阅读说明：本技术 离子型环烯烃聚合物、基于该离子型环烯烃聚合物的光自修复材料及其制备方法和应用 (Ionic cyclic olefin polymer, light self-repairing material based on ionic cyclic olefin polymer, and preparation method and application of light self-repairing material ) 是由 李悦生 聂凤敏 潘莉 于 2021-10-09 设计创作，主要内容包括：本发明公开了一种离子型环烯烃聚合物、基于该离子型环烯烃聚合物的光自修复材料及其制备方法和应用,属于自修复材料技术领域。本发明制备的离子型环烯烃聚合物结构中存在可逆离子,且该聚合物在红外光下展现优异的光热转换能力,使得该聚合物在光照刺激下具有高效的修复性能；同时,自修复材料制备过程中所采用的Grubbs 3钌催化剂,不仅用于催化开环易位聚合,在聚合反应完成加入终止剂后,其与终止剂反应所得的Grubbs 3衍生物还具有优异的光热效应,因此不需要额外加入光热转化剂,扩宽了Grubbs 3钌催化剂的应用。(The invention discloses an ionic cycloolefin polymer, a light self-repairing material based on the ionic cycloolefin polymer, and a preparation method and application of the light self-repairing material, and belongs to the technical field of self-repairing materials. The ionic cycloolefin polymer prepared by the invention has reversible ions in the structure, and the polymer shows excellent photo-thermal conversion capability under infrared light, so that the polymer has high-efficiency repair performance under illumination stimulation; meanwhile, the Grubbs 3 ruthenium catalyst adopted in the preparation process of the self-repairing material is not only used for catalyzing ring-opening metathesis polymerization, but also has excellent photo-thermal effect with the Grubbs 3 derivative obtained by the reaction of the Grubbs 3 catalyst and the terminator after the polymerization reaction is finished and the terminator is added, so that the photo-thermal conversion agent does not need to be additionally added, and the application of the Grubbs 3 ruthenium catalyst is widened.)

1. An ionic cycloolefin polymer is characterized by having a chemical structure shown in a formula I, wherein y represents the polymerization degree of 50-2000, X represents bis (trifluoromethyl) sulfonyl imide anion, perfluorobutyl sulfonate anion, trifluoromethyl sulfonate anion or methylsulfonate anion, m and n are side chain lengths, m is more than or equal to 1 and less than or equal to 5, and n is more than or equal to 0 and less than or equal to 8;

2. the ionic cycloolefin polymer according to claim 1, wherein in the formula I, y is 100. ltoreq. y.ltoreq.800, X is a perfluorobutanesulfonic acid anion, m is 3, and n is 0. ltoreq.4.

3. A photo-self-healing material comprising the ionic cyclic olefin polymer of claim 1; the thickness of the light self-repairing material is 0.2-0.5 mm.

4. The method for preparing the light self-repairing material as claimed in claim 3, characterized by comprising the following steps: under the action of a dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] (benzylidene) bis (3-bromopyridine) ruthenium (II) catalyst, carrying out ring-opening metathesis polymerization on an ionic norbornene derivative with a structure shown in a formula II in a polymerization reaction solvent, adding a terminator after the reaction is finished, drying the obtained polymer solution, and carrying out hot press molding to obtain the light self-repairing material;

wherein X represents bis (trifluoromethyl) sulfonyl imide anion, perfluorobutyl sulfonic acid anion, trifluoromethyl sulfonic acid anion or methylsulfonic acid anion, m and n are side chain lengths, m is more than or equal to 1 and less than or equal to 5, and n is more than or equal to 0 and less than or equal to 8.

5. The preparation method according to claim 4, wherein the ionic norbornene derivative having the structure of formula II and the catalyst are fed in a molar ratio of 50-2000: 1; the temperature of the polymerization reaction is 0-40 ℃, and the time of the polymerization reaction is 5-24 h.

6. The preparation method according to claim 4, wherein the mass ratio of the ionic norbornene derivative having the structure represented by the formula II to the polymerization solvent is 1 (3-50).

7. The preparation method according to claim 4, wherein the terminator is vinyl ethyl ether, the molar ratio of the terminator to the catalyst is 100-500: 1, and the time for terminating the polymerization reaction is 20-40 min.

