CN109608624B - Mechanical-property-controllable ion self-repairing high polymer material and preparation method thereof - Google Patents

Mechanical-property-controllable ion self-repairing high polymer material and preparation method thereof Download PDF

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CN109608624B
CN109608624B CN201811337578.0A CN201811337578A CN109608624B CN 109608624 B CN109608624 B CN 109608624B CN 201811337578 A CN201811337578 A CN 201811337578A CN 109608624 B CN109608624 B CN 109608624B
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李悦生
崔静
潘莉
马哲
王彬
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Abstract

Under the action of dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] (benzylidene) bis (3-bromopyridine) ruthenium (II) catalyst, carrying out ring-opening metathesis polymerization on a bis (biphenyl) norbornene compound and a norbornene derivative containing imidazole ions in a dichloromethane solvent by adopting a one-time feeding or sequential feeding method, and after the reaction is finished, terminating the reaction by using a terminator to respectively obtain random, two-block and three-block ionic copolymer self-repairing materials; wherein: the molar ratio of the bis (biphenyl) norbornene, the derivative of norbornene containing an imidazole ion and the catalyst is 150-250: 25-75: 1. The invention has simple process, easily obtained raw materials, controllable mechanical property and repair property compared with the prior material, can realize the high-efficiency repair of the hard material and improve the application range of the self-repair material.

Description

Mechanical-property-controllable ion self-repairing high polymer material and preparation method thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an ion self-repairing high polymer material with controllable mechanical properties and a preparation method thereof.
Background
The polymer material is more and more widely applied in industry and life due to the characteristics of light weight, wear resistance and easy processing, but microcracks inside the material inevitably appear due to the influence of various factors such as machinery, heat, chemistry and the like in the forming processing and using processes of the polymer material, and the microcracks are the root of generating macroscopic cracks, so that the overall performance of the polymer material is damaged. If the self-repairing performance of the high polymer material can be endowed, the service life, the safety and the reliability of the high polymer material can be improved, so that the energy efficiency is improved, the resource waste is reduced, and the pressure of the environment is relieved.
At present, self-repairing materials are classified into two categories, namely an exopathic type and an intrinsic type according to whether a repairing agent is used or not. The external aid type repair method uses microcapsules or hollow fibers to encapsulate the repair agent. The development of the material is limited due to the fact that the preparation method and the process conditions of the material are complex and harsh and the repair times are limited. The intrinsic type repairing principle is self-repairing by utilizing reversible chemical or physical action in a system, and the action force comprises Diels-Alder reaction, disulfide bond reaction, hydrogen bond, pi-pi stacking, ion interaction and host-guest interaction. The repairing method can realize repeated repairing, but because the chain motion is the main power for realizing the repairing of the material and is limited by the chain motion, the intrinsic self-repairing high polymer material prepared at present is soft and weak rubber and even gel with lower mechanical property. In practical application, the material is required to have good mechanical properties, and is particularly applied to the fields of aerospace, microelectronics, building industry and the like.
Disclosure of Invention
In order to solve the problems, the invention aims to disclose an ion self-repairing high polymer material with controllable mechanical properties and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides an ion self-repairing high polymer material with controllable mechanical properties, which has a structure shown in a formula I:
Figure BDA0001861629070000011
wherein x is 5 or 9; tf2N is trifluoromethyl sulfonyl imino. In the present invention, m and n are polymerization degrees, m is 150 to 250, and n is 25 to 75.
In the present invention, o is a bis (biphenyl) norbornene structural unit having a structure represented by formula II, and ● is an imidazole salt ion-containing norbornene derivative structural unit having a structure represented by formula III. The arrangement sequence of the two structural units in the polymer is different, so that random, diblock and triblock copolymers are obtained.
Figure BDA0001861629070000021
In formula III, x is 5 or 9; tf2N is bis (trifluoromethyl) sulfonylimino.
Under the action of dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] (benzylidene) bis (3-bromopyridine) ruthenium (II) catalyst, carrying out ring-opening metathesis polymerization on a compound with a structure shown in a formula II and a compound with a structure shown in a formula III of a norbornene derivative containing imidazole ions in a dichloromethane solvent by adopting a one-time feeding or sequential feeding method, and after the reaction is finished, stopping stirring and reacting for a period of time by using a terminator to respectively obtain a random, two-block and three-block ionic copolymer self-repairing material with a structure shown in a formula I; wherein: the molar ratio of the bis (biphenyl) norbornene, the derivative of norbornene containing an imidazole ion and the catalyst is 150-250: 25-75: 1.
