to 25°C, 3.4 kg of triethylamine was added, and the mixture was stirred for 1.5 h to obtain a modified waterborne polyurethane polymer;

[0293] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer is transferred to an emulsifier, and 600 kg of ice water is added to the modified waterborne polyurethane polymer under high-speed stirring at 10,000 r / min. After emulsification, 1 kg of 1,3-propylenediamine is added, and then the speed is adjusted to 600 r / min and stirring is continued for 5 hours; the obtained polyurethane emulsion is heated to 60° C., and acetone is removed under a vacuum condition of -0.08 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products;

[0294] (3) Film forming method is the same as in Example 1

[0295] The structure of the long-chain alkane polysiloxane terminated with a terminal hydroxyl group is: The structure of perfluoropolyether diol is: HO(CH2CH2O)3CH2CF2O(CF2CF2O) 10 (CF2O)5CF2CH2(OCH2CH2)3OH.

[0296] Embodiment 18

[0297] ① First, add 6.5 kg of synthetic metal complex 0.3kg ferric chloride, 45kg acetone, stir and heat to 50℃ for 0.8h;

[0298] ② Synthesis of prepolymer: 0.5 kg of perfluoropolyether diol, 3 kg of amino-terminated alkyl-capped amide polysiloxane, 3.5 kg of DMPA and 69.5 kg of polybutadiene diol-2000 were added to a new reactor, heated to 110 ° C with stirring, vacuum dehydration for 2.5 hours, cooled to 55 ° C, and 56.8 kg of The complex solution of iron ions and 1.5 kg of trimethylolpropane were stirred for reaction for 0.5 h, then 34.9 kg of hydrogenated phenylmethane diisocyanate was added, the temperature was raised to 80 ° C with stirring for reaction for 0.5 h, 0.1 kg of bismuth neodecanoate was added, the temperature was raised to 95 ° C with stirring for reaction for 1 h, 30 kg of n-propyl acetate was added for reaction for 5 h, the temperature was lowered to 65 ° C with stirring, 2.2 kg of azelaic acid dihydrazide and 50 kg of acetone were added for reaction for 3 h, then the temperature was lowered to 20 ° C, 1.4 kg of sodium hydroxide was added, and the mixture was stirred for 2 h to obtain a modified waterborne polyurethane polymer;

[0299] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer is transferred to an emulsifier, and 500 kg of ice water is added to the modified waterborne polyurethane polymer under high-speed stirring at 8000 r / min. After emulsification, 15 kg of polyetheramine is added, and then the speed is adjusted to 400 r / min, and stirring is continued for 7 hours; 600 kg of distilled water is added to dilute the emulsion, and then 1.5 g of zinc acetate is added and stirred for 2 hours. The obtained polyurethane emulsion is heated to 60° C., and acetone is removed under a vacuum condition of -0.09 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products;

[0300] (3) Film forming method is the same as in Example 1

[0301] The structure of the amide polysiloxane terminated with a terminal hydroxyl hydrocarbon group is: The structure of perfluoropolyether diol is: HO(CH2CH2O)3CH2CF2O(CF2CF2O) 10 (CF2O)5CF2CH2(OCH2CH2)3OH.

[0302] Comparative Example 1

[0303] The commercial condom brand is Okamoto, and the sample model is Okamoto 001.

[0304] Comparative Example 2

[0305] The commercial condom brand is Sagami, and the sample model is Sagami 001.

[0306] Comparative Example 3

[0307] The commercial condom brand is Durex, and the sample model is Durex 001.

[0308] Comparative Example 4

[0309] The commercial condom brand is Durex, and the sample model is Durex 001.

[0310] Comparative Example 5

[0311] (1) Preparation of modified waterborne polyurethane polymer

[0312] 3 kg of amino-terminated polydimethylsiloxane, 5 kg of DMBA and 70 kg of PTMG-2000 were added to a new reactor, heated to 120°C with stirring, vacuum dehydrated for 2 hours, cooled to 65°C, added with 2.8 kg of dimethylglyoxime, 0.3 kg of zinc chloride and 1.5 kg of triethanolamine, stirred and reacted for 0.3 hours, then added with 29.6 kg of IPDI, stirred and heated to 75°C for reaction for 0.8 hours, added with 0.06 kg of bismuth laurate, stirred and heated to 95°C for reaction for 1 hour, added with 30 kg of n-propyl acetate for reaction for 5 hours, stirred and cooled to 50-65°C, added with 1.7 kg of adipic acid dihydrazide and 80 kg of acetone for reaction for 5 hours, then cooled to 30°C, added with 3.4 kg of triethylamine, stirred for 0.5 hours to obtain a modified waterborne polyurethane polymer;

[0313] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer was transferred to an emulsifier, and 600 kg of ice water was added to the modified waterborne polyurethane polymer under high-speed stirring at 10,000 r / min. After emulsification, 1.7 kg of IPDA was added, and then the speed was adjusted to 600 r / min and stirring was continued for 5 hours. The obtained polyurethane emulsion was heated to 60° C., and acetone was removed under a vacuum condition of -0.09 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products.

