阅读说明：本技术 一种自愈合疏水型聚氨酯及其制备方法与应用 (Self-healing hydrophobic polyurethane and preparation method and application thereof ) 是由 应邬彬 张若愚 朱锦 黄骏成 杨勇 于 2019-09-30 设计创作，主要内容包括：本发明公开了一种自愈合疏水型聚氨酯及其制备方法与应用。所述聚氨酯包括具有疏水性能的软段结构和具有自愈合功能的硬段结构,所述硬段结构包括短链硬段,以及由所述短链硬段形成的、连续相的连续硬段；其中,所述连续硬段的两端分别与所述软段结构连接,所述短链硬段分布于所述软段结构中,所述软段结构包含疏水型聚二醇,所述硬段结构包含具有动态共价键的扩链剂与异氰酸酯。本发明提供的聚氨酯具有优异的抗撕裂能力,其在50％破裂的情况下,还具有324％的断裂伸长；同时,此聚氨酯在室温下的自愈合速度为1.33μm/min,并且随着温度的升高自愈合能力逐渐增强。另外,本发明提供的制备方法具有工艺简单,原料易得,材料性能可控性强等特点,有非常广泛的应用前景。(The invention discloses self-healing hydrophobic polyurethane and a preparation method and application thereof. The polyurethane comprises a soft segment structure with hydrophobic property and a hard segment structure with self-healing function, wherein the hard segment structure comprises short-chain hard segments and continuous hard segments of continuous phases formed by the short-chain hard segments; the two ends of the continuous hard segment are respectively connected with the soft segment structure, the short-chain hard segment is distributed in the soft segment structure, the soft segment structure comprises hydrophobic polyglycol, and the hard segment structure comprises a chain extender with a dynamic covalent bond and isocyanate. The polyurethane provided by the invention has excellent tear resistance, and also has 324% of elongation at break under the condition of 50% of rupture; meanwhile, the self-healing speed of the polyurethane at room temperature is 1.33 mu m/min, and the self-healing capability is gradually enhanced along with the increase of the temperature. In addition, the preparation method provided by the invention has the characteristics of simple process, easily obtained raw materials, strong controllability of material performance and the like, and has very wide application prospect.)

1. A self-healing hydrophobic polyurethane, which is characterized in that the polyurethane comprises a soft segment structure with hydrophobic property and a hard segment structure with self-healing function, wherein the hard segment structure comprises short-chain hard segments and continuous hard segments which are formed by the short-chain hard segments and are in continuous phase; the two ends of the continuous hard segment are respectively connected with the soft segment structure, the short-chain hard segment is distributed in the soft segment structure, the soft segment structure comprises hydrophobic polyglycol, and the hard segment structure comprises a chain extender with a dynamic covalent bond and isocyanate.

2. A self-healing hydrophobic polyurethane according to claim 1, wherein the hydrophobic polyglycol has hydroxyl groups at both ends of a molecular chain thereof, and a contact angle of a surface of the hydrophobic polyglycol with water is 60 ° or more;

preferably, the hydrophobic polyglycol comprises any one or a combination of two or more of polyester glycol, polyolefin glycol, polyfluoride glycol and polyether glycol;

preferably, the molecular weight of the hydrophobic polyglycol is 600-5000 g/mol.

3. A self-healing hydrophobic polyurethane according to claim 1, wherein the chain extender comprises a small molecule diol having dynamic covalent bonds;

preferably, the small molecule diol has a structure shown in formula (I):

wherein R is any one of alkyl, alkenyl and alkynyl, and n and m are both selected from 1-10;

preferably, the dynamic bond comprises any one of a dynamic disulfide bond, a dynamic borate isocyanate and a dynamic schiff base bond;

preferably, the molecular weight of the small-molecule diol is 600-5000 g/mol.

4. A self-healing hydrophobic polyurethane according to claim 1, wherein the isocyanate comprises a diisocyanate; preferably, the diisocyanate includes any one or a combination of two or more of isophorone diisocyanate, toluene diisocyanate, 1, 6-hexamethylene diisocyanate, xylylene diisocyanate, 1, 5-naphthalene diisocyanate, and dicyclohexylmethane diisocyanate.

5. A self-healing hydrophobic polyurethane according to any one of claims 1 to 4, wherein: the self-healing speed of the self-healing hydrophobic polyurethane at room temperature is 0.1-1.33 mu m/min;

preferably, the contact angle of the self-healing hydrophobic polyurethane surface and water is 60-180 degrees.