Further, the norbornene derivatives containing an imidazole ion in formula III are 5-norbornene-2-methylene-1-decyl-3 hydro-imidazole bistrifluoromethylsulfonyl imide (x ═ 5) and 5-norbornene-2-methylene-1-hexyl-3 hydro-imidazole bistrifluoromethylsulfonyl imide (x ═ 9), respectively.
Furthermore, the distribution of the structural units in the polymer as random, two-block and three-block is realized by changing the feeding mode of the monomers in the ring-opening metathesis polymerization process, and the feeding can be one-time feeding or multiple feeding;
the two monomers are copolymerized for 6-24 hours simultaneously to obtain a random copolymer;
firstly, adding a compound with a formula II structure for polymerization for 0.5-2 h, then adding a compound with a formula III structure for polymerization for 6-24 h, and obtaining a diblock copolymer;
firstly, adding half of the fed compound with the structure of the formula II for polymerization for 0.5-2 h, then adding the compound with the structure of the formula III for polymerization for 6-24 h, and then adding half of the fed compound with the structure of the formula II for polymerization for 0.5-2 h to obtain the triblock copolymer.
In the present invention, the total reaction time of the ring-opening metathesis polymerization is preferably 7 to 28 hours, more preferably 10 to 20 hours, and most preferably 12 hours.
The temperature of the ring-opening metathesis polymerization reaction is preferably 20-40 ℃, more preferably 25-35 ℃, and most preferably 30 ℃.
Further, a terminator adopted after the reaction is vinyl ethyl ether; the molar ratio of the terminating agent to the catalyst is (100-500): 1, and the time for terminating the polymerization reaction is 20-40 min.
Further, the structural unit distribution is adjusted by adjusting x to be 5 or 9 and/or changing the feeding sequence of two monomers of a formula II and a formula III, so that the self-repairing high polymer material with controllable mechanical properties from strong toughness to soft toughness is obtained, wherein the Young modulus of the copolymer is controlled to be 12-243 MPa, the yield strength is controlled to be 5-19 MPa, the breaking strength is controlled to be 1-12 MPa, and the breaking elongation is controlled to be 340-1190%.
The source of the bis (biphenyl) norbornene compound is not particularly limited in the present invention, and can be prepared by a preparation method well known to those skilled in the art, referring to patent US7550546B 2.
The source of the 5-norbornene-2-methylene-1-decyl-3 hydro-imidazole bistrifluoromethylsulfonyl imide compound and the 5-norbornene-2-methylene-1-hexyl-3 hydro-imidazole bistrifluoromethylsulfonyl imide compound is not particularly limited, and the compound can be prepared by a preparation method known by a person skilled in the art by referring to literatures (Macromolecules 2011,44, 5075).
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 IV:
Figure BDA0001861629070000031
in formula IV, Mes is 2,4, 6-trimethylphenyl.
The catalyst adopted by the invention has the advantages of high activity, good polymerization tolerance, no need of adding a cocatalyst in the process of preparing the self-repairing polymer, high initiation rate, catalytic conversion rate of 100 percent, no occurrence of side reactions such as crosslinking and the like. In the present invention, the catalyst having the structure represented by formula IV is not particularly limited in its source, and is commercially available or can be prepared by referring to the literature (Angew. chem. int. Ed.1995,34,2039; J.Am. chem. Soc.1996,118, 100; Angew. chem. int. Ed.2002,41,4035).
In the present invention, the solvent for the polymerization reaction and the catalyst solution are both 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. In the invention, the mass ratio of the compound having the structure shown in the formula II to the polymerization reaction solvent is preferably 1 (2-10), and more preferably 1 (4-6).
After the polymerization reaction is finished, the preferable terminator of the invention terminates the polymerization reaction to obtain a polymerization reaction solution; and carrying out vacuum drying on the polymerization reaction solution to obtain a polymerization reaction product.