[0314] (3) Film forming method is the same as in Example 1

[0315] The structure of the amino-terminated polydimethylsiloxane is:

[0316] Comparative Example 6

[0317] (1) Preparation of modified waterborne polyurethane polymer

[0318] 5 kg of DMBA and 75 kg of PTMG-2000 were added to a new reactor, heated to 120°C with stirring, vacuum dehydrated for 2 h, cooled to 65°C, added with 2.8 kg of dimethylglyoxime, 0.3 kg of zinc chloride and 6 kg of triethanolamine, stirred and reacted for 0.3 h, then added with 29.6 kg of IPDI, stirred and heated to 75°C and reacted for 0.8 h, added with 0.06 kg of bismuth laurate, stirred and heated to 95°C and reacted for 1 h, added with 30 kg of n-propyl acetate and reacted for 5 h, then cooled to 30°C, added with 3.4 kg of triethylamine, and stirred for 0.5 h to obtain a modified waterborne polyurethane polymer;

[0319] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer was transferred to an emulsifier, and 600 kg of ice water was added to the modified waterborne polyurethane polymer under high-speed stirring at 10,000 r / min. After emulsification, 1.7 kg of IPDA was added, and then the speed was adjusted to 600 r / min and stirring was continued for 5 hours. The obtained polyurethane emulsion was heated to 60° C., and acetone was removed under a vacuum condition of -0.09 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products.

[0320] (3) Film forming method is the same as in Example 1

[0321] Comparative Example 7

[0322] (1) Preparation of modified waterborne polyurethane polymer

[0323] ① First, add 5.3 kg of synthetic metal complex 0.2kg calcium chloride, 45kg acetone, stir and heat to 50℃ for 0.6h;

[0324] ② Synthesis of prepolymer: 4.5kg DMPA and 75kg PTMG-2000 were put into a new reactor, heated to 120℃ with stirring, vacuum dehydration for 3h, cooled to 65℃, and 50.5kg The complex solution of calcium ions and 1.5 kg of triethanolamine were stirred for reaction for 0.3 h, then 31.4 kg of IPDI was added, the temperature was raised to 80°C for reaction for 0.5 h, 0.07 kg of dibutyltin dilaurate was added, the temperature was raised to 95°C for reaction for 1 h, 30 kg of n-propyl acetate was added for reaction for 5 h, the temperature was lowered to 50°C with stirring, 1.7 kg of adipic acid dihydrazide and 70 kg of acetone were added for reaction for 4 h, then the temperature was lowered to 30°C, 3.4 kg of triethylamine was added, and the reaction was stirred for 0.5 h to obtain a modified waterborne polyurethane polymer;

[0325] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer is transferred to an emulsifier, and 600 kg of ice water is added to the modified waterborne polyurethane polymer under high-speed stirring at 10,000 r / min. After emulsification, 0.7 kg of 1,3-propylenediamine is added, and then the speed is adjusted to 200 r / min, and stirring is continued for 7 hours; the obtained polyurethane emulsion is heated to 60° C., and acetone is removed under a vacuum condition of -0.09 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products;

[0326] (3) Film forming method is the same as in Example 1

[0327] Comparative Example 8

[0328] (1) Preparation of modified waterborne polyurethane polymer

[0329] Synthesis of prepolymer: 3 kg of amino-terminated polydimethylsiloxane, 5 kg of DMBA and 70 kg of PTMG-2000 were put into a new reactor, heated to 120°C with stirring, vacuum dehydrated for 2 h, cooled to 65°C, 2.8 kg of dimethylglyoxime and 1.5 kg of triethanolamine were added, stirred and reacted for 0.3 h, then 29.6 kg of IPDI was added, stirred and heated to 75°C for reaction for 0.8 h, 0.06 kg of bismuth laurate was added, stirred and heated to 95°C for reaction for 1 h, 30 kg of n-propyl acetate was added for reaction for 5 h, then cooled to 30°C, 3.4 kg of triethylamine was added, and stirred for 0.5 h to obtain a modified waterborne polyurethane polymer;

[0330] (2) Emulsification and desolventization: The modified waterborne polyurethane polymer was transferred to an emulsifier, and 600 kg of ice water was added to the modified waterborne polyurethane polymer under high-speed stirring at 10,000 r / min. After emulsification, 1.7 kg of IPDA was added, and then the speed was adjusted to 600 r / min and stirring was continued for 5 hours. The obtained polyurethane emulsion was heated to 60° C., and acetone was removed under a vacuum condition of -0.09 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products.