6. The method for preparing self-healing hydrophobic polyurethane according to any one of claims 1 to 5, comprising: in a protective atmosphere, reacting a uniformly mixed reaction system containing hydrophobic polyglycol, isocyanate, a chain extender, a catalyst and a solvent at 25-100 ℃ for 1-24h, and performing post-treatment to obtain the self-healing hydrophobic polyurethane.

7. The method according to claim 6, comprising: uniformly mixing hydrophobic polyglycol, isocyanate, a chain extender, a catalyst and an organic solvent in a protective atmosphere to form the uniformly mixed reaction system, controlling the concentration of reactants in the uniformly mixed reaction system to be 10-50 wt%, then reacting for 1-24h at 25-100 ℃, and then carrying out post-treatment to obtain the self-healing hydrophobic polyurethane.

8. The method of claim 7, wherein: the molar ratio of hydroxyl groups to isocyanate groups in the uniformly mixed reaction system is 0.5:1-2: 1;

and/or the molar ratio of the chain extender to the hydrophobic polyglycol is 1: 99-99: 1;

and/or, the amount of the catalyst is 0.1-1 wt%;

and/or, the protective atmosphere comprises an inert atmosphere and/or nitrogen, preferably an argon atmosphere;

and/or the catalyst comprises any one or the combination of more than two of bis-dimethylamino ethyl ether, pentamethyl diethylenetriamine, dimethyl cyclohexylamine, dibutyltin dilaurate, organic bismuth and triazine trimerization catalyst.

9. The method for preparing according to claim 6 or 7, characterized in that the post-treatment comprises: after the reaction is finished, washing a solid obtained by the reaction with a washing solution, and then carrying out vacuum drying at the temperature of 60-100 ℃ for 12-36h to obtain the self-healing hydrophobic polyurethane; preferably, the washing liquid comprises distilled water.

10. Use of the self-healing hydrophobic polyurethane according to any one of claims 1 to 5 in the field of flexible devices; preferably, the use comprises the use of a self-healing hydrophobic polyurethane in a flexible electronic device, preferably an electronic skin matrix material.

Technical Field

The invention belongs to the technical field of polyurethane, and particularly relates to self-healing hydrophobic polyurethane as well as a preparation method and application thereof.

Background

The polyurethane has a low glass transition temperature (T)_g) Soft segment and has a higher T_gThe hard segment of (2). In the condensed state, the two thermodynamically incompatible components undergo microphase separation, forming soft and hard phase domains, respectively. Lower T of soft phase region_gMaking it reversibly deformable while the hard phase region has strong hydrogen bonds or crystalline states, which can provide good shape fixing effect. Thus, polyurethanes have superior toughness and tear resistance compared to other homopolymer-type elastomers. Meanwhile, the elastic matrix with the required modulus and deformability can be obtained by adjusting the ratio of the soft segment and the hard segment. Polyurethanes are increasingly favored in the field of flexible electronic skins due to their excellent mechanical properties and are used to develop various functional composites based on them.

Recently, in order to further simulate the function of human skin, researchers have conducted studies on the self-healing functionality in addition to high-toughness polyurethane. In the research of self-healing materials, researchers often introduce reversible (dynamic) covalent bonds or self-assembly groups to achieve goals such as hydrogen bonding, Diels-Alder bonds, metal ligand bonds, urea chemistry, dynamic disulfide bonds, etc., but self-healing efficiency is low. However, the introduction of these dynamic covalent bonds or self-assembling groups into polyurethanes and the achievement of high efficiency self-healing have been rarely reported. At the same time, polyurethanes have a major disadvantage-hydrophilicity. Polyurethanes are strongly hydrophilic due to the presence of urethane linkages and typically contain polyether-Polytetrahydrofuran (PTMG) as a soft segment, making them prone to absorb water in humid environments, which can cause signal interference to flexible electronics.

Thus, both self-healing and hydrophobicity of the polyurethane are important prerequisites to ensure stable operation of the flexible electronic skin. Up to now, no documents and patents of polyurethane having both high-efficiency self-healing and hydrophobic properties have been reported in the prior art.

Disclosure of Invention

The invention mainly aims to provide self-healing hydrophobic polyurethane, and a preparation method and application thereof, so as to overcome the defects of the prior art.

In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:

the embodiment of the invention provides self-healing hydrophobic polyurethane, which comprises a soft segment structure with hydrophobic property and a hard segment structure with self-healing function, wherein the hard segment structure comprises short-chain hard segments and continuous hard segments which are formed by the short-chain hard segments and are continuous in phase; the two ends of the continuous hard segment are respectively connected with the soft segment structure, the short-chain hard segment is distributed in the soft segment structure, the soft segment structure comprises hydrophobic polyglycol, and the hard segment structure comprises a chain extender with a dynamic covalent bond and isocyanate.