8. The preparation method according to claim 4, wherein the hot press forming temperature is 120-160 ℃, the pressure is 2-6 MPa, and the hot press time is 10 min.

9. Use of the ionic cyclic olefin polymer according to any one of claims 1 to 2 or the photo self-healing material according to claim 3 in the field of photo-healing.

The application of the Grubbs 3 derivative as a self-repairing material photo-thermal conversion agent is characterized in that the Grubbs 3 derivative is dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidine subunit ] (ethoxymethylene) bis (3-bromopyridine) ruthenium (II); the self-healing material is the photo self-healing material of claim 3.

Technical Field

The invention relates to the technical field of self-repairing materials, in particular to an ionic cycloolefin polymer, a light self-repairing material based on the ionic cycloolefin polymer, and a preparation method and application of the light self-repairing material.

Background

In recent years, inspired by the unique and efficient wound healing process in biological systems, researchers have developed a variety of synthetic polymeric materials that achieve nearly complete repair after being subjected to external damage. In the field of self-repairing materials, there is always an inherent contradiction between the repairing efficiency and the mechanical performance of the materials, which means that the self-repairing process of the high mechanical strength materials is realized or accelerated, and external stimulation needs to be applied. These include heat, light, solvent, pH, etc., where traditional heating methods result in a limited range of self-healing effects, and the heating process may also damage structures outside of the damaged area of the material, resulting in wasted energy and economic loss. In contrast, the self-repairing mode based on the photo-thermal effect has many advantages, such as: the method has the advantages of long operation distance, high precision, adjustable strength, high repair efficiency, small influence on surrounding areas, low cost and the like, and has wide application prospect (Habault D.etc. chem.Soc.Rev.,2013,42, 7244). Therefore, the development of the high-efficiency light self-repairing material has very important practical significance.

The existing photothermal conversion agent used in the light self-repairing material is mainly inorganic nano material, such as noble metal nano particles, carbon material and the like, and the compatibility of the inorganic nano material and the polymer material is poor, so that the mechanical property of the composite material is reduced, and the application range of the composite material is greatly limited. In view of the disadvantages of inorganic nanomaterials, organic photothermal materials are highly regarded, and recently, carbon-dragon complexes (metal heteroaromatic compounds) reported in the shahaiping problem group can be covalently bonded into polymers through chemical reactions, so that the polymers have excellent photothermal effects (Xia h.etc. acc. chem. res.2018,51,1691). However, the preparation process is relatively complex, and further popularization is limited to a certain extent.

Therefore, the development of the photo-thermal material which has simple synthetic process, convenience and easy obtaining and better compatibility with the polymer has important significance for developing high-performance photo-self-repairing materials.

Disclosure of Invention

The invention aims to provide an ionic cycloolefin polymer, a light self-repairing material based on the ionic cycloolefin polymer, and a preparation method and application of the light self-repairing material, so as to solve the problems in the prior art, and enable the light self-repairing material to have good photo-thermal effect and repairing performance.

In order to achieve the purpose, the invention provides the following scheme:

one technical scheme of the invention is to provide an ionic cycloolefin polymer which has a chemical structure shown in a formula I, wherein y represents the polymerization degree of more than or equal to 50 and less than or equal to 2000, and X represents bis (trifluoromethyl) sulfimide anion (Tf)₂N^-) Perfluorobutanesulfonic acid anion (CF)₃(CF₂)₃SO₃ ^-) Triflate anion (CF)₃SO₃ ^-) Or methylsulfonate anion (CH)₃SO₃ ^-) M and n are the lengths of side chains, m is more than or equal to 1 and less than or equal to 5, and n is more than or equal to 0 and less than or equal to 8;

preferably, in the formula I, y is more than or equal to 100 and less than or equal to 800, and X is perfluorobutyl sulfonate anion (CF)₃(CF₂)₃SO₃ ^-)，m＝3，0≤n≤4。

The second technical scheme of the invention provides a light self-repairing material which comprises the ionic cycloolefin polymer.

Preferably, the light self-repairing material is a thin film material with the thickness of 0.2-0.5 mm.