[0331] (3) Film forming method is the same as in Example 1

[0332] The structure of the amino-terminated polydimethylsiloxane is:

[0333] The prepared elastic film products and existing commercial samples were tested for performance according to YYT 1850-2023. The test results are shown in Table 1 below:

[0334]

[0335] In Table 1, comparison sample 1 is the water-based polyurethane condom sample of Okamoto 001, comparison sample 2 is the water-based polyurethane condom sample of Sagami 001, comparison sample 3 is the water-based polyurethane condom sample of Durex 001, comparison sample 4 is the water-based polyurethane condom sample of Jissbon 001, comparison sample 5 is the condom sample of Comparative Example 5, comparison sample 6 is the condom sample of Comparative Example 6, comparison sample 7 is the condom sample of Comparative Example 7, and comparison sample 8 is the condom sample of Comparative Example 8.

[0336] Comparative samples 1 to 4 are commercial samples. Except for comparative sample 2 Sagami 001, whose sample breaking force and water resistance have just reached the latest condom industry standard that will be implemented on January 15, 2024, that is, according to the YYT 1850-2023 test, the breaking force must be greater than or equal to 20N, and the breaking force in the water resistance test must be greater than or equal to 15N. The breaking force and water resistance of the remaining comparative commercial samples cannot meet the standards required by YYT 1850-2023. However, the modulus of the Sagami 001 sample reaches 2.0MPa, which means that the Sagami 001 condom is relatively hard. This greatly affects the user experience of condoms. Among them, Figure 1 The figure shows the stress-strain curve of the comparative sample 2 Sagami 001 condom sample. The tensile strength of the comparative sample 2 Sagami 001 condom sample in the figure is 27MPa, its elongation is 490%, its Young's modulus is 7.4MPa, and its 100% tensile modulus is 2MPa.

[0337] Comparative samples 5 to 8 are condom samples prepared in comparative examples 5 to 8. In comparative example 5, a ligand compound is added as a chain extender during the synthesis of a modified waterborne polyurethane polymer, and metal ions are added for coordination, i.e., the metal-coordination effect is generated during the polymer chain extension process; and the synthesized modified waterborne polyurethane polymer structure contains polysiloxane units. In comparative example 6, the synthesized modified waterborne polyurethane polymer structure does not contain a strong supramolecular dynamic crosslinking unit, and the polymer has a high degree of crosslinking. In comparative example 7, the synthesized modified waterborne polyurethane polymer structure contains a strong supramolecular dynamic crosslinking unit and does not contain a polysiloxane unit. In comparative example 8, the synthesized modified waterborne polyurethane polymer structure does not contain a strong supramolecular dynamic crosslinking unit and contains a polysiloxane unit. The film of comparative sample 5 prepared in comparative example 5 has low strength and poor elasticity, and cannot meet the industry standard for condoms. The film of comparative sample 6 prepared in comparative example 6 has a 100% tensile modulus of 4MPa, which is too hard, and has a low elongation, and cannot meet the industry standard for condoms. Comparative Example 7 The film of Comparative Sample 7 prepared has poor water resistance and cannot meet the industry standard. At the same time, the film has high surface viscosity and self-repairing performance. Comparative Example 8 The film of Comparative Sample 8 prepared has low tensile strength and cannot meet the industry standard.

[0338] Figure 2 The figure is a physical picture of Example 7; Figure 3 The Tg value of the condom sample in Example 7 in a is 23°C; Figure 3 b is the infrared spectrum of the condom sample of Example 7, where 1724 cm -1 C=O peak, 1538cm -1 NH peak, 1307cm -1 Si-C peak, 1223 cm -1 CF peak, 1063 cm -1CO(Si-O) peak, 800cm -1 is the SiO-H peak, and this spectrum shows that the condom sample of Example 7 is a water-based polyurethane material; Figure 3 c is the thermogravimetric curve of Example 7, which shows that the decomposition temperature of the sample of Example 7 starts at about 180°C; Figure 3 d is the particle size distribution diagram of the emulsion of Example 7, which shows that the particle size distribution of the emulsion of Example 7 in the initial state is in the range of 1 to 13 nm, mainly in the range of 5 to 8 nm, and the particle size distribution after being placed for half a year is in the range of 1 to 13 nm, mainly in the range of 5 to 8 nm. The particle size distribution after being placed for half a year is similar to the particle size distribution in the initial state.

[0339] The condom samples prepared in Examples 1 to 18 can all meet the latest condom industry standards. Under the premise that the burst pressure and burst volume of the samples in the examples meet the standards, the Young's modulus of the samples in the examples is large, indicating that they have good initial elasticity, which allows the film products to be tightly attached to the skin surface, and the film is not easy to slip during use; at the same time, the 100% tensile modulus of the examples is lower than 1.2MPa, indicating that the samples in the examples are soft and can provide comfort to the film users. The thickness of the samples in the examples is less than or equal to 20 microns, and its tear force is greater than 15N, and the elongation is greater than or equal to 550%, indicating that the samples in the examples are ultra-thin and highly flexible. This series of condoms gives condom users a better experience; the samples in the examples are tested for water resistance according to YYT 1850-2023. The test conditions of the film are soaked in deionized water at 50°C for one hour. The water resistance of the samples in the examples is greater than 15N, which meets the industry standards for condoms.