The embodiment of the invention also provides a preparation method of the polyurethane, which comprises the following steps:

in a protective atmosphere, reacting a uniformly mixed reaction system containing hydrophobic polyglycol, isocyanate, a chain extender, a catalyst and a solvent at 25-100 ℃ for 1-24h, and performing post-treatment to obtain the self-healing hydrophobic polyurethane.

The preparation method of the polyurethane adopts a one-step synthesis method, has the characteristics of simple method, easily obtained raw materials, strong controllability of material performance and the like, and has very wide application prospect.

The embodiment of the invention also provides application of the self-healing hydrophobic polyurethane in the field of flexible devices.

Compared with the prior art, the polyurethane provided by the invention has excellent tear resistance, and also has 324% of breaking elongation under the condition of 50% of rupture; meanwhile, the self-healing speed of the polyurethane at room temperature is 1.33 mu m/min, and the self-healing capability is gradually enhanced along with the increase of the temperature. In addition, the preparation method provided by the invention has the characteristics of simple process, easily obtained raw materials, strong controllability of material performance and the like, and has very wide application prospect.

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.

FIG. 1 is a schematic structural view of a polyurethane according to the present invention;

FIG. 2 is a schematic structural view of a hydrophobic polyglycol of the present invention;

FIG. 3 is a NMR chart of the self-healing hydrophobic polyurethane of examples 1 to 4 of the present invention;

FIG. 4 is a microscope image of the results of a self-healing test of polyurethane at room temperature in example 1 of the present invention;

FIG. 5 is a microscope image of the results of a self-healing test of polyurethane at 60 ℃ in example 1 of the present invention;

FIG. 6 is a graph of the contact angle of the polyurethane surface with water and the contact angles after soaking for 1 day and 3 days in example 1 of the present invention;

fig. 7 is a graph of the mechanical properties of the self-healing hydrophobic polyurethanes of examples 1-4 of the present invention.

Detailed Description

In view of the defects of the prior art, the inventor of the present invention provides a technical scheme of the present invention through long-term research and a great deal of practice, wherein self-healing hydrophobic polyurethane is synthesized by adopting a one-step method through a hydrophobic polyglycol soft segment, micromolecule diol containing dynamic covalent bonds and isocyanate, and the hydrophobic soft segment is introduced, so that the hydrophobic capacity of the material is improved, and the problem of water-borne deformation of polyurethane caused by a urethane bond and a hydrophilic soft segment is solved.

The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

An aspect of an embodiment of the present invention provides a self-healing hydrophobic polyurethane, which includes a soft segment structure having hydrophobic property and a hard segment structure having self-healing function, where the hard segment structure includes a short-chain hard segment and a continuous hard segment of a continuous phase formed by the short-chain hard segment; the two ends of the continuous hard segment are respectively connected with the soft segment structure, the short-chain hard segment is distributed in the soft segment structure, the soft segment structure comprises hydrophobic polyglycol, and the hard segment structure comprises a chain extender with a dynamic covalent bond and isocyanate.

The structural schematic of the polyurethane of the present invention is shown in FIG. 1.

In some embodiments, the hydrophobic polyglycol has hydroxyl groups at both ends of the molecular chain, and the contact angle of the hydrophobic polyglycol surface with water is 60 ° or more.

Further, the hydrophobic polyglycol includes any one or a combination of two or more of polyester glycol, polyolefin glycol, polyfluoride glycol, and polyether glycol, and is not limited thereto.

Further, the molecular weight of the hydrophobic polyglycol is 600-5000g/mol, wherein the structural diagram of the hydrophobic polyglycol is shown in FIG. 2.

In some embodiments, the chain extender includes a small molecule diol having dynamic covalent bonds, and is not limited thereto.

Further, the small molecule diol has a structure shown in a formula (I):

wherein R is any one of alkyl, alkenyl and alkynyl, and n and m are both selected from 1-10;

further, the dynamic bond includes any one of a dynamic disulfide bond, a dynamic boronate isocyanate, and a dynamic schiff base bond, but is not limited thereto.

Further, the molecular weight of the small molecular diol is 600-5000 g/mol.

In some embodiments, the isocyanate comprises a diisocyanate.

