CN114163606B - Preparation and detection method of dynamic cross-linked self-repairing film - Google Patents
Preparation and detection method of dynamic cross-linked self-repairing film Download PDFInfo
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- CN114163606B CN114163606B CN202111641432.7A CN202111641432A CN114163606B CN 114163606 B CN114163606 B CN 114163606B CN 202111641432 A CN202111641432 A CN 202111641432A CN 114163606 B CN114163606 B CN 114163606B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000001514 detection method Methods 0.000 title abstract description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 42
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 30
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims abstract description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 14
- 150000002009 diols Chemical class 0.000 claims abstract description 14
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 14
- 239000004417 polycarbonate Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000009833 condensation Methods 0.000 claims abstract description 4
- 230000005494 condensation Effects 0.000 claims abstract description 4
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 4
- 238000010992 reflux Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 2
- 238000001291 vacuum drying Methods 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 229920006264 polyurethane film Polymers 0.000 abstract description 11
- 230000008439 repair process Effects 0.000 abstract description 11
- 239000004814 polyurethane Substances 0.000 abstract description 8
- 229920002635 polyurethane Polymers 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 6
- 239000002861 polymer material Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000013003 healing agent Substances 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000013473 artificial intelligence Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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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
- C08G18/75—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
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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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
- C08G18/83—Chemically modified polymers
- C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N3/00—Investigating strength properties of solid materials by application of mechanical stress
- G01N3/08—Investigating strength properties of solid materials by application of mechanical stress by applying steady tensile or compressive forces
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
- G01N2021/3572—Preparation of samples, e.g. salt matrices
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2203/00—Investigating strength properties of solid materials by application of mechanical stress
- G01N2203/0058—Kind of property studied
- G01N2203/0069—Fatigue, creep, strain-stress relations or elastic constants
- G01N2203/0075—Strain-stress relations or elastic constants
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation and detection method of a dynamic cross-linking self-repairing film, which comprises the steps of firstly adding isophorone diisocyanate, polycarbonate diol and a catalyst into a three-neck flask with mechanical stirring and condensation reflux, and heating to 80 ℃ for reaction for 2 hours to obtain a polyurethane prepolymer; then dissolving N-methyldiethanolamine in tetrahydrofuran, slowly dripping the N-methyldiethanolamine into the polyurethane prepolymer by using a constant pressure dropping funnel, and carrying out chain extension reaction for 2 hours at 80 ℃ after the dripping is finished; then adding citric acid and reacting for 0.5 hour at 80 ℃, and finally obtaining amphoteric polyurethane, which has the beneficial effects that: the zwitterionic polyurethane film designed and synthesized by the experiment improves the repeated damage repair efficiency and mechanical property of polyurethane, and provides a theoretical basis for designing and preparing self-repairing polyurethane.
Description
Technical Field
The invention relates to the technical field of material science, in particular to a preparation and detection method of a dynamic cross-linked self-repairing film.
Background
Material science, new energy, informatization and life science are considered as four major subjects of current times development. The material science is used as the first place, and is the material foundation for development of various industries. Among them, the organic polymer materials are most widely used. With the development of the age, the requirements of people on materials are increasingly increased, and the functionalization is gradually changed into intelligentization. The self-repairing material is also a novel intelligent material, and in daily life, the self-repairing material has a function similar to biological self-repairing, so that the self-repairing material is more convenient and efficient to use. In some high-end science and technology fields, the self-repairing material also has great remarkable color, such as aerospace science and technology, artificial intelligence, electronic science and technology, sensors and the like, and has very wide application prospect and great value. The polymer material is damaged under the external effects of heat, light, ultraviolet and the like, so that the mechanical property strength of the polymer material is affected, and the service life and the safety of the polymer material are reduced. The self-repairing material can perfectly solve the defect, prolong the service life of the material and improve the safety and reliability of the material.
Self-repair of polyurethane materials can be categorized into external and intrinsic repair. The foreign-assistance repair can be divided into: self-healing of loading a healing agent in microcapsules; self-healing of loading a healing agent on a pipe. Its repair effect is affected by the effect of the external aid. Intrinsic polyurethane self-repair is achieved by using the internal reversible molecular chemical structure of the polymer material. Compared with the external-assistance type, the self-repairing method can realize multiple times of self-repairing. The most widely used repair methods at present are microreactors and reversible chemistry. The microreactor method has high repair efficiency, but cannot realize multiple repairs. Reversible chemical repair can be initiated by stimulation by heat, light, etc. In summary, the self-repairing polyurethane materials in the current market have lower flexibility, the mechanical properties are reduced along with the increase of repairing times, the self-repairing cycle times are limited, and the practical application performance is limited.
Disclosure of Invention
The invention aims to provide a preparation and detection method of a dynamic cross-linked self-repairing film, which aims to solve the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions: a preparation method of a dynamic cross-linked self-repairing film comprises the following steps:
step one: preparing materials, namely preparing 2-4 parts of isophorone diisocyanate, 1-2 parts of polycarbonate diol, 1-2 parts of N-methyldiethanolamine, 1-2 parts of citric acid, a proper amount of catalyst and 1-4 parts of tetrahydrofuran according to relative molecular mass;
step two: firstly, adding isophorone diisocyanate, polycarbonate diol and a catalyst into a three-neck flask with mechanical stirring and condensation reflux, and heating to 80 ℃ for reaction for 2 hours to obtain a polyurethane prepolymer;
step three: then dissolving N-methyldiethanolamine in tetrahydrofuran, slowly dripping the N-methyldiethanolamine into the polyurethane prepolymer obtained in the step two by using a constant pressure dropping funnel, and carrying out chain extension reaction for 2 hours at 80 ℃ after the dripping is finished;
step four: citric acid was then added and reacted at 80 degrees celsius for 0.5 hours, and the amphoteric urethane was finally obtained.
As a further scheme of the invention: in the second step, the catalyst is specifically dibutyl tin dilaurate, and the dropping amount of the catalyst is 5-10 g.
As a further scheme of the invention: in the third step, when the reactant becomes viscous while the chain extension reaction is performed, tetrahydrofuran is continuously added to reduce the viscosity.
As a further scheme of the invention: in step one, the material is vacuum dried for 1-2 hours while it is being prepared.
A detection test method of a dynamic cross-linked self-repairing film comprises the following steps:
s1: cutting the amphoteric polyurethane film into two sections from the middle by using scissors, then tightly attaching the fracture parts of the two sections together, and adding deionized water at the room temperature of 30 ℃;
s2: repeating the step S1, selecting 2-5 groups of samples, and performing record inspection on each group of samples;
s3: shooting microscopic fracture pictures every 5 minutes until fracture repair between two sections of amphoteric polyurethane films is not changed any more;
s4: and stretching and bending the repaired film, simultaneously adopting the amphoteric polyurethane films manufactured in different proportions to continuously test the sample, and finally analyzing to obtain the optimal reagent proportion.
Compared with the prior art, the invention has the beneficial effects that: the zwitterionic polyurethane film designed and synthesized by the experiment improves the repeated damage repair efficiency and mechanical property of polyurethane, and provides a theoretical basis for designing and preparing self-repairing polyurethane.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a table of ratios of films according to the present invention;
FIG. 2 is a schematic illustration of the reaction principle of the present invention for the synthesis of an amphoteric urethane;
FIG. 3 is a graph showing the stretching curves of films according to the present invention at various ratios;
FIG. 4 is an infrared spectrum of a film according to the present invention at different scales;
FIG. 5 is a thermogravimetric analysis of films according to the present invention at various scales.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1-3, in an embodiment of the invention, a method for preparing a dynamic cross-linked self-repairing film includes the following steps:
step one: preparing materials, namely preparing 2-4 parts of isophorone diisocyanate, 1-2 parts of polycarbonate diol, 1-2 parts of N-methyldiethanolamine, 1-2 parts of citric acid, a proper amount of catalyst and 1-4 parts of tetrahydrofuran according to relative molecular mass;
step two: firstly, adding isophorone diisocyanate, polycarbonate diol and a catalyst into a three-neck flask with mechanical stirring and condensation reflux, and heating to 80 ℃ for reaction for 2 hours to obtain a polyurethane prepolymer;
step three: then dissolving N-methyldiethanolamine in tetrahydrofuran, slowly dripping the N-methyldiethanolamine into the polyurethane prepolymer obtained in the step two by using a constant pressure dropping funnel, and carrying out chain extension reaction for 2 hours at 80 ℃ after the dripping is finished;
step four: citric acid was then added and reacted at 80 degrees celsius for 0.5 hours, and the amphoteric urethane was finally obtained.