[0340] The condom films prepared in Examples 1 and 3 contain supramolecular crosslinking units and polysiloxane units, wherein the supramolecular crosslinking units act as metal ligands. The performance of the films prepared in Examples 1 and 3 just reaches the industry standard specified in YYT 1850-2023. Figure 4 a is a stress-strain curve of the condom sample of Example 1, in which the tensile strength of the condom sample of Example 1 is 30 MPa, its elongation is 590%, its Young's modulus is 16 MPa, and its 100% tensile modulus is 0.9 MPa; Figure 4 b is the stress-strain curve of the condom sample of Example 3, in which the tensile strength of the condom sample of Example 3 is 28 MPa, its elongation is 550%, its Young's modulus is 16 MPa, and its 100% tensile modulus is 0.9 MPa;

[0341] The condom films prepared in Examples 2, 4, 5, 8 to 13, and 15 contain supramolecular crosslinking units and polysiloxane units, wherein the supramolecular crosslinking units are metal ligands and strong hydrogen bonds. The performance of the condom films prepared in Examples 2, 4, 5, 8 to 13, and 15 is higher than or equal to that of the condom films prepared in Examples 1 and 3. This indicates that adding strong hydrogen bonds to the supramolecular crosslinking can further enhance toughness. Figure 5 a is a stress-strain curve of the condom sample of Example 2, in which the tensile strength of the condom sample of Example 2 is 33 MPa, its elongation is 590%, its Young's modulus is 26 MPa, and its 100% tensile modulus is 0.9 MPa; Figure 5 b is the stress-strain curve of the condom sample of Example 4, in which the tensile strength of the condom sample of Example 4 is 34 MPa, its elongation is 600%, its Young's modulus is 16 MPa, and its 100% tensile modulus is 1.1 MPa; Figure 5 c is the stress-strain curve of the condom sample of Example 5, in which the tensile strength of the condom sample of Example 5 is 28 MPa, its elongation is 710%, its Young's modulus is 20 MPa, and its 100% tensile modulus is 1.1 MPa; Figure 5 d is the stress-strain curve of the condom sample of Example 8. In the figure, the tensile strength of the condom sample of Example 8 is 28 MPa, its elongation is 710%, its Young's modulus is 17 MPa, and its 100% tensile modulus is 1.1 MPa. Figure 6 a is a stress-strain curve of the condom sample of Example 9, in which the tensile strength of the condom sample of Example 9 is 26 MPa, its elongation is 720%, its Young's modulus is 15 MPa, and its 100% tensile modulus is 1.1 MPa; Figure 6 b is a stress-strain curve of the condom sample of Example 10, in which the tensile strength of the condom sample of Example 10 is 30 MPa, its elongation is 680%, its Young's modulus is 20 MPa, and its 100% tensile modulus is 1 MPa; Figure 6 c is the stress-strain curve of the condom sample of Example 11, in which the tensile strength of the condom sample of Example 11 is 31 MPa, its elongation is 660%, its Young's modulus is 15 MPa, and its 100% tensile modulus is 1 MPa; Figure 6 d is the stress-strain curve of the condom sample of Example 12. In the figure, the tensile strength of the condom sample of Example 12 is 28 MPa, its elongation is 620%, its Young's modulus is 17 MPa, and its 100% tensile modulus is 0.9 MPa. Figure 7a is a stress-strain curve of the condom sample of Example 13, in which the tensile strength of the condom sample of Example 13 is 27 MPa, its elongation is 660%, its Young's modulus is 16 MPa, and its 100% tensile modulus is 1.1 MPa; Figure 7 b is the stress-strain curve of the condom sample of Example 15. In the figure, the tensile strength of the condom sample of Example 15 is 29 MPa, its elongation is 680%, its Young's modulus is 15 MPa, and its 100% tensile modulus is 1 MPa.

[0342] In the embodiments, the preferred polymer diol is added to prepare the film with better water resistance. For example, the polymer diol added in embodiments 9, 10, 12, and 15 is not a preferred option. The films prepared in these embodiments are tested for water resistance according to YYT 1850-2023, and their tear force is reduced by about 25% compared with the original tear force. Embodiments 1 to 8, 11, 13, 14, 16, and 17 are added with preferred polymer diols. The films prepared in these embodiments are tested for water resistance according to YYT 1850-2023, and their tear force is reduced by about 20% or less than 20% compared with the original tear force.