The third technical scheme of the invention is to provide a preparation method of the light self-repairing material, which comprises the following steps: under the action of a dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] (benzylidene) bis (3-bromopyridine) ruthenium (II) catalyst, carrying out ring-opening metathesis polymerization on an ionic norbornene derivative with a structure shown in a formula II in a polymerization reaction solvent, adding a terminator after the reaction is finished, drying the obtained polymer solution, and carrying out hot press molding to obtain the light self-repairing material;

wherein X represents bis (trifluoromethyl) sulfonyl imide anion, perfluorobutyl sulfonic acid anion, trifluoromethyl sulfonic acid anion or methylsulfonic acid anion, m and n are side chain lengths, m is more than or equal to 1 and less than or equal to 5, and n is more than or equal to 0 and less than or equal to 8.

The invention has no special limitation on the source of the ionic norbornene derivative with the structure shown in the formula II, and the ionic norbornene derivative is prepared by a method well known to a person skilled in the art in the references (Nie F. M. etc. macromolecules 2019,52, 5289).

In the present invention, the dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] (benzylidene) bis (3-bromopyridine) ruthenium (II) catalyst is a compound having a structure represented by formula III, the source thereof is not particularly limited, and it can be obtained commercially or prepared by reference (Grubbs r., etc. angelw.chem.int.ed.2002, 41(21), 4035.);

preferably, the feeding molar ratio of the ionic norbornene derivative with the structure of the formula II to the catalyst is 50-2000: 1; more preferably 100-800: 1.

Preferably, the temperature of the polymerization reaction is 0-40 ℃, and the time of the polymerization reaction is 5-24 hours, more preferably 12 hours.

Preferably, the mass ratio of the ionic norbornene derivative having the structure represented by the formula II to the polymerization reaction solvent is 1 (3-50), and more preferably 1 (10-20).

In the invention, the catalyst is prepared into a catalyst solution and then added into a reaction system, and the solvent for the polymerization reaction and the catalyst solution are dichloromethane solvents. The amount of the methylene chloride solvent used in the present invention is not particularly limited, and the amount of the solvent used in the polymerization reaction, which is well known to those skilled in the art, may be used.

Preferably, the terminating agent is vinyl ethyl ether, and the molar ratio of the terminating agent to the catalyst is 100-500: 1, more preferably (200-400): 1, and most preferably 300: 1; the time for terminating the polymerization reaction is 20 to 40min, more preferably 25 to 35min, and most preferably 30 min.

The present invention is not particularly limited in kind and source of the terminator, and any terminator used in the preparation of the cycloolefin polymer, which is well known to those skilled in the art, can be used and can be commercially available. In the present invention, the terminator is preferably vinyl ethyl ether.

In the invention, after the polymerization is finished and the terminator is added, the Grubbs 3 catalyst reacts with the terminator to obtain the Grubbs 3 derivative, and the mass content of the Grubbs 3 derivative in the polymer is 0.08-1.60%.

The method for drying the polymer is not particularly limited in the present invention, and a vacuum drying method well known to those skilled in the art may be used. In the invention, the temperature for vacuum drying of the polymerization reaction product is preferably 30-60 ℃, more preferably 35-55 ℃, and most preferably 40 ℃. In the invention, the drying time of the polymerization product is preferably 12-24 h, more preferably 16-20 h, and most preferably 18 h.

Preferably, the hot-press molding temperature is 120-160 ℃, the pressure is 2-6 MPa, and the hot-press time is 10 min.

The fourth technical scheme of the invention is to provide the application of the ionic cycloolefin polymer or the light self-repairing material in the field of light repair.

The fifth technical scheme of the invention is to provide an application of Grubbs 3 derivatives as a self-repairing material photo-thermal conversion agent, wherein the Grubbs 3 derivatives are dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidine subunit ] (ethoxymethylene) bis (3-bromopyridine) ruthenium (II); the self-repairing material is the light self-repairing material.