A detection test method of a dynamic cross-linked self-repairing film comprises the following steps:
s1: cutting the amphoteric polyurethane film into two sections from the middle by using scissors, then tightly attaching the fracture parts of the two sections together, and adding deionized water at the room temperature of 30 ℃;
s2: repeating the step S1, selecting 2-5 groups of samples, and performing record inspection on each group of samples;
s3: shooting microscopic fracture pictures every 5 minutes until fracture repair between two sections of amphoteric polyurethane films is not changed any more;
s4: and stretching and bending the repaired film, simultaneously adopting the amphoteric polyurethane films manufactured in different proportions to continuously test the sample, and finally analyzing to obtain the optimal reagent proportion.
Embodiment one:
preparing 4 parts of isophorone diisocyanate, 2 parts of polycarbonate diol, 2 parts of N-methyldiethanolamine, 2 parts of citric acid, 40 g of a catalyst and 4 parts of tetrahydrofuran, wherein each part of isophorone diisocyanate is 222 g, each part of polycarbonate diol is 1000 g, each part of N-methyldiethanolamine is 119 g, each part of citric acid is 192 g, and each part of tetrahydrofuran is 8 ml;
detecting tensile mechanical properties, namely detecting a stress-strain curve of the amphoteric polyurethane film by using a stretcher, wherein the stretching speed is 60mm/min, preferentially measuring the width and thickness of the film, taking the average value of the film after multiple times of testing, and drawing a stress-strain curve graph after obtaining data;
embodiment two:
preparing 4 parts of isophorone diisocyanate, 2 parts of polycarbonate diol, 1 part of N-methyldiethanolamine, 2 parts of citric acid, 36 g of a catalyst and 3 parts of tetrahydrofuran, wherein each part of isophorone diisocyanate is 222 g, each part of polycarbonate diol is 1000 g, each part of N-methyldiethanolamine is 119 g, each part of citric acid is 192 g, and each part of tetrahydrofuran is 8 ml;
infrared spectrum detection, namely infrared spectrum detection is carried out on the amphoteric polyurethane film by utilizing an infrared spectrometer, and the test range is 4000-500cm -1 Resolution of 4cm -1 ；
Embodiment III:
preparing 4 parts of isophorone diisocyanate, 2 parts of polycarbonate diol, 2 parts of N-methyldiethanolamine, 0 part of citric acid, 30 g of a catalyst and 3 parts of tetrahydrofuran, wherein each part of isophorone diisocyanate is 222 g, each part of polycarbonate diol is 1000 g, each part of N-methyldiethanolamine is 119 g, each part of citric acid is 192 g, and each part of tetrahydrofuran is 8 ml;
and (3) performing thermogravimetric analysis on the amphoteric polyurethane film, testing the film by using a thermal analyzer, wherein the heating speed is 10 ℃/min, the test scanning range is 30-700 ℃, and the nitrogen flow rate is protected to be 20mL/min.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (2)
1. The preparation method of the dynamic cross-linked self-repairing film is characterized by comprising the following steps of:
step one: the preparation of the material, which comprises the steps of weighing the following raw materials, by weight, 2-4 parts of isophorone diisocyanate, 1-2 parts of polycarbonate diol, 1-2 parts of N-methyldiethanolamine, 1-2 parts of citric acid, a proper amount of catalyst and 1-4 parts of tetrahydrofuran, and carrying out vacuum drying on the raw materials for 1-2 hours;
wherein, the isophorone diisocyanate is 222 g per part, the polycarbonate diol is 1000 g per part, the N-methyl diethanolamine is 119 g per part, the citric acid is 192 g per part, and the tetrahydrofuran is 8 ml per part;
step two: firstly, adding isophorone diisocyanate, polycarbonate diol and a catalyst into a three-neck flask with mechanical stirring and condensation reflux, and heating to 80 ℃ for reaction for 2 hours to obtain a polyurethane prepolymer;
step three: then dissolving N-methyldiethanolamine in tetrahydrofuran, slowly dripping the N-methyldiethanolamine into the polyurethane prepolymer obtained in the step two by using a constant pressure dropping funnel, and carrying out chain extension reaction for 2 hours at 80 ℃ after the dripping is finished;
step four: citric acid was then added and reacted at 80 degrees celsius for 0.5 hours, and the amphoteric urethane was finally obtained.
2. The method for preparing a dynamic crosslinked self-repairing film according to claim 1, wherein in the second step, the catalyst is dibutyltin dilaurate, and the dropping amount is 5-10 g.
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