[0343] The film structure prepared in the embodiment contains a polysiloxane structure and a fluorine-containing structure, and the flexibility and water resistance of the prepared film are better. For example, in Examples 16 and 17, the film prepared by adding perfluoropolyether diol, after the water resistance test, the tear force of the film is reduced by about 15% compared with the original tear force, which shows that its water resistance is better. The film structure prepared in the embodiment contains a polysiloxane structure and a fluorine-containing structure, and the film structure contains a supramolecular dynamic cross-linking structure and a dynamic covalent bond, and the comprehensive performance of the prepared film is the best. For example, in Examples 7 and 14, fluorine-modified silicone and dihydrazide containing dynamic covalent bonds are added, and the obtained film has a tear force of 28 to 30N, a 100% tensile modulus of 0.7 to 0.8MPa, and a Young's modulus of 26 to 30MPa at a thickness of 15 to 18 microns, which shows that this condom film is ultra-thin, ultra-elastic, and ultra-flexible. These properties give the condom an ultra-comfortable use experience. Among them, Figure 4 c is the stress-strain curve of the condom sample of Example 16, in which the tensile strength of the condom sample of Example 16 is 37 MPa, its elongation is 600%, its Young's modulus is 28 MPa, and its 100% tensile modulus is 1 MPa; Figure 4 d is the stress-strain curve of the condom sample of Example 17. In the figure, the tensile strength of the condom sample of Example 17 is 34 MPa, its elongation is 610%, its Young's modulus is 15 MPa, and its 100% tensile modulus is 1 MPa. Figure 8a is a stress-strain curve of the condom sample of Example 6, in which the tensile strength of the condom sample of Example 6 is 45 MPa, its elongation is 690%, its Young's modulus is 15 MPa, and its 100% tensile modulus is 0.9 MPa; Figure 8 b is the stress-strain curve of the condom sample of Example 7, in which the tensile strength of the condom sample of Example 7 is 43 MPa, its elongation is 670%, its Young's modulus is 26 MPa, and its 100% tensile modulus is 0.8 MPa; Figure 8 c is the stress-strain curve of the condom sample of Example 14. In the figure, the tensile strength of the condom sample of Example 14 is 47MPa, its elongation is 650%, its Young's modulus is 30MPa, and its 100% tensile modulus is 0.7MP.

[0344] In the examples, the metal-coordination effect is further enhanced to prepare a film with super high elasticity, flexibility and water resistance. For example, in Example 18, zinc acetate is further coordinated with carboxylic acid ions based on the experimental steps of Example 6 to prepare a film with a tensile strength of 45 MPa, a Young's modulus of 29 MPa, and a 100% tensile modulus of 0.9 MPa, which is nearly twice as high as the Young's modulus of 15 MPa of the film prepared in Example 6, that is, a super high elasticity, super flexibility and water resistance film is obtained. Figure 8 d is the stress-strain curve of the condom sample of Example 18. In the figure, the tensile strength of the condom sample of Example 7 is 45 MPa, its elongation is 640%, its Young's modulus is 29 MPa, and its 100% tensile modulus is 0.9 MPa.

[0345] The 100% tensile modulus of the prepared example film sample is lower than 1.2 MPa, which is 0.9-1.3 MPa lower than the 100% tensile modulus of the commercially available brand Sagami 001, and 0.4-1 MPa lower than the 100% tensile modulus of the commercially available brands Okamoto 001, Durex 001, and Jissbon 001, indicating that the film prepared by the present invention is super flexible; the Young's modulus of the prepared example film sample is 15-30 MPa, and the Young's modulus of the commercially available brands Sagami 001, Okamoto 001, Durex 001, and Jissbon 001 is below 8 MPa, which indicates that the initial elasticity of the film prepared by the present invention has super resilience, that is, the film has high elasticity; the water resistance of the prepared example film samples meets the latest industry standard for condoms that will be implemented on January 15, 2024, that is, the water resistance test is carried out in accordance with YYT 1850-2023, and the tearing force in the water resistance test is greater than or equal to 15N. The sample prepared in the above examples has excellent flexibility, high elasticity and water resistance.

[0346] It can be seen that the highly elastic, water-resistant and flexible water-based polyurethane elastic film product of the present invention is used to prepare water-based polyurethane condoms. The prepared water-based polyurethane condoms are as thin as 20 μm or less, the elongation at break of the film is more than 550%, the tear force of the film is more than 20N, the 100% tensile modulus of the film is less than 1.2MPa, the Young's modulus of the film is more than 15MPa, and the tear force of the film after soaking in 50°C hot water for one hour is more than 15N. This shows that the highly elastic, water-resistant and flexible water-based polyurethane elastic film product prepared by the present invention can be used to prepare water-based polyurethane condoms. The prepared condoms have good water resistance, flexibility and high elasticity, solve the shortcomings of the current water-based polyurethane condoms that are easy to fall off, easy to break and too hard, and meet the higher requirements for condoms in the new era.

[0347] At the same time, the highly elastic, water-resistant and flexible water-based polyurethane elastic film product of the present invention has excellent water resistance, high elasticity and high flexibility, and can be used to prepare organ belts, medical gloves and finger cots with similar performance requirements as water-based polyurethane condoms.