The invention researches the photothermal effect of the ionic cycloolefin polymer film material, tests the photothermal conversion of the polymer film by using a 808nm laser, and has the laser power density of 1W/cm²During the process, an infrared camera is used for recording and shooting photothermal images in real time, and the temperature of the polymer film under laser irradiation is measured in real time. The test result shows that the material has good photo-thermal effect.

The invention researches the repairing performance of the ionic cycloolefin polymer film under laser, namely, the ionic cycloolefin polymer film is prepared by the following stepsThe sample strip is cut through the middle, and the two fracture surfaces are lightly connected and placed. The test power is 1W/cm²808nm laser, restoration of mechanical properties of the polymer sample. The mechanical properties of the ionic polymer to be repaired were tested using an INSTRON 5969 instrument in the repair experiments. The test result shows that the ionic cycloolefin polymer has good repairing performance.

The ionic polyolefin polymer provided by the invention has good photo-thermal effect and excellent mechanical property and photo-repairing property. The content of Grubbs 3 derivatives in the polymer is adjusted by regulating the proportion of Grubbs 3 catalyst and ionic norbornene derivatives, the photo-thermal effect of the cycloolefin material is changed, and the photo-repair efficiency of the material is further regulated. Specifically, when near-infrared light irradiates the ionic cycloolefin polymer film, the Grubbs 3 derivative in the polymer absorbs the near-infrared light to heat the polymer film, the reversibility of the ionic action in the polymer film and the motion capability of a chain segment are improved, the self-repairing of the damaged film is realized, and the repairing efficiency is greatly improved. The results of the examples show that when microcracks appear on the surface of the near infrared light repairing ionic cycloolefin polymer material prepared by the invention, the microcracks disappear after the material is irradiated for 1-10 minutes under an infrared lamp with the wavelength of 808nm, and the mechanical properties of the material are completely repaired.

The invention discloses the following technical effects:

the ionic cycloolefin polymer with the photo-thermal effect is prepared, and due to the existence of reversible ions in the polymer, the polymer has high-efficiency repairing performance under illumination, so that the photo-self-repairing material based on the ionic cycloolefin polymer can simply and efficiently realize the photo-repairing effect, has the characteristics of mild repairing process conditions, good substrate universality and high atom utilization rate, and has guiding significance for preparation of similar materials.

Meanwhile, the Grubbs 3 ruthenium catalyst adopted in the preparation process can be used for catalyzing ring-opening metathesis polymerization, the ruthenium metal complex obtained by the reaction of the Grubbs 3 ruthenium catalyst and the terminator has excellent photo-thermal effect after the polymerization reaction is finished and the terminator is added, and can efficiently convert light energy into heat energy under the action of near infrared light, so that the photo-thermal conversion agent does not need to be additionally added in the subsequent preparation of the photo-self-repairing material, the prepared photo-self-repairing material has obvious photo-thermal effect, the application of the Grubbs 3 ruthenium catalyst is widened, and the rapid repair of the material is realized.

The Grubbs 3 derivative as an organic photothermal material has similar photothermal effect compared with the reported organic photothermal material, has stable photothermal effect and has wide application prospect.

Due to the action of a large amount of ions in the ionic cycloolefin polymer material, the polymer material has certain ionic conductivity, so that the ionic cycloolefin polymer material can be independently used as a flexible electronic sensor.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in 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 it is obvious for those skilled in the art to obtain other drawings without creative efforts.

FIG. 1 is a nuclear magnetic hydrogen spectrum of a polymerization solution in the ionic type cycloolefin polymerization process according to example 1 of the present invention; wherein the upper figure is a monomer and the lower figure is a polymer.

FIG. 2 shows the near infrared light (λ: 808nm, 1W/cm) of the ionic cycloolefin polymer film in example 1 of the present invention²) The change trend of the surface temperature of the film along with the time under the irradiation;

FIG. 3 shows the near infrared light (λ: 808nm, 1W/cm) of the ionic cycloolefin polymer film in example 1 of the present invention²) Repairing the stress-strain curve after 3min under irradiation;

FIG. 4 is a UV-visible absorption spectrum of dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] (ethoxymethylene) bis (3-bromopyridine) Grubbs 3 derivative in example 5 of the present invention;

FIG. 5 shows dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazole in different concentrations according to example 5 of the present inventionAlkylidene group](ethoxymethylene) bis (3-bromopyridine) Grubbs 3 derivative solution in near infrared light (lambda: 808nm, 1W/cm)²) The temperature of the solution under irradiation has a tendency to change with time.