Further, the diisocyanate includes any one or a combination of two or more of isophorone diisocyanate, toluene diisocyanate, 1, 6-hexamethylene diisocyanate, xylylene diisocyanate, 1, 5-naphthalene diisocyanate, and dicyclohexylmethane diisocyanate, and is not limited thereto.

In some embodiments, the self-healing hydrophobic polyurethane has an elongation at break of 324% at 50% rupture.

Further, the self-healing speed of the polyurethane at room temperature is 0.1-1.33 μm/min;

further, the contact angle between the self-healing hydrophobic polyurethane surface and water is 60-180 degrees.

One aspect of the embodiment of the present invention further provides a preparation method of the self-healing hydrophobic polyurethane, including:

in a protective atmosphere, reacting a uniformly mixed reaction system containing hydrophobic polyglycol, isocyanate, a chain extender, a catalyst and a solvent at 25-100 ℃ for 1-24h, and performing post-treatment to obtain the self-healing hydrophobic polyurethane.

In some embodiments, the method of making specifically comprises: uniformly mixing hydrophobic polyglycol, isocyanate, a chain extender, a catalyst and an organic solvent in a protective atmosphere to form the uniformly mixed reaction system, controlling the concentration of reactants in the uniformly mixed reaction system to be 10-50 wt%, then reacting for 1-24h at 25-100 ℃, and then carrying out post-treatment to obtain the self-healing hydrophobic polyurethane.

Further, the molar ratio of hydroxyl groups to isocyanate groups in the uniformly mixed reaction system is 0.5:1-2: 1.

Further, the molar ratio of the chain extender to the hydrophobic polyglycol is 1: 99-99: 1.

Further, the catalyst is used in an amount of 0.1 to 1 wt%.

Further, the protective atmosphere comprises an inert atmosphere and/or nitrogen, preferably an argon atmosphere.

Further, the catalyst includes any one or a combination of two or more of DY-1 (bis-dimethylaminoethyl ether), DY-5 (pentamethyldiethylenetriamine), DY-8 (dimethylcyclohexylamine), DY-12 (dibutyltin dilaurate), DY-20 (organic bismuth) and DY-41 (triazine trimerization catalyst), and is not limited thereto.

Further, the post-processing comprises: after the reaction is finished, washing a solid obtained by the reaction with a washing solution, and then carrying out vacuum drying at the temperature of 60-100 ℃ for 12-36h to obtain the self-healing hydrophobic polyurethane; preferably, the washing liquid comprises distilled water.

The embodiment of the invention also provides the application of the self-healing hydrophobic polyurethane in the field of flexible devices; preferably, the use comprises the use of a self-healing hydrophobic polyurethane in a flexible electronic device, preferably an electronic skin matrix material.

The technical solution of the present invention is further described in detail with reference to several preferred embodiments, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following embodiments.

In the examples of the present invention, NMR spectroscopy¹H-NMR was measured using 400AVANCE type III Spectrometer (Spectrometer) from Bruker, 400MHz, deuterated chloroform (CDCl)₃) (ii) a The self-healing test was performed by means of an optical microscope (Olympus/BX 51TF Instec H601, Japan) equipped with a hot stage.

Example 1

Fresh hydroxyl-terminated polybutadiene, isophorone diisocyanate, dibutyltin dilaurate, bis (4-hydroxyphenyl) disulfide and tetrahydrofuran were poured into a three-necked reactor equipped with a mechanical stirrer in a glove box charged with 99.999% Ar for a one-shot reaction. Wherein [ hydroxyl-terminated polybutadiene ]/[ bis (4-hydroxyphenyl) disulfide ] - [ 1/99 (mass ratio), the molecular weight of the hydroxyl-terminated polybutadiene was 600g/mol, dibutyltin dilaurate was 0.1 wt% of the total mass of the reactants, the molar ratio of hydroxyl groups to isocyanate groups was 0.5:1, the concentration of all reactants was 10 wt%, the reaction temperature was 25 ℃, and the reaction time was 1 h. Finally, the polymer precipitate is washed with distilled water for several times, and is dried in vacuum at 60 ℃ for 12h to constant weight, so as to obtain the polyurethane PU-1 (shown in a nuclear magnetic resonance hydrogen spectrum chart in figure 3, self-healing performance in figures 4 a-4 f and 5 a-5 f, hydrophobic performance in figures 6a-6c, and mechanical performance in figure 7).