[0348] 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 highly elastic, water-resistant and flexible waterborne polyurethane elastic film product, characterized in that: The invention relates to an emulsion made of a modified waterborne polyurethane polymer and obtained by a film-forming process; wherein the modified waterborne polyurethane polymer contains a strong supramolecular dynamic crosslinking unit and a polysiloxane unit in its structure, and the strong supramolecular dynamic crosslinking unit is introduced at least through the polymerization reaction of a metal complex and a diisocyanate; wherein the metal complex contains at least three reactive groups, which are preformed by at least two ligand compounds and a metal ion; The modified waterborne polyurethane polymer is prepared from the following raw materials in parts by weight:

2. The highly elastic, water-resistant and flexible waterborne polyurethane elastic film product according to claim 1, characterized in that: The ligand compound has the following general structure: R1-R3-M-R4-R2, wherein R1 and R2 are reactive groups independently selected from hydroxyl, amino, and thiol; R3 and R4 are absent or are carbon chain linking groups selected from C 1-24 Alkylidene, substituted C 1-24 Alkylene; M contains at least the following ligand structure:

3. The highly elastic, water-resistant and flexible waterborne polyurethane elastic film product according to claim 1, characterized in that: The metal ions in the metal complex are selected from one or more of the following: calcium ions, zinc ions, iron ions, cuprous ions, ferrous ions, cupric ions, and lanthanide metal ions.

4. The highly elastic, water-resistant and flexible waterborne polyurethane elastic film product according to claim 1, characterized in that: The polysiloxane unit is introduced through the polymerization reaction of polysiloxane and isocyanate, and the polysiloxane is selected from at least one of hydroxyl-terminated polysiloxane, amino-terminated polysiloxane and mercapto-terminated polysiloxane.

5. The highly elastic, water-resistant and flexible waterborne polyurethane elastic film product according to claim 4, characterized in that: The polysiloxane has a structure shown in the following general formula: Wherein R5 and R6 are independently selected from hydroxyl, amino, and thiol, L1 and L2 are divalent linking groups independently selected from C 1-20 Alkylidene, substituted C 1-20 Alkylidene, -(CH2)3O(CH2CH2O) m [CH(CH3)CH2O] n CH(CH3)CH2-, J and Q are independently selected from methyl, long-chain alkyl, phenyl, epoxy, trifluoropropyl, perfluoroalkyl oxasulfonylpropyl, CF3OCF(CF3)CF2OCF2(CH2)2-; x and y are integers of 5 to 40, and m, n and o are integers of 1 to 30.

6. The highly elastic, water-resistant and flexible waterborne polyurethane elastic film product according to claim 1, characterized in that: The strong supramolecular dynamic cross-linking unit also contains a strong hydrogen bond unit.

7. The highly elastic, water-resistant and flexible waterborne polyurethane elastic film product according to claim 6, characterized in that: The strong hydrogen bonding unit is introduced by preforming hydrogen bonding compounds from hydrogen bonding monomer compounds and / or by forming hydrogen bonding units from hydrogen bonding monomers generated from reactants that can generate hydrogen bonding monomers when polymerizing the modified waterborne polyurethane polymer.

8. The highly elastic, water-resistant and flexible waterborne polyurethane elastic film product according to claim 7, characterized in that: The hydrogen bonding monomer is selected from at least one of the following structures: Wherein R7 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 selected from C 1-15 Alkylidene, substituted C 1-15 The hydrocarbyl group; the dynamic bond-containing linking group is selected from a linking group containing a dynamic disulfide bond, a dynamic diselenide bond, a dynamic ketal bond, a dynamic acetal bond, a dynamic thioketal bond, a dynamic thioacetal bond, a dynamic imine bond, and a dynamic oxime bond.

9. The highly elastic, water-resistant and flexible waterborne polyurethane elastic film product according to claim 7, characterized in that: The hydrogen bond monomer compound is selected from the following compounds:

10. The highly elastic, water-resistant and flexible waterborne polyurethane elastic film product according to claim 1, characterized in that: The emulsion is further enhanced by metal-coordination, wherein the metal-coordination is formed by the coordination of carboxylic acid ligands with zinc ions.