Detailed Description

Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.

It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.

It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.

As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.

Example 1

The structural general formula of the ionic cycloolefin polymer is as follows:

wherein the side chain length m is 3, n is 0, the degree of polymerization y is 100, and X is perfluorobutylsulfonic acid anion (CF)₃(CF₂)₃SO₃ ^-) The synthesis steps are as follows:

the following operations were all performed in a braun (Mbraun) glove box: 3- (2- (bicyclo [2.2.1] hept-5-en-2-ylmethoxy) -2-oxoalkyl) -1-methyl-1 h-imidazole perfluorobutylsulfonate (1.0g,1.74mmol) and 10mL extra dry methylene chloride were added to a 50mL polymerization flask and mixed with stirring for 15 minutes. To a 5mL ampoule were added 15.4mg (0.0174mmol) of dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] (benzylidene) bis (3-bromopyridine) ruthenium (II) catalyst and 2mL of dichloromethane to obtain a catalyst solution. Adding the catalyst solution into the polymerization bottle under the condition of stirring, carrying out polymerization reaction for 12 hours at 25 ℃, and detecting the reaction progress by a nuclear magnetic technology from a reaction stock solution. After the polymerization is completed, the following catalysts are added into the polymerization reaction bottle under the condition of stirring: the polymerization was terminated by adding 375.84mg (5.22mmol) of vinyl ethyl ether to the molar ratio of the terminator: 1:300, and after 30min, the resulting polymerization solution was dried in a vacuum oven at 40 ℃ for 18h to give 0.993g of a polymerization product in a yield of 99.3% and a content of Grubbs 3 derived substances of 1.52%.

After nuclear magnetic resonance detection of a nuclear magnetic stock solution spectrogram, as shown in fig. 1, the vibration absorption peak of the double bond on the norbornene ring with the delta being 5.8-6.2ppm in the monomer is completely disappeared, and the nuclear magnetic resonance spectrogram shows a peak of the double bond of the main chain after ring-opening metathesis polymerization at the position with the delta being 5.0-5.5ppm, which proves that the monomer is completely converted and the polymerization is successful.

The polymer obtained in example 1 was hot-pressed at 120 ℃ under a pressure of 2MPa for 10 minutes to obtain a polymer film having a thickness of 0.3 mm.

Photothermal effect test of ionic cycloolefin polymer film material:

the photo-thermal conversion of the polymer film is tested by using a 808nm laser, and the laser power density is 1W/cm²During the process, an infrared camera is used for recording and shooting photothermal images in real time, and the temperature of the polymer film under laser irradiation is measured in real time.

The photothermal effect test results of the ionic cycloolefin polymer film obtained in example 1 of the present invention are shown in FIG. 2, which is 1W/cm²After the 808nm infrared light irradiates for 80s, the surface temperature of the polymer film rises to 100 ℃, and the test result shows that the material has good photo-thermal effect.

Repairing performance of the ionic cycloolefin polymer film under laser:

the repair experiment uses an INSTRON 5969 instrument to test the mechanical properties of the ionic polymer to be repaired: cutting off the middle of the tensile sample strip, then lightly connecting the two fracture surfaces together, and placing the tensile sample strip at a test power of 1W/cm²808nm laser, restoration of mechanical properties of the polymer sample.

The results of the photorepair test of the ionic cycloolefin polymer film obtained in example 1 of the present invention are shown in FIG. 3, which is at 1W/cm²Under the irradiation of 808nm infrared light, the repair can be realized by being close to 100 percent within 3 min. The test result shows that the ionic cycloolefin polymer has good repairing performance.