Example 2

Fresh hydroxyl-terminated polybutadiene, isophorone diisocyanate, dibutyltin dilaurate, bis (4-hydroxyphenyl) disulfide and tetrahydrofuran were poured into a three-necked reactor equipped with a mechanical stirrer in a glove box charged with 99.999% Ar for a one-shot reaction. Wherein [ hydroxyl-terminated polybutadiene ]/[ bis (4-hydroxyphenyl) disulfide ] - [ 50/50 (mass ratio), the molecular weight of the hydroxyl-terminated polybutadiene was 600g/mol, dibutyltin dilaurate was 0.1 wt% of the total mass of the reactants, the molar ratio of hydroxyl groups to isocyanate groups was 0.5:1, the concentration of all reactants was 10 wt%, the reaction temperature was 25 ℃, and the reaction time was 1 h. Finally, washing the polymer precipitate with distilled water for several times, and drying in vacuum at 60 ℃ for 12h to constant weight to obtain the polyurethane PU-2 (shown in a nuclear magnetic resonance hydrogen spectrum figure 3, and shown in a mechanical property figure 7).

Example 3

Fresh hydroxyl-terminated polybutadiene, isophorone diisocyanate, dibutyltin dilaurate, bis (4-hydroxyphenyl) disulfide and tetrahydrofuran were poured into a three-necked reactor equipped with a mechanical stirrer in a glove box charged with 99.999% Ar for a one-shot reaction. Wherein [ hydroxyl-terminated polybutadiene ]/[ bis (4-hydroxyphenyl) disulfide ] - [ 99/1 (mass ratio), the molecular weight of the hydroxyl-terminated polybutadiene was 600g/mol, dibutyltin dilaurate was 0.1 wt% of the total mass of the reactants, the molar ratio of hydroxyl groups to isocyanate groups was 0.5:1, the concentration of all reactants was 10 wt%, the reaction temperature was 25 ℃, and the reaction time was 1 h. Finally, washing the polymer precipitate with distilled water for several times, and drying in vacuum at 60 ℃ for 12h to constant weight to obtain the polyurethane PU-3 (shown in a nuclear magnetic resonance hydrogen spectrum figure 3, and shown in a mechanical property figure 7).

Example 4

Fresh hydroxyl-terminated polybutadiene, isophorone diisocyanate, dibutyltin dilaurate, bis (4-hydroxyphenyl) disulfide and tetrahydrofuran were poured into a three-necked reactor equipped with a mechanical stirrer in a glove box charged with 99.999% Ar for a one-shot reaction. Wherein [ hydroxyl-terminated polybutadiene ]/[ bis (4-hydroxyphenyl) disulfide ] - [ 1/99 (mass ratio), the molecular weight of the hydroxyl-terminated polybutadiene was 5000g/mol, dibutyltin dilaurate was 0.1 wt% of the total mass of the reactants, the molar ratio of hydroxyl groups to isocyanate groups was 0.5:1, the concentration of all reactants was 10 wt%, the reaction temperature was 25 ℃, and the reaction time was 1 h. Finally, washing the polymer precipitate with distilled water for several times, and drying in vacuum at 60 ℃ for 12h to constant weight to obtain the polyurethane PU-4 (shown in a nuclear magnetic resonance hydrogen spectrum figure 3, and shown in a mechanical property figure 7).

Example 5

In a glove box charged with 99.999% Ar, fresh hydroxyl-terminated polybutadiene, toluene diisocyanate, bis-dimethylaminoethyl ether, bis (4-hydroxyphenyl) disulfide and tetrahydrofuran were poured into a three-necked reactor equipped with a mechanical stirrer to conduct the one-step reaction. Wherein [ hydroxyl-terminated polybutadiene ]/[ bis (4-hydroxyphenyl) disulfide ] - [ 1/99 (mass ratio), the molecular weight of the hydroxyl-terminated polybutadiene was 2000g/mol, bis-dimethylaminoethyl ether accounted for 0.1 wt% of the total mass of the reactants, the molar ratio of hydroxyl groups to isocyanate groups was 0.5:1, the concentration of all reactants was 10 wt%, the reaction temperature was 25 ℃, and the reaction time was 1 h. And finally washing the polymer precipitate with distilled water for several times, and drying in vacuum at 60 ℃ for 12h to constant weight to obtain the polyurethane PU-5.