11. A method for preparing a highly elastic, water-resistant and flexible waterborne polyurethane elastic film product according to any one of claims 1 to 5, characterized in that: The steps include: (1) Preparation of modified waterborne polyurethane polymer ① To synthesize the metal complex, first add 2.8-5 parts by weight of the ligand compound, 0.2-0.5 parts by weight of the metal ion salt, and 35-50 parts by weight of the organic solvent, and heat to 50-55°C with stirring for 0.5-1h; ② Synthesis of prepolymer: 3-4 parts by weight of polysiloxane, 4.5-5 parts by weight of hydrophilic chain extender and 60-70 parts by weight of polymer diol are added into a new reactor, heated to 100-120°C with stirring, vacuum dehydrated for 2-3 hours, cooled to 45-65°C, added with 38.1-55.5 parts by weight of metal complex solution and 1.4-1.5 parts by weight of trifunctional crosslinking agent, stirred for 0.3-0.6 hours, and then added with 2 9.6-31.4 parts by weight of diisocyanate, stirring and heating to 65-80°C for reaction for 0.5-1h, adding 0.06-0.07 parts by weight of catalyst, stirring and heating to 90-95°C for reaction for 1-1.5h, adding 30-60 parts by weight of organic solvent for reaction for 4-5h, then cooling to 20-30°C, adding 3.4-3.5 parts by weight of salt-forming agent, stirring for 0.5-2h to obtain a modified waterborne polyurethane polymer; (2) Emulsification and desolventization: The modified waterborne polyurethane polymer is transferred to an emulsifier, and 400 to 600 parts by weight of ice water are added to the prepolymer under high-speed stirring at 6500 to 10000 r / min. After emulsification, 0.7 to 1.7 parts by weight of a post-chain extender are added, and then the rotation speed is adjusted to 300 to 600 r / min, and stirring is continued for 5 to 7 hours; the obtained polyurethane emulsion is heated to 45 to 60° C., and the organic solvent is removed under a vacuum condition of -0.08 to -0.09 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products; (3) Film formation ① Glass mold cleaning: The glass mold is first cleaned with an alkaline detergent, then with an acidic detergent, and finally with neutral deionized water, and dried to 70°C; ② Dip the mold release agent: immerse the glass mold at 70℃ in the mold release agent for 30s, then slowly take it out at a uniform speed and dry it at 70℃; ③ Dipping in emulsion: immerse the 70°C glass mold with a release agent in polyurethane emulsion for 10 seconds, then slowly take it out at a uniform speed, dry it at 90°C for 10 seconds, immerse it in polyurethane emulsion for 10 seconds, then slowly take it out at a uniform speed, dry it at 90°C for 20 seconds, immerse it in polyurethane emulsion for 10 seconds, then slowly take it out at a uniform speed, and finally dry it at 80°C for 7 minutes; ④ Curling and drying: The film obtained in step ③ is curled to a suitable position, and the mold after curling is dried at 90°C for 5 minutes; ⑤Immersing in anti-adhesive agent, drying, and demoulding: After curling and drying, the mold is cooled to 30°C, immersed in anti-adhesive agent, dried at 90°C, and then demoulded to obtain a polyurethane elastic film product; The organic solvent is selected from one or more of acetone, acetonitrile, tetrahydrofuran, ethyl acetate and n-propyl acetate.

12. A method for preparing a highly elastic, water-resistant and flexible waterborne polyurethane elastic film product according to any one of claims 6 to 9, characterized in that: The steps include: (1) Preparation of modified waterborne polyurethane polymer ① To synthesize the metal complex, first add 4.3-10.7 parts by weight of the ligand compound, 0.2-0.6 parts by weight of the metal ion salt, and 30-50 parts by weight of the organic solvent, and heat to 40-55°C with stirring for 0.5-1h; ② Synthesis of prepolymer: 3-5 parts by weight of polysiloxane, 3.5-5 parts by weight of hydrophilic chain extender and 50-70 parts by weight of polymer diol are added into a new reaction kettle, heated to 100-120°C with stirring, vacuum dehydration for 2-3 hours, cooled to 45-65°C, added with 35-61.3 parts by weight of metal complex solution and 1-1.5 parts by weight of trifunctional crosslinking agent, stirred for 0.3-1 hour, then added with 22.4-34.9 parts by weight of diisocyanate, stirred and heated to 65-80°C for reaction for 0.5 ~1h, add 0.07~0.1 weight part of catalyst, stir and heat to 80~95℃ for reaction for 1~2h, add 30~60 weight parts of organic solvent for reaction for 3~5h, stir and cool to 50~65℃, add 1.3~4.1 weight parts of reactant or hydrogen bond monomer compound capable of generating hydrogen bond monomer and 50~80 weight parts of organic solvent for reaction for 3~5h, then cool to 20~30℃, add 1.4~4.9 weight parts of salt-forming agent, stir for 0.5~2h to obtain modified waterborne polyurethane polymer; (2) Emulsification and desolventization: The modified waterborne polyurethane polymer is transferred to an emulsifier, and 300 to 600 parts by weight of ice water are added to the prepolymer under high-speed stirring at 4000 to 10000 r / min. After emulsification, 0.3 to 15 parts by weight of a post-chain extender are added, and then the rotation speed is adjusted to 200 to 600 r / min, and stirring is continued for 5 to 7 hours; the obtained polyurethane emulsion is heated to 40 to 60° C., and the organic solvent is removed under a vacuum condition of -0.08 to -0.1 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products; (3) Film formation ① Glass mold cleaning: The glass mold is first cleaned with an alkaline detergent, then with an acidic detergent, and finally with neutral deionized water, and dried to 70°C; ② Dip the mold release agent: immerse the glass mold at 70℃ in the mold release agent for 30s, then slowly take it out at a uniform speed and dry it at 70℃; ③ Dipping in emulsion: immerse the 70°C glass mold with a release agent in polyurethane emulsion for 10 seconds, then slowly take it out at a uniform speed, dry it at 90°C for 10 seconds, immerse it in polyurethane emulsion for 10 seconds, then slowly take it out at a uniform speed, dry it at 90°C for 20 seconds, immerse it in polyurethane emulsion for 10 seconds, then slowly take it out at a uniform speed, and finally dry it at 80°C for 7 minutes; ④ Curling and drying: The film obtained in step ③ is curled to a suitable position, and the mold after curling is dried at 90°C for 5 minutes; ⑤Immersing in anti-adhesive agent, drying, and demoulding: After curling and drying, the mold is cooled to 30°C, immersed in anti-adhesive agent, dried at 90°C, and then demoulded to obtain a polyurethane elastic film product; The organic solvent is selected from one or more of acetone, acetonitrile, tetrahydrofuran, ethyl acetate and n-propyl acetate.