Example 2

The structural general formula of the ionic cycloolefin polymer is as follows:

wherein the side chain length m is 3, n is 0, the degree of polymerization y is 800, and X is perfluorobutylsulfonic acid anion (CF)₃(CF₂)₃SO₃ ^-) The synthesis steps are as follows:

the following operations were all performed in a braun (Mbraun) glove box: 3- (2- (bicyclo [2.2.1] hept-5-en-2-ylmethoxy) -2-oxoalkyl) -1-methyl-1 h-imidazole perfluorobutylsulfonate (1.0g,1.74mmol) and 10mL extra dry methylene chloride were added to a 50mL polymerization flask and mixed with stirring for 15 minutes. To a 5mL ampoule, 1.93mg (0.0022mmol) of dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] (benzylidene) bis (3-bromopyridine) ruthenium (II) catalyst and 0.5mL of methylene chloride were added to obtain a catalyst solution. Adding the catalyst solution into the polymerization bottle under the condition of stirring, carrying out polymerization reaction for 12 hours at the temperature of 40 ℃, and detecting the reaction progress by a nuclear magnetic technology from a reaction stock solution. After the polymerization is completed, the following catalysts are added into the polymerization reaction bottle under the condition of stirring: vinyl ethyl ether 47.5mg (0.66mmol) was added to terminate the polymerization at a terminator molar ratio of 1:300, and after 30min, the resulting polymerization solution was dried in a vacuum oven at 40 ℃ for 18h to give 0.996g of a polymerization product, the yield was 99.6%, and the content of Grubbs 3 derived material was 0.193%.

The polymer obtained in example 2 was hot-pressed at 160 ℃ under a pressure of 6MPa for 10min to obtain a polymer film having a thickness of 0.3 mm.

The ionic cycloolefin polymer film obtained in the embodiment 2 of the invention is subjected to a photothermal effect test (the test method is the same as that in the embodiment 1), and the test result shows that the ionic cycloolefin polymer film is 1W/cm²The surface temperature of the polymer film rises to 80 ℃ after 180 seconds of 808nm infrared light irradiation.

The ionic cycloolefin polymer film obtained in the example 2 of the invention is subjected to the photorepair experiment test (the test method is the same as that in the example 1), and the test result shows that the ionic cycloolefin polymer film is 1W/cm²Under the irradiation of 808nm infrared light, the repair can be realized by nearly 100 percent in 8 min.

Example 3

The structural general formula of the ionic cycloolefin polymer is as follows:

wherein the side chain length m is 3, n is 4, the degree of polymerization y is 100, and X is bis (trifluoromethyl) sulfonimide anion (Tf)₂N^-) The synthesis steps are as follows:

the following operations were all performed in a braun (Mbraun) glove box: 3- (2- (bicyclo [2.2.1] hept-5-en-2-ylmethoxy) -2-oxoalkyl) -1-methyl-1 h-imidazole perfluorobutylsulfonate (1.0g,1.64mmol) and 10mL extra dry methylene chloride were added to a 50mL polymerization flask and mixed with stirring for 15 minutes. To a 5mL ampoule were added 14.48mg (0.0164mmol) of dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] (benzylidene) bis (3-bromopyridine) ruthenium (II) catalyst and 2mL of dichloromethane, to obtain a catalyst solution. Adding the catalyst solution into the polymerization bottle under the condition of stirring, carrying out polymerization reaction for 12 hours at the temperature of 30 ℃, and detecting the reaction progress by a nuclear magnetic technology from a reaction stock solution. After the polymerization is completed, the following catalysts are added into the polymerization reaction bottle under the condition of stirring: the polymerization was terminated by adding 236.16mg (3.28mmol) of vinyl ethyl ether to the molar ratio of the terminator: 1:200, and after 30min, the resulting polymerization solution was dried in a vacuum oven at 40 ℃ for 18h to give 0.995g of the polymerization product in 99.5% yield and 1.43% content of Grubbs 3 derived substances.

The polymer obtained in example 3 was hot-pressed at 140 ℃ under a pressure of 4MPa for 10 minutes to obtain a polymer film having a thickness of 0.3 mm.

The ionic cycloolefin polymer film obtained in the example 3 of the present invention was subjected to a photothermal effect test (the test method is the same as that of the example 1), and the test result shows that the ionic cycloolefin polymer film is 1W/cm²The surface temperature of the polymer film rises to 95 ℃ after 100 seconds of 808nm infrared light irradiation.

The ionic cycloolefin polymer film obtained in the embodiment 3 of the invention is subjected to the photorepair experiment test (the test method is the same as the embodiment 1), and the test result shows that the ionic cycloolefin polymer film is 1W/cm²Under the irradiation of 808nm infrared light, the repair can be realized by being close to 100 percent within 3 min.

Example 4

The structural general formula of the ionic cycloolefin polymer is as follows:

wherein the side chain length m is 3, n is 8, the degree of polymerization y is 2000, and X is trifluoromethanesulfonate anion (CF)₃SO₃ ^-) The synthesis steps are as follows:

the following operations were all performed in a braun (Mbraun) glove box: 3- (2- (bicyclo [2.2.1] hept-5-en-2-ylmethoxy) -2-oxoalkyl) -1-methyl-1 h-imidazole perfluorobutylsulfonate (3.0g,5.60mmol) and 30mL extra dry methylene chloride were added to a 50mL polymerization flask and mixed with stirring for 15 minutes. To a 5mL ampoule were added 2.48mg (0.0028mmol) of dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] (benzylidene) bis (3-bromopyridine) ruthenium (II) catalyst and 0.5mL of dichloromethane to obtain a catalyst solution. Adding the catalyst solution into the polymerization bottle under the condition of stirring, carrying out polymerization reaction for 12 hours at the temperature of 40 ℃, and detecting the reaction progress by a nuclear magnetic technology from a reaction stock solution. After the polymerization is completed, the following catalysts are added into the polymerization reaction bottle under the condition of stirring: the polymerization was terminated by adding 80.64mg (1.12mmol) of vinyl ethyl ether to the molar ratio of the terminator: 1:400, and after 30min, the resulting polymerization solution was dried in a vacuum oven at 40 ℃ for 18h to give 2.90g of a polymerization product in a yield of 96.7% and a content of Grubbs 3-derived substances of 0.08%.

The polymer obtained in example 4 was hot-pressed at 140 ℃ under a pressure of 4MPa for 10 minutes to obtain a polymer film having a thickness of 0.5 mm.

The ionic cycloolefin polymer film obtained in the example 4 of the present invention was subjected to a photothermal effect test (the test method was the same as in the example 1), and the test result shows that the thickness of the ionic cycloolefin polymer film was 1W/cm²The surface temperature of the polymer film rises to 60 ℃ after 240 seconds of 808nm infrared light irradiation.

The ionic cycloolefin polymer film obtained in the embodiment 4 of the invention is subjected to the photorepair experiment test by the method according to the technical scheme (the test method is the same as the embodiment 1), and the test result shows that the ionic cycloolefin polymer film is 1W/cm²Under the irradiation of 808nm infrared light, the repair can be realized by nearly 100 percent within 10 min.

Example 5

The structural general formula of the ionic cycloolefin polymer is as follows:

wherein the length of side chain is m-1, n-8, polymerization degree is y-1000, and X-methylsulfonate anion is separatedSon (CH)₃SO₃ ^-) The synthesis steps are as follows:

the following operations were all performed in a braun (Mbraun) glove box: 3- (2- (bicyclo [2.2.1] hept-5-en-2-ylmethoxy) -2-oxoalkyl) -1-methyl-1 h-imidazole perfluorobutylsulfonate (2.0g,4.40mmol) and 30mL extra dry methylene chloride were added to a 50mL polymerization flask and mixed with stirring for 15 minutes. To a 5mL ampoule were added 3.90mg (0.0044mmol) of dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] (benzylidene) bis (3-bromopyridine) ruthenium (II) catalyst and 0.5mL of dichloromethane to obtain a catalyst solution. Adding the catalyst solution into the polymerization bottle under the condition of stirring, carrying out polymerization reaction for 12 hours at 25 ℃, and detecting the reaction progress by a nuclear magnetic technology from a reaction stock solution. After the polymerization is completed, the following catalysts are added into the polymerization reaction bottle under the condition of stirring: the polymerization was terminated by adding 126.72mg (1.76mmol) of vinyl ethyl ether to the molar ratio of the terminator: 1:400, and after 30min, the resulting polymerization solution was dried in a vacuum oven at 40 ℃ for 18h to give 1.90g of a polymerization product in a yield of 95.0% and a content of Grubbs 3-derived substances of 0.19%.