Example 6

In a glove box charged with 99.999% Ar, fresh hydroxyl-terminated polybutadiene, xylylene diisocyanate, dimethylcyclohexylamine, bis (4-hydroxyphenyl) disulfide and tetrahydrofuran were poured into a three-necked reactor equipped with a mechanical stirrer to conduct a one-step reaction. Wherein [ hydroxyl-terminated polybutadiene ]/[ bis (4-hydroxyphenyl) disulfide ] - [ 1/99 (mass ratio), the molecular weight of the hydroxyl-terminated polybutadiene was 600g/mol, dimethylcyclohexylamine was present in an amount of 1 wt% based on the total mass of the reactants, the molar ratio of hydroxyl groups to isocyanate groups was 0.5:1, the concentration of all reactants was 10 wt%, the reaction temperature was 25 ℃, and the reaction time was 1 h. And finally washing the polymer precipitate with distilled water for several times, and drying in vacuum at 60 ℃ for 12h to constant weight to obtain the polyurethane PU-6.

Example 7

Fresh hydroxyl-terminated polybutadiene, isophorone diisocyanate, dibutyltin dilaurate, bis (4-hydroxyphenyl) disulfide and tetrahydrofuran were poured into a three-necked reactor equipped with a mechanical stirrer in a glove box charged with 99.999% Ar for a one-shot reaction. Wherein [ hydroxyl-terminated polybutadiene ]/[ bis (4-hydroxyphenyl) disulfide ] - [ 1/99 (mass ratio), the molecular weight of the hydroxyl-terminated polybutadiene was 600g/mol, dibutyltin dilaurate was 0.5 wt% of the total mass of the reactants, the molar ratio of hydroxyl groups to isocyanate groups was 0.5:1, the concentration of all reactants was 10 wt%, the reaction temperature was 25 ℃, and the reaction time was 1 h. And finally washing the polymer precipitate with distilled water for several times, and drying in vacuum at 60 ℃ for 12h to constant weight to obtain the polyurethane PU-7.

Example 8

Fresh hydroxyl-terminated polybutadiene, isophorone diisocyanate, dibutyltin dilaurate, bis (4-hydroxyphenyl) disulfide and tetrahydrofuran were poured into a three-necked reactor equipped with a mechanical stirrer in a glove box charged with 99.999% Ar for a one-shot reaction. Wherein [ hydroxyl-terminated polybutadiene ]/[ bis (4-hydroxyphenyl) disulfide ] - [ 1/99 (mass ratio), the molecular weight of the hydroxyl-terminated polybutadiene was 600g/mol, dibutyltin dilaurate was 0.1 wt% of the total mass of the reactants, the molar ratio of hydroxyl groups to isocyanate groups was 2:1, the concentration of all reactants was 10 wt%, the reaction temperature was 25 ℃, and the reaction time was 1 h. And finally washing the polymer precipitate with distilled water for several times, and drying in vacuum at 60 ℃ for 12h to constant weight to obtain the polyurethane PU-8.

Example 9

In a glove box charged with 99.999% Ar, fresh hydroxyl-terminated polybutadiene, 1, 5-naphthalene diisocyanate, organobismuth, bis (4-hydroxyphenyl) disulfide and tetrahydrofuran were poured into a three-necked reactor equipped with a mechanical stirrer to perform a one-step reaction. Wherein [ hydroxyl-terminated polybutadiene ]/[ bis (4-hydroxyphenyl) disulfide ] - [ 1/99 (mass ratio), the molecular weight of the hydroxyl-terminated polybutadiene was 600g/mol, the organic bismuth accounted for 0.1 wt% of the total mass of the reactants, the molar ratio of hydroxyl groups to isocyanate groups was 1:1, the concentration of all reactants was 10 wt%, the reaction temperature was 25 ℃, and the reaction time was 1 h. And finally washing the polymer precipitate with distilled water for several times, and drying in vacuum at 60 ℃ for 12h to constant weight to obtain the polyurethane PU-9.

Example 10

Fresh hydroxyl-terminated polybutadiene, isophorone diisocyanate, dibutyltin dilaurate, bis (4-hydroxyphenyl) disulfide and tetrahydrofuran were poured into a three-necked reactor equipped with a mechanical stirrer in a glove box charged with 99.999% Ar for a one-shot reaction. Wherein [ hydroxyl-terminated polybutadiene ]/[ bis (4-hydroxyphenyl) disulfide ] - [ 1/99 (mass ratio), the molecular weight of the hydroxyl-terminated polybutadiene was 600g/mol, dibutyltin dilaurate was 0.1 wt% of the total mass of the reactants, the molar ratio of hydroxyl groups to isocyanate groups was 0.5:1, the concentration of all reactants was 50 wt%, the reaction temperature was 25 ℃, and the reaction time was 1 h. And finally washing the polymer precipitate with distilled water for several times, and drying in vacuum at 60 ℃ for 12h to constant weight to obtain the polyurethane PU-10.