13. A method for preparing a highly elastic, water-resistant and flexible waterborne polyurethane elastic film product according to any one of claims 6 to 10, characterized in that: The steps include: (1) Preparation of modified waterborne polyurethane polymer ① To synthesize the metal complex, first add 6.5 parts by weight of the ligand compound, 0.3 parts by weight of the metal ion salt, and 45 parts by weight of the organic solvent, and heat to 50°C with stirring for 0.8h; ② Synthesis of prepolymer: 3 parts by weight of polysiloxane, 3.5 parts by weight of hydrophilic chain extender and 70 parts by weight of polymer diol are put into a new reactor, heated to 110°C with stirring, vacuum dehydrated for 2.5 hours, cooled to 55°C, 56.8 parts by weight of metal complex solution and 1.5 parts by weight of trifunctional crosslinking agent are put in, stirred for 0.5 hours, then 34.9 parts by weight of diisocyanate are put in, stirred and heated to 80°C for reaction for 0.5 hours, 0.1 parts by weight of catalyst are added, stirred and heated to 95°C for reaction for 1 hour, 30 parts by weight of organic solvent are put in for reaction for 5 hours, then cooled to 65°C, 2.2 parts by weight of reactant or hydrogen bond monomer compound capable of generating hydrogen bond monomer and 50 parts by weight of organic solvent are put in for reaction for 3 hours, then cooled to 20°C, 1.4 parts by weight of salt-forming agent are added, stirred for 2 hours to obtain a modified waterborne polyurethane polymer; (2) Emulsification and desolventization: The modified waterborne polyurethane polymer is transferred to an emulsifier, and 500 parts by weight of ice water is added to the prepolymer under high-speed stirring at 8000 r / min. After emulsification, 15 parts by weight of a post-chain extender is added, and then the speed is adjusted to 400 r / min and stirring is continued for 7 hours; 600 parts by weight of distilled water is added to dilute the emulsion, and then 1.5 parts by weight of zinc acetate is added and stirred for 2 hours. The obtained polyurethane emulsion is heated to 60° C. and the organic solvent is removed under a vacuum condition of -0.09 MPa to obtain an aqueous emulsion for preparing polyurethane elastic film products; (3) Film formation ① Glass mold cleaning: The glass mold is first cleaned with an alkaline detergent, then with an acidic detergent, and finally with neutral deionized water, and dried to 70°C; ② Dip the mold release agent: immerse the glass mold at 70℃ in the mold release agent for 30s, then slowly take it out at a uniform speed and dry it at 70℃; ③ Dipping in emulsion: immerse the 70°C glass mold with a release agent in polyurethane emulsion for 10 seconds, then slowly take it out at a uniform speed, dry it at 90°C for 10 seconds, immerse it in polyurethane emulsion for 10 seconds, then slowly take it out at a uniform speed, dry it at 90°C for 20 seconds, immerse it in polyurethane emulsion for 10 seconds, then slowly take it out at a uniform speed, and finally dry it at 80°C for 7 minutes; ④ Curling and drying: The film obtained in step ③ is curled to a suitable position, and the mold after curling is dried at 90°C for 5 minutes; ⑤Immersing in anti-adhesive agent, drying, and demoulding: After curling and drying, the mold is cooled to 30°C, immersed in anti-adhesive agent, dried at 90°C, and then demoulded to obtain a polyurethane elastic film product; The organic solvent is selected from one or more of acetone, acetonitrile, tetrahydrofuran, ethyl acetate and n-propyl acetate.

14. The use of a highly elastic, water-resistant and flexible waterborne polyurethane elastic film product according to claim 1, characterized in that: The highly elastic, water-resistant and flexible waterborne polyurethane elastic film product is used for preparing condoms, organ bands, finger cots and medical gloves.

15. The use of a highly elastic, water-resistant and flexible waterborne polyurethane elastic film product according to claim 6, characterized in that: The highly elastic, water-resistant and flexible waterborne polyurethane elastic film product is used for preparing condoms, organ bands, finger cots and medical gloves.

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