CN113061230A - Self-closed polyurethane prepolymer - Google Patents
Self-closed polyurethane prepolymer Download PDFInfo
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- CN113061230A CN113061230A CN202110320247.1A CN202110320247A CN113061230A CN 113061230 A CN113061230 A CN 113061230A CN 202110320247 A CN202110320247 A CN 202110320247A CN 113061230 A CN113061230 A CN 113061230A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
Abstract
The invention relates to a self-closed polyurethane prepolymer, in particular to a self-closed isocyanate-terminated polyurethane prepolymer which is prepared by taking N- (4-hydroxy-3-formylbenzyl) -N-hydroxyl-terminated polyether quaternary ammonium salt and polyisocyanate as raw materials and tertiary amine as an alkali reagent for catalytic addition reaction and polymerization reaction. When the self-sealing polyurethane prepolymer is deblocked by heating, the sealing agent generated by pyrolysis is still linked on the polyurethane prepolymer polymer chain and serves as a functional modifier of the filler or material, so that the optimized utilization of material resources is realized, and the material is not released into the air or products to cause environmental pollution or resource waste.
Description
Technical Field
The invention relates to a closed polyurethane prepolymer, in particular to a self-closed end isocyanate-based polyurethane prepolymer, belonging to the field of functional polymer materials.
Background
The polyurethane prepolymer is prepared by reacting polyisocyanates and polyols in a non-equimolar ratio, so that the chain structure of the polyurethane prepolymer contains chemically active end groups. Polyurethane prepolymers can be classified according to their reactive end groups into: the polyurethane prepolymer comprises isocyanate-terminated polyurethane prepolymer, hydroxyl-terminated polyurethane prepolymer, closed polyurethane prepolymer, polyurethane prepolymer with terminal group being terminal acrylate group or terminal silane group, and the like. The isocyanate-terminated polyurethane prepolymer is one of the commonly used varieties and is mainly used as a curing agent of an adhesive or a coating, and a post-chemical modifier or finishing agent of cotton fabric, silk, wood, phenolic resin, amino resin, polyamide or polyurethane and other materials. However, the isocyanate-terminated polyurethane prepolymer has short natural storage time and is easily affected by humid air in the use process, and people invent a chemically inert blocked polyurethane prepolymer under natural conditions.
The blocked polyurethane prepolymer is prepared by reacting a blocked isocyanate group of a blocked isocyanate polyurethane prepolymer with a blocking agent. Commonly used blocking agents include organic alcohols, thiols, arylamine amides, phenols, ethyl acetoacetate, imidazole, acetoxime, sodium bisulfite, boric acid, and the like. The molecular structures of the sealing agents contain active N-H, C-H, O-H or S-H groups, and the sealing agents can perform addition reaction with isocyanate groups of the isocyanate group-terminated polyurethane prepolymer to prepare polyurethane prepolymer containing urethane structural units, namely the sealing polyurethane prepolymer. The terminal isocyanate group of the closed polyurethane prepolymer loses chemical activity temporarily, and the closed polyurethane prepolymer has high stability under natural conditions and is easy to store, transport or use.
In the application process of the blocked polyurethane prepolymer, the blocked polyurethane prepolymer is generally heated to decompose and lose the blocking agent, and the isocyanate-terminated polyurethane prepolymer is reproduced. However, the sealing agent released by the blocked polyurethane prepolymer during thermal pyrolysis is usually released in the air or products, is not easy to recover, causes pollution or harm to production environment and field workers, and causes no-end waste of material resources. In recent years, attention has been paid to the development of novel blocking agents having low toxicity, high efficiency and low deblocking temperature. However, there is still no consideration of the secondary use of the blocking agent released upon deblocking. Therefore, the invention creates a self-sealing end isocyanate-based polyurethane prepolymer, aiming at realizing the optimized utilization of material resources by connecting a sealing agent which is not released due to deblocking on a high molecular chain of the end isocyanate-based polyurethane prepolymer and is still connected on the high molecular chain of the end isocyanate-based polyurethane prepolymer when the sealing agent is deblocked by heating.