The polymer obtained in example 5 was hot-pressed at 140 ℃ under a pressure of 4MPa for 10 minutes to obtain a polymer film having a thickness of 0.5 mm.

The ionic cycloolefin polymer film obtained in example 5 of the present invention was subjected to photothermal effect test (the test method was the same as in example 1), and the test result showed that it was 1W/cm²The surface temperature of the polymer film rises to 80 ℃ after 180 seconds of 808nm infrared light irradiation.

The ionic cycloolefin polymer film obtained in the embodiment 5 of the invention is subjected to the photorepair experiment test by the method according to the technical scheme (the test method is the same as the embodiment 1), and the test result shows that the ionic cycloolefin polymer film is 1W/cm²Under the irradiation of 808nm infrared light, the repair can be realized by nearly 100 percent in 8 min.

Example 6

The structural general formula of the ionic cycloolefin polymer is as follows:

wherein the side chain length m is 5, n is 0, the degree of polymerization y is 500, and X is methylsulfonate anion (CH)₃SO₃ ^-) The synthesis steps are as follows:

the following operations were all performed in a braun (Mbraun) glove box: 3- (2- (bicyclo [2.2.1] hept-5-en-2-ylmethoxy) -2-oxoalkyl) -1-methyl-1 h-imidazole perfluorobutylsulfonate (1.0g,2.51mmol) and 30mL extra dry methylene chloride were added to a 50mL polymerization flask and mixed with stirring for 15 minutes. A5 mL ampoule was charged with 4.44mg (0.0050mmol) of dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] (benzylidene) bis (3-bromopyridine) ruthenium (II) catalyst and 0.5mL of methylene chloride to obtain a catalyst solution. Adding the catalyst solution into the polymerization bottle under the condition of stirring, carrying out polymerization reaction for 12 hours at 25 ℃, and detecting the reaction progress by a nuclear magnetic technology from a reaction stock solution. After the polymerization is completed, the following catalysts are added into the polymerization reaction bottle under the condition of stirring: the polymerization was terminated by adding 144mg (2mmol) of vinyl ethyl ether to the molar ratio of the terminator: 1:400, and after 30min, the resulting polymerization solution was dried in a vacuum oven at 40 ℃ for 18h to give 0.950g of a polymerization product, the yield was 95.0%, and the content of Grubbs 3-derived substances was 0.44%.

The polymer obtained in example 6 was hot-pressed at 140 ℃ under a pressure of 4MPa for 10 minutes to obtain a polymer film having a thickness of 0.3 mm.

The ionic cycloolefin polymer film obtained in example 6 of the present invention was subjected to photothermal effect test (the test method was the same as in example 1), and the test result showed that it was 1W/cm²The surface temperature of the polymer film rises to 90 ℃ after 150 seconds of 808nm infrared light irradiation.

The ionic cycloolefin polymer film obtained in the embodiment 6 of the invention is subjected to the photorepair experiment test by the method according to the technical scheme (the test method is the same as the embodiment 1), and the test result shows that the ionic cycloolefin polymer film is 1W/cm²Under the irradiation of 808nm infrared light, the repair can be realized by about 100 percent within 5 min.

Example 7

Dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene was tested using an ultraviolet-visible spectrophotometerBase of]The spectral absorption peak position of the (ethoxymethylene) bis (3-bromopyridine) ruthenium (II) Grubbs 3 derivative is shown in FIG. 4, which shows that the catalyst has a stronger absorption peak in the infrared region. Dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] was also tested]Dissolving a catalyst in a chloroform solution to prepare catalyst solutions (0.5mg/mL, 1.0mg/mL and 2.0mg/mL) with different concentrations, and testing the photothermal conversion of the catalyst solution by using a 808nm laser, wherein the laser power density is 1W/cm²And during the process, an infrared camera is used for recording and shooting photo-thermal images in real time, and the temperature of the catalyst solution under laser irradiation is measured in real time. The test results show that the catalyst has good photothermal effect as shown in fig. 5.

The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.