The present invention is not particularly limited in kind and source of the terminator, and any terminator known to those skilled in the art to be used in the preparation of cycloolefin copolymers can be used and commercially available. In the present invention, the terminator is preferably vinyl ethyl ether. In the present invention, the molar ratio of the terminating agent to the catalyst is preferably (100 to 500):1, more preferably (200 to 400):1, and most preferably 300: 1. In the present invention, the time for terminating the polymerization reaction is preferably 20 to 40min, more preferably 25 to 35min, and most preferably 30 min.
In the present invention, the polymerization reaction solution is preferably dried under vacuum to obtain a polymerization reaction product. The method of vacuum drying is not particularly limited in the present invention, and the technical scheme of vacuum drying known to those skilled in the art can be adopted. 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.
The nuclear magnetic resonance hydrogen spectrum detection is carried out on the obtained ion self-repairing polymer, and the detection method adopts a Bruker-400 nuclear magnetic resonance spectrometer to carry out measurement at 25 ℃, Tetramethylsilane (TMS) is used as an internal standard, and deuterated chloroform is used as a solvent. The detection result shows that the ion self-repairing polymer provided by the invention has a structure shown in a formula I. The content of the compound with the structure shown in the formula II in the ion self-repairing polymer obtained by calculation according to the formula V is as follows:
compound having the structure represented by formula II,% by mol ═ I4.7～6.0-I3.5～4.6/2)/I4.7～6.0]X 100% of formula V.
In the formula V, I3.5～4.6The peak area of chemical shift in the hydrogen spectrum of nuclear magnetic resonance is 3.5-4.6, I4.7～6.0The peak area of the chemical shift in the hydrogen spectrum of nuclear magnetic resonance is 4.7-6.0.
The molecular weight and the distribution of the ionic self-repairing polymer are obtained by adopting a gel permeation chromatography test, a Waters 515 high performance liquid chromatography pump and a Waters 2414 differential refraction detector are adopted for detection, the detection temperature is 40 ℃, I-MBHMW-3078 and I-MBLMW-3078 of Viscotek are taken as gel chromatographic columns, N-dimethylformamide containing 50mM lithium bromide is taken as an eluent, the outflow rate of the eluent is 1.0mL/min, and PL EasiCal PS-1 is taken as a standard sample.
The invention adopts dynamic thermal mechanical analysis to obtain the glass transition temperature of the ion self-repairing high polymer material, and adopts a TA Q800 dynamic thermal mechanical analyzer to measure, so as to prepare a film tensile sample strip (10 multiplied by 0.5 multiplied by 1 mm)3) The test frequency is 1Hz, the amplitude is 15 μm, and the temperature range is
Figure BDA0001861629070000041
The heating rates are all 3 ℃/min.
The invention adopts a thermal weight loss analysis method to research the thermal stability behavior of the ionic polymer, and adopts a TA Q50 instrument to carry out measurement.
The mechanical properties of the ion self-repairing high polymer material obtained by testing on an INSTRON 5969 instrument are detected according to the standard of GB/T1040-1992, Plastic tensile property test method, the sample strip clamping distance is 10.0mm, the test speed is 100mm/min, and each sample is tested for at least 5 times to ensure the reliability of data.
The invention researches the repairing performance of the ionic polymer material, cuts off the middle of a tensile sample strip, and then lightly connects two fracture surfaces together for placement. The polymer samples were tested for restoration of mechanical properties at various times and temperatures. The mechanical property of the ionic polymer material to be repaired is tested by adopting an INSTRON 5969 instrument in the repairing experiment.
Has the advantages that: the invention has the beneficial effects that:
the ion self-repairing high molecular material uses bis (biphenyl) norbornene and norbornene derivatives containing imidazole ions as raw materials, adopts dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] (benzylidene) bis (3-bromopyridine) ruthenium (II) as a catalyst to carry out ring-opening metathesis polymerization, and adopts a method of one-time feeding or fractional feeding to respectively obtain random, two-block and three-block copolymers. The sequence distribution of structural units in the polymer and the length of alkyl chains in the norbornene derivative containing the imidazole ion are controlled to control the mechanical properties and repair properties of the polymer. The preparation process is simple, the raw materials are simple and easy to obtain, the cost is low, compared with the prior art, the mechanical property and the repair property of the material are controllable, the high-efficiency repair of hard materials can be realized, and the application range of the self-repairing material is greatly enlarged.
The invention provides a high-strength high-toughness ion self-repairing polymer material which has a structure shown in a formula I, wherein m and n are polymerization degrees, m is 200, and n is 50. The ionic polymer provided by the invention has excellent mechanical strength and good repairing performance.