Disclosure of Invention
The invention provides a self-closed end isocyanate-based polyurethane prepolymer, which is characterized by having a structure shown in a general formula (I):
wherein R in the general formula (I)1And R2Alkyl refers to C1～C18A hydrocarbon group,
is selected from C1～C18Alkylene or
Wherein q is a natural number between 1 and 200; n is selected from natural numbers between 2 and 2000, and m is selected from natural numbers between 1 and 2000.
The preparation method of the self-closed end isocyanate-based polyurethane prepolymer comprises the following steps: weighing polyisocyanate and an organic solvent in a reactor, controlling the temperature to be 50-90 ℃, then weighing hydroxyl-terminated polyether quaternary ammonium salt and a catalyst according to the molar ratio of isocyanate (-NCO) to hydroxyl (-OH) (namely a polyurethane R value) being 2.0-2.2, slowly adding the hydroxyl-terminated polyether quaternary ammonium salt and the catalyst into the reactor, stirring and reacting for 2-12 hours, wherein a di-n-butylamine titration analysis method is adopted, after analyzing and detecting that the-NCO content in reaction materials in the reactor is consistent with a preset value, the temperature of the materials in the reactor is reduced to room temperature, and a solution of isocyanate-terminated polyurethane is prepared; adding an alkali reagent into the isocyanate-terminated polyurethane prepolymer solution, stirring for reacting for 2-4 hours, increasing the temperature of materials in the reactor to 50-90 ℃ for reacting until-NCO cannot be detected in the materials in the reactor, and distilling to recover volatile substances, wherein the volatile substances comprise an organic solvent, a catalyst and an alkali reagent; then adding water with the quality similar to that of the solid remained in the reactor into the reaction system, stirring and dispersing, then blowing oxygen, detecting that the pH value of the material in the reactor is not reduced any more, sending the reaction product in the reaction kettle into a vacuum drier, and drying in vacuum at 60 ℃ to obtain the self-closed end isocyanate-based polyurethane prepolymer; the following reaction illustrates the preparation and deblocking of the self-sealing closed-end isocyanate-based polyurethane prepolymer:
wherein the hydroxyl-terminated polyether quaternary ammonium salt has a structure shown in a general formula (II):
wherein R in the general formula (II)1And R2Are respectively selected from C1～C18One of the hydrocarbon groups, m is a natural number of 1 to 2000. The polyisocyanate has a structure represented by general formula (III):
wherein in the general formula (III)
Is selected from C1～C18Alkylene or
Wherein q is a natural number between 1 and 200.
The organic solvent is one or more of acetone, butanone, cyclohexanone, tetrahydrofuran, 1, 4-dioxane, chlorobenzene, chloroform, 1, 2-dichloroethane, toluene, xylene, decalin, methyl acetate, ethyl acetate, butyl acetate, N-methylpyrrolidone, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, N, N-dimethylformamide, N, N-dimethylacetamide, triethylamine, tributylamine, p-dimethylaminopyridine, N, N, N ', N ' -tetramethylethylenediamine, triethylenediamine, N, N ' -dimethylpiperazine, N-methylmorpholine or dimethyl sulfoxide.
The catalyst refers to a compound of organic amine and organic tin, and the mass ratio of the organic amine to the organic tin is 1: 0.5-5;
wherein the organic amine refers to one of triethylamine, tributylamine, 4-dimethylamino pyridine, N, N, N ', N ' -tetramethyl ethylenediamine, triethylene diamine, N, N ' -dimethyl piperazine or N-methyl morpholine;
the organic tin refers to one of dibutyltin dilaurate, stannous octoate, stannous oxalate, dibutyltin dimaleate, dibutyltin dilauryl sulfide or dibutyltin diacetate;
the alkali reagent is selected from one of triethylamine, tributylamine, 4-dimethylamino pyridine, N, N, N ', N ' -tetramethyl ethylenediamine, triethylene diamine, N, N ' -dimethyl piperazine or N-methyl morpholine;
the mass ratio of the polyisocyanate to the hydroxyl-terminated polyether quaternary ammonium salt to the catalyst to the alkali reagent to the organic solvent is 100/50-500/0.5-5/5-500/100-1000.