Example 11

Fresh hydroxyl-terminated polybutadiene, isophorone diisocyanate, dibutyltin dilaurate, bis (4-hydroxyphenyl) disulfide and tetrahydrofuran were poured into a three-necked reactor equipped with a mechanical stirrer in a glove box charged with 99.999% Ar for a one-shot reaction. Wherein [ hydroxyl-terminated polybutadiene ]/[ bis (4-hydroxyphenyl) disulfide ] - [ 1/99 (mass ratio), the molecular weight of the hydroxyl-terminated polybutadiene was 600g/mol, dibutyltin dilaurate was 0.1 wt% of the total mass of the reactants, the molar ratio of hydroxyl groups to isocyanate groups was 0.5:1, the concentration of all reactants was 30 wt%, the reaction temperature was 25 ℃, and the reaction time was 1 h. Finally, washing the polymer precipitate with distilled water for several times, and drying in vacuum at 60 ℃ for 12h to constant weight to obtain the polyurethane PU-11.

Example 12

Fresh polyolefin diol, isophorone diisocyanate, dibutyltin dilaurate, bis (4-hydroxyphenyl) disulfide and tetrahydrofuran were poured into a three-necked reactor equipped with a mechanical stirrer in a glove box charged with 99.999% Ar for a one-shot reaction. Wherein [ hydroxyl-terminated polybutadiene ]/[ bis (4-hydroxyphenyl) disulfide ] - [ 1/99 (mass ratio), the molecular weight of the hydroxyl-terminated polybutadiene was 600g/mol, dibutyltin dilaurate was 0.1 wt% of the total mass of the reactants, the molar ratio of hydroxyl groups to isocyanate groups was 0.5:1, the concentration of all reactants was 10 wt%, the reaction temperature was 100 ℃, and the reaction time was 1 h. And finally washing the polymer precipitate with distilled water for several times, and drying in vacuum at 60 ℃ for 12h to constant weight to obtain the polyurethane PU-12.

Example 13

Fresh polyfluoride diol, isophorone diisocyanate, dibutyltin dilaurate, bis (4-hydroxyphenyl) disulfide and tetrahydrofuran were poured into a three-necked reactor equipped with a mechanical stirrer in a glove box charged with 99.999% Ar for a one-shot reaction. Wherein [ hydroxyl-terminated polybutadiene ]/[ bis (4-hydroxyphenyl) disulfide ] - [ 1/99 (mass ratio), the molecular weight of the hydroxyl-terminated polybutadiene was 600g/mol, dibutyltin dilaurate was 0.1 wt% of the total mass of the reactants, the molar ratio of hydroxyl groups to isocyanate groups was 0.5:1, the concentration of all reactants was 10 wt%, the reaction temperature was 60 ℃, and the reaction time was 1 h. Finally, washing the polymer precipitate with distilled water for several times, and drying in vacuum at 60 ℃ for 12h to constant weight to obtain the polyurethane PU-13.

Example 14

In a glove box charged with 99.999% Ar, fresh polyether diol, isophorone diisocyanate, dibutyltin dilaurate, bis (4-hydroxyphenyl) disulfide and tetrahydrofuran were poured into a three-necked reactor equipped with a mechanical stirrer for one-shot reaction. Wherein [ hydroxyl-terminated polybutadiene ]/[ bis (4-hydroxyphenyl) disulfide ] - [ 1/99 (mass ratio), the molecular weight of the hydroxyl-terminated polybutadiene was 600g/mol, dibutyltin dilaurate was 0.1 wt% of the total mass of the reactants, the molar ratio of hydroxyl groups to isocyanate groups was 0.5:1, the concentration of all reactants was 10 wt%, the reaction temperature was 25 ℃, and the reaction time was 24 hours. Finally, washing the polymer precipitate with distilled water for several times, and drying in vacuum at 60 ℃ for 12h to constant weight to obtain the polyurethane PU-14.

Example 15

Fresh hydroxyl-terminated polybutadiene, isophorone diisocyanate, dibutyltin dilaurate, bis (4-hydroxyphenyl) disulfide and tetrahydrofuran were poured into a three-necked reactor equipped with a mechanical stirrer in a glove box charged with 99.999% Ar for a one-shot reaction. Wherein [ hydroxyl-terminated polybutadiene ]/[ bis (4-hydroxyphenyl) disulfide ] - [ 1/99 (mass ratio), the molecular weight of the hydroxyl-terminated polybutadiene was 600g/mol, dibutyltin dilaurate was 0.1 wt% of the total mass of the reactants, the molar ratio of hydroxyl groups to isocyanate groups was 0.5:1, the concentration of all reactants was 10 wt%, the reaction temperature was 25 ℃, and the reaction time was 1 h. And finally washing the polymer precipitate with distilled water for several times, and drying in vacuum at 100 ℃ for 12h to constant weight to obtain the polyurethane PU-15.