Drawings
FIGS. 1(a) to (f) are nuclear magnetic resonance hydrogen spectra of the ionic polymer materials obtained in examples 1 to 6 of the present invention, respectively;
FIGS. 2(a) to (f) are gel permeation chromatograms of the ionic polymer materials obtained in examples 1 to 6 of the present invention, respectively;
FIGS. 3(a) - (f) are dynamic thermo-mechanical analysis diagrams of the ionic polymer materials obtained in examples 1-6 of the present invention, respectively;
FIGS. 4(a) - (f) are the thermogravimetric plots of the ionic polymer materials obtained in examples 1-6 of the present invention, respectively;
FIGS. 5(a) - (f) are the stress-strain curves of the ionic polymer materials obtained in examples 1-6 of the present invention;
FIGS. 6(a) - (f) are the stress-strain curves of the ion polymer materials with different repairing degrees obtained in examples 1-6 of the present invention, respectively;
FIG. 7 shows the scratch repair of the ionic polymer material observed under the optical microscope in example 1 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
The compounds having the structure shown in formula II, the compounds having the structure shown in formula III and the compounds having the structure shown in formula IV, which are used in the following examples of the present invention, can be prepared by the above-mentioned documents or methods, and other reaction raw materials are commercially available.
Example 1
At 20 ℃, 1.014g of bis (biphenyl) norbornene compound, 5g of 5-norbornene-2-methylene-1-hexyl-3 h-imidazole bistrifluoromethylsulfonyl imide compound and 25mL of methylene chloride were added to a dry polymerization flask, respectively, and stirred and mixed for 10min to obtain a mixture; adding 29.72mg of dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] (benzylidene) bis (3-bromopyridine) ruthenium (II) catalyst and 5mL of dichloromethane into a ampoule, and then carrying out ultrasonic treatment for 3min to fully dissolve the catalyst in the dichloromethane to obtain a catalyst solution; the catalyst solution was added to the above polymerization flask with stirring for 6 hours of polymerization. After the polymerization is completed, 100eqv of vinyl ethyl ether is added into the polymerization reaction bottle under the condition of stirring to terminate the polymerization reaction; after 20min, the resulting polymerization solution was dried in a vacuum oven at 60 ℃ for 18h to give 5.9g of a polymerization product. The polymerization process provided in example 1 of the present invention gave a polymerization product with a yield of 99.6%.
According to the method of the technical scheme, the polymerization reaction product obtained in the embodiment 1 of the invention is a random polymer, and nuclear magnetic resonance hydrogen spectrum detection is performed, and the detection result is shown in fig. 1 a. The ionic self-repairing polymer obtained in the embodiment 1 has a structure shown in a formula I, wherein m is 250, and n is 75. According to the formula V, the molar content of the compound having the structure shown in the formula II in the ionic self-repairing polymer obtained in example 1 of the present invention is 23%.
The ion self-repairing polymer obtained in example 1 of the present invention is subjected to a gel permeation chromatography test according to the method described in the above technical scheme, and the test result is shown in fig. 2 a. The number average molecular weight of the self-repairing polymer obtained in example 1 of the invention is 11.6 × 104g/mol, molecular weight distribution 1.50.
The dynamic thermo-mechanical property analysis of the ion self-repairing polymer obtained in the embodiment 1 of the present invention is performed according to the method described in the above technical solution, and the test result is shown in fig. 3 a. The glass transition temperature of the ionic self-repairing polymer obtained in the embodiment 1 of the invention is 53.4 ℃.
The ion self-repairing polymer obtained in example 1 of the present invention is subjected to a thermogravimetric test according to the method described in the above technical solution, and the test result is shown in fig. 4 a. The ion self-repairing polymer obtained in the embodiment 1 of the invention is degraded at 300 ℃, and has better thermal stability.
The mechanical properties of the ionic self-repairing polymer obtained in example 1 of the present invention are tested according to the method described in the above technical solution, and the test result is shown in a curve in fig. 5 a. The Young modulus of the ionic self-repairing polymer obtained in the embodiment 1 of the invention is 243.2MPa, the yield strength is 18.9MPa, the breaking strength is 12.0MPa, and the elongation at break is 340%, which indicates that the ionic self-repairing polymer obtained in the embodiment 1 of the invention has higher mechanical strength.