The preparation method of the hydroxyl-terminated polyether quaternary ammonium salt is realized by the following steps: weighing 5-chloromethyl salicylaldehyde and tertiary amine polyethylene glycol according to the proportion of equal molar ratio, dissolving in a solvent to respectively prepare a 5-chloromethyl salicylaldehyde solution and a tertiary amine polyethylene glycol solution, controlling the temperature to be 0-100 ℃, adding the 5-chloromethyl salicylaldehyde solution into the tertiary amine polyethylene glycol solution, stirring for reaction for 2-20 hours, filtering, and drying a filter cake to prepare the hydroxyl-terminated polyether quaternary ammonium salt with the general formula (II).
Wherein the tertiary amino polyethylene glycol has a structure shown in a general formula (IV):
wherein R in the general formula (IV)1And R2Are respectively selected from C1～C18One of the hydrocarbon groups, m is a natural number of 1 to 2000.
The solvent is selected from one or more of methanol, ethanol, propanol, butanol, cyclohexanol, acetone, butanone, cyclohexanone, tetrahydrofuran, 1, 4-dioxane, chlorobenzene, chloroform, 1, 2-dichloroethane, toluene, xylene, decalin, methyl acetate, ethyl acetate, butyl acetate, N-methylpyrrolidone, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide; the dosage of the solvent is 0.5-2.5 times of the mass of the 5-chloromethyl salicylaldehyde or the mass of the tertiary amine polyethylene glycol.
The self-closed end isocyanate-based polyurethane prepolymer provided by the invention has the following characteristics:
the self-sealing end isocyanate-based polyurethane prepolymer generates end isocyanate-based polyurethane prepolymer containing carboxylic acid betaine when subjected to deblocking reaction by heating, and can be used as a post-chemical modifier of organic materials containing active groups such as O-H/N-H, and the like, wherein the blocking agent is still connected to the organic materials through polyurethane chains and endows the organic materials with zwitterionic characteristics.
② the preparation method of the self-closed end isocyanate-based polyurethane prepolymer is simple and easy, and the used raw materials are cheap; the preparation process can realize a one-pot boiling mode; after the preparation process is finished, the alkali reagent is still available and can be distilled, separated and recovered.
Detailed Description
EXAMPLE 1 preparation of self-blocked isocyanate-based polyurethane prepolymer-1
Weighing 17 g of 5-chloromethyl salicylaldehyde and dissolving in 20 g of ethyl acetate, dissolving 118 g of tertiary amino polyethylene glycol of the formula (III-1) in 100 g of ethyl acetate to respectively prepare a 5-chloromethyl salicylaldehyde solution and a tertiary amino polyethylene glycol solution, controlling the temperature to be 25-30 ℃, adding the 5-chloromethyl salicylaldehyde solution into the tertiary amino polyethylene glycol solution, stirring and reacting for 4 hours, separating out an upper layer clear solution, and weighing about 130 g of the residual precipitate, namely the hydroxyl-terminated polyether quaternary ammonium salt of the formula (II-1).
According to the ratio of NCO/OH molar ratio of 2.08, 30 g of toluene diisocyanate and 30 g of butanone are weighed and put into a reactor, and 130 g of hydroxyl-terminated polyether quaternary ammonium salt of formula (II-1), 0.5 g of stannous octoate and 1.8 g of 4-dimethylamino pyridine are added under the protection of nitrogen and stirringHeating the mixture to 65-70 ℃ for reacting for 4 hours, reducing the temperature of the materials in the reaction kettle to 20-25 ℃ when the NCO content reaches 9.85% by a di-n-butylamine titration method, adding a mixture of 30 g of 4-dimethylaminopyridine and 30 g of butanone, stirring for reacting for 2 hours, increasing the temperature of the materials in the reaction kettle to 85-90 ℃, stirring for reacting until no-NCO is detected, wherein the reaction time is about 12 hours, and then performing rotary evaporation or negative-pressure rotary evaporation to respectively recover the butanone and the 4-dimethylaminopyridine. Then adding 150 g of water into the reaction kettle to just dissolve the residual solids in the reaction kettle, stirring and introducing oxygen for 2 hours, and then drying at 60 ℃ in vacuum to obtain the light yellow waxy self-closed end isocyanate-based polyurethane prepolymer-1. N is a radical of2Under protection, the product can be stored for a long time without deterioration. The deblocking temperature of the sample is 102-118 ℃ according to analysis and test.
Wherein the tertiary amine polyethylene glycol of the formula (III-1) and the hydroxyl-terminated polyether quaternary ammonium salt of the formula (II-1) respectively have the following structures:
example 2 preparation of self-blocked isocyanate-based polyurethane prepolymer-2
According to the method and the operation steps of the example 1, the toluene diisocyanate in the example 1 is changed into 1, 6-hexamethylene diisocyanate, and the hydroxyl-terminated polyether quaternary ammonium salt with the structure shown in the formula (II-1) is changed into the hydroxyl-terminated polyether quaternary ammonium salt with the structure shown in the formula (II-2), so that the self-closed isocyanate-terminated polyurethane prepolymer-2 is prepared. The analysis and detection result shows that the deblocking temperature is about 112 ℃; and at normal temperature, the self-sealing end isocyanate-based polyurethane prepolymer-2 is sealed and stored for a long time and guaranteed.
Wherein the hydroxyl-terminated polyether quaternary ammonium salt of the formula (II-2) has the following structure:
example 3 preparation of self-blocked isocyanate-based polyurethane prepolymer-3
According to the method and the operation steps of the embodiment 1, the toluene diisocyanate in the embodiment 1 is changed into the diphenylmethane diisocyanate, and the hydroxyl-terminated polyether quaternary ammonium salt with the structure shown in the formula (II-1) is changed into the hydroxyl-terminated polyether quaternary ammonium salt with the structure shown in the formula (II-2), so that the self-closed end isocyanate-based polyurethane prepolymer-3 is prepared. The analysis and detection result shows that the deblocking temperature is about 112 ℃; and (3) storing the self-closed end isocyanate-based polyurethane prepolymer-3 in a closed manner for a long time at normal temperature.
Wherein the hydroxyl-terminated polyether quaternary ammonium salt of the formula (II-2) has the following structure:
example 4 preparation of self-blocked isocyanate-based polyurethane prepolymer-4
According to the method and the operation steps of the embodiment 1, the toluene diisocyanate in the embodiment 1 is changed into isophorone diisocyanate, and the hydroxyl-terminated polyether quaternary ammonium salt with the structure shown in the formula (II-1) is changed into the hydroxyl-terminated polyether quaternary ammonium salt with the structure shown in the formula (II-3), so that the self-closed isocyanate-terminated polyurethane prepolymer-4 is prepared. The analysis and detection result shows that the deblocking temperature is about 115 ℃; and (3) storing the self-closed end isocyanate-based polyurethane prepolymer-4 in a closed manner for a long time at normal temperature.
Wherein the hydroxyl-terminated polyether quaternary ammonium salt of the formula (II-3) has the following structure:
Claims (8)
1. a self-sealing polyurethane prepolymer is characterized by having a structure represented by general formula (I):
wherein R in the general formula (I)1And R2Alkyl refers to C1～C18A hydrocarbyl group;
is selected from C1～C18Alkylene or
Wherein q is a natural number between 1 and 200; n is selected from natural numbers between 2 and 2000, and m is selected from natural numbers between 1 and 2000.
2. A self-closing polyurethane prepolymer according to claim 1, characterised in that said self-closing polyurethane prepolymer is prepared by a process comprising: weighing polyisocyanate and an organic solvent in a reactor, and controlling the temperature to be 50-90 ℃; according to the molar ratio of isocyanate (-NCO) to hydroxyl (-OH) of 2.0-2.2, then weighing hydroxyl-terminated polyether quaternary ammonium salt and a catalyst, slowly adding the weighed hydroxyl-terminated polyether quaternary ammonium salt and the catalyst into a reactor, and stirring and reacting for 2-12 hours; in the process, a di-n-butylamine titration analysis method is adopted, after the-NCO content in the reaction materials in the reactor is checked and analyzed to be consistent with a preset value, the temperature of the materials in the reactor is reduced to room temperature, and the solution of the isocyanate-terminated polyurethane prepolymer is prepared; adding an alkali reagent into the isocyanate-terminated polyurethane prepolymer solution, stirring and reacting for 2-4 hours, and then increasing the temperature of the materials in the reactor to 50-90 ℃ for reaction until no-NCO is detected in the materials in the reactor; distilling to recover the organic solvent, the catalyst and the alkali reagent; then adding water with the quality similar to that of the solid remained in the reactor into the reaction system, stirring and dispersing, then blowing oxygen, detecting that the pH value of the material in the reactor is not reduced any more, sending the reaction product in the reaction kettle into a vacuum drier, and drying in vacuum at 60 ℃ to obtain the self-closed end isocyanate-based polyurethane prepolymer;
wherein the hydroxyl-terminated polyether quaternary ammonium salt has a structure shown in a general formula (II):
wherein R in the general formula (II)1And R2Are respectively selected from C1～C18One of the hydrocarbon groups, m is a natural number of 1 to 2000.
The mass ratio of the polyisocyanate to the hydroxyl-terminated polyether quaternary ammonium salt to the catalyst to the alkali reagent to the organic solvent is 100/50-500/0.5-5/5-500/100-1000.
3. A self-closing polyurethane prepolymer according to claim 2 characterised in that the polyisocyanate has the structure of formula (iii):
wherein in the general formula (III)
Is selected from C1～C18Alkylene or
Wherein q is a natural number between 1 and 200.
4. The self-sealing polyurethane prepolymer according to claim 2, wherein the organic solvent is one or more selected from acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, 1, 4-dioxane, chlorobenzene, chloroform, 1, 2-dichloroethane, toluene, xylene, decalin, methyl acetate, ethyl acetate, butyl acetate, N-methylpyrrolidone, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, N-dimethylformamide, N-dimethylacetamide, triethylamine, tributylamine, p-dimethylaminopyridine, N '-tetramethylethylenediamine, triethylenediamine, N' -dimethylpiperazine, N-methylmorpholine and dimethylsulfoxide.
5. The self-sealing polyurethane prepolymer as claimed in claim 2, wherein the catalyst is a compound of organic amine and organic tin, and the mass ratio of the organic amine to the organic tin is 1: 0.5-5;
wherein the organic amine refers to one of triethylamine, tributylamine, 4-dimethylamino pyridine, N, N, N ', N ' -tetramethyl ethylenediamine, triethylene diamine, N, N ' -dimethyl piperazine or N-methyl morpholine;
the organic tin refers to one of dibutyltin dilaurate, stannous octoate, stannous oxalate, dibutyltin dimaleate, dibutyltin didodecyl sulfide or dibutyltin diacetate.
6. The self-sealing polyurethane prepolymer of claim 2, wherein the base reagent is selected from one of triethylamine, tributylamine, 4-dimethylaminopyridine, N '-tetramethylethylenediamine, triethylenediamine, N' -dimethylpiperazine, or N-methylmorpholine.
7. The self-sealing polyurethane prepolymer according to claim 2, wherein the hydroxyl-terminated polyether quaternary ammonium salt of the general formula (ii) is prepared by weighing 5-chloromethyl salicylaldehyde and tertiary amino polyethylene glycol in an equimolar ratio, dissolving the weighed 5-chloromethyl salicylaldehyde and tertiary amino polyethylene glycol in a solvent to obtain a 5-chloromethyl salicylaldehyde solution and a tertiary amino polyethylene glycol solution, controlling the temperature at 0-100 ℃, adding the 5-chloromethyl salicylaldehyde solution to the tertiary amino polyethylene glycol solution, stirring for reaction for 2-20 hours, filtering, and drying a filter cake to obtain the hydroxyl-terminated polyether quaternary ammonium salt of the general formula (ii);
wherein the tertiary amino polyethylene glycol has a structure shown in a general formula (IV):
wherein R in the general formula (IV)1And R2Are respectively selected from C1～C18One of the hydrocarbon groups, m is a natural number of 1 to 2000.
8. The self-sealing polyurethane prepolymer according to claim 7, wherein the solvent is one or more selected from the group consisting of methanol, ethanol, propanol, butanol, cyclohexanol, acetone, butanone, cyclohexanone, tetrahydrofuran, 1, 4-dioxane, chlorobenzene, chloroform, 1, 2-dichloroethane, toluene, xylene, decalin, methyl acetate, ethyl acetate, butyl acetate, N-methylpyrrolidone, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, N-dimethylformamide, N-dimethylacetamide, and dimethylsulfoxide; the dosage of the solvent is 0.5-2.5 times of the mass of the 5-chloromethyl salicylaldehyde or the mass of the tertiary amine polyethylene glycol.
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