Example 16

Fresh hydroxyl-terminated polybutadiene, isophorone diisocyanate, dibutyltin dilaurate, bis (4-hydroxyphenyl) disulfide and tetrahydrofuran were poured into a three-necked reactor equipped with a mechanical stirrer in a glove box charged with 99.999% Ar for a one-shot reaction. Wherein [ hydroxyl-terminated polybutadiene ]/[ bis (4-hydroxyphenyl) disulfide ] - [ 1/99 (mass ratio), the molecular weight of the hydroxyl-terminated polybutadiene was 600g/mol, dibutyltin dilaurate was 0.1 wt% of the total mass of the reactants, the molar ratio of hydroxyl groups to isocyanate groups was 0.5:1, the concentration of all reactants was 10 wt%, the reaction temperature was 25 ℃, and the reaction time was 1 h. Finally, washing the polymer precipitate with distilled water for several times, and drying in vacuum at 80 ℃ for 12h to constant weight to obtain the polyurethane PU-16.

Example 17

Fresh hydroxyl-terminated polybutadiene, isophorone diisocyanate, dibutyltin dilaurate, bis (4-hydroxyphenyl) disulfide and tetrahydrofuran were poured into a three-necked reactor equipped with a mechanical stirrer in a glove box charged with 99.999% Ar for a one-shot reaction. Wherein [ hydroxyl-terminated polybutadiene ]/[ bis (4-hydroxyphenyl) disulfide ] - [ 1/99 (mass ratio), the molecular weight of the hydroxyl-terminated polybutadiene was 600g/mol, dibutyltin dilaurate was 0.1 wt% of the total mass of the reactants, the molar ratio of hydroxyl groups to isocyanate groups was 0.5:1, the concentration of all reactants was 10 wt%, the reaction temperature was 25 ℃, and the reaction time was 1 h. Finally, washing the polymer precipitate with distilled water for several times, and drying in vacuum at 60 ℃ for 36h to constant weight to obtain the polyurethane PU-17.

And (3) performance characterization:

nuclear magnetic resonance (¹H-NMR)

At room temperature, the reaction was carried out at AVANCE III (400MHz) using tetramethylsilane as an internal standard¹H-NMR spectrum, sample concentration 1-5 wt%.

Self-healing performance

The self-healing test was performed as follows: the 0.4mm polyurethane film was cut into several small rectangular films, and the middle portions of the small rectangular films were completely cut off to perform a self-healing test. The recovery of the cut was observed under an optical microscope (Olympus/BX 51TF Instec H601, Japan) equipped with a hot stage.

As can be seen from FIGS. 4a to 4f, the polyurethane prepared by the embodiment of the invention can realize self-healing within 300min at normal temperature, and under the heating condition of 60 ℃, the self-healing of the polyurethane can be realized within 11 min.

Hydrophobic property

Water contact angle analysis was performed on a contact angle goniometer (OCA25, Dataphysics, Germany). The hydrophilicity and hydrophobicity of the material was determined by depositing a water droplet using a syringe directed down to the surface of the sample membrane and analyzing the angle of the water droplet to the membrane surface.

As can be seen from FIGS. 6a to 6c, the contact angle of the polyurethane prepared in the examples is 89.4 + -0.2 degrees, the contact angles after soaking for 1 day and 3 days are 89.4 + -0.2 degrees and 89.2 + -0.2 degrees, respectively, and the contact angles are basically unchanged, which indicates that the polyurethane prepared by the method has stable performance and good hydrophobic effect.

Mechanical Properties

The mechanical properties of the samples were measured with a universal tester (UTM, Instrument, model: 5567), the tensile rate being maintained at 5 mm/min.

As can be seen from FIG. 7, the mechanical tensile properties of the polyurethanes prepared in examples 1 to 4 can be adjusted according to the different ratios of the soft segment to the hard segment, so as to meet the requirements of different fields.

In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.

The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.

The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.

Throughout this disclosure, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition taught by the present invention also consists essentially of, or consists of, the recited components and the process taught by the present invention also consists essentially of, or consists of, the recited process steps.

It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.

While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.