According to the technical scheme, the ion self-repairing polymer obtained in the embodiment 1 of the invention is subjected to a repair experiment test, the test result is shown in fig. 6a, repair can be carried out at 70 ℃, and repair of nearly 100% can be realized within 12 hours, which shows that the ion self-repairing polymer obtained in the embodiment 1 of the invention has good self-repairing performance. FIG. 7 can be seen under an optical microscope to repair the cross section, and the fracture of the material is obviously blurred after 3h and is completely eliminated after 12 h.
Example 2
In a dry polymerization flask, 557.9mg of bis (biphenyl) norbornene compound and 10mL of methylene chloride were mixed under stirring at 25 ℃ for 10min to obtain a mixture; adding 45.9mg of dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] (benzylidene) bis (3-bromopyridine) ruthenium (II) catalyst and 5mL of dichloromethane into a ampoule, and then carrying out ultrasonic treatment for 3min to fully dissolve the catalyst in the dichloromethane to obtain a catalyst solution; the catalyst solution was added to the above polymerization flask with stirring for 0.5h of polymerization. 5g of 5-norbornene-2-methylene-1-hexyl-3H-imidazole bistrifluoromethylsulfonyl imide compound and 10mL of methylene chloride were added to a ampoule, followed by 3min of ultrasonic treatment, and the monomer solution was added to the above polymerization flask with stirring for 6 hours of polymerization. After the polymerization is completed, adding 400eqv of vinyl ethyl ether into the polymerization reaction bottle under the condition of stirring to terminate the polymerization reaction; after 30min, the resulting polymerization solution was dried in a vacuum oven at 40 ℃ for 18h to give 5.88g of a polymerization product. The yield of the polymerization product obtained by the polymerization method provided in example 2 of the present invention was 99.5%.
According to the method of the technical scheme, the polymerization reaction product obtained in the embodiment 2 of the invention is a diblock copolymer, and the nuclear magnetic resonance hydrogen spectrum detection is performed, and the detection result is shown in fig. 1 b. The ion self-repairing polymer obtained in the embodiment 2 has a structure shown in a formula I, wherein m is 150, and n is 25. According to the formula V, the molar content of the compound having the structure shown in the formula II in the ionic self-repairing polymer obtained in example 2 of the present invention is 14.3%.
The ion self-repairing polymer obtained in the embodiment 2 of the present invention is subjected to a gel permeation chromatography test according to the method described in the above technical scheme, and the test result is shown in fig. 2 b. When bis (biphenyl) norbornenes are addedAfter the completion of the reaction 0.5h, the polymer was found to have a monomodal distribution with a molecular weight of 2.04X 10 in the first stage4g/mol, the molecular weight distribution is 1.56, 5-norbornene-2-methylene-1-hexyl-3H-imidazole bistrifluoromethylsulfonyl imine compound is added to react for 12 hours, and the number average molecular weight of the obtained ion self-repairing polymer is 14.5 multiplied by 104g/mol, molecular weight distribution 1.29, GPC curve showing a monomodal distribution and shift to high molecular weight, indicating successful preparation of the diblock copolymer.
The dynamic thermo-mechanical property analysis of the ion self-repairing polymer obtained in the embodiment 2 of the present invention is performed according to the method described in the above technical solution, and the test result is shown in fig. 3 b. The glass transition temperature of the ionic self-repairing polymer obtained in the embodiment 2 of the invention is 22.6 ℃.
The ion self-repairing polymer obtained in example 2 of the present invention is subjected to a thermogravimetric method test according to the method described in the above technical solution, and the test result is shown in fig. 4 b. The ion self-repairing polymer obtained in the embodiment 2 of the invention is degraded at 300 ℃, and has better thermal stability.
The mechanical properties of the ionic self-repairing polymer obtained in example 2 of the present invention were tested according to the method described in the above technical solution, and the test results are shown in fig. 5 b. The Young modulus, the breaking strength and the breaking elongation of the ionic self-repairing polymer obtained in the embodiment 2 are 16.3MPa, 3.6MPa and 680%, which shows that when a monomer distribution sequence in the polymer is changed into a diblock, the mechanical strength of a high molecular material is reduced, the breaking elongation is increased, and compared with the embodiment 1, when the content of the monomer distribution sequence in the polymer is changed into the diblock, the mechanical strength of the ionic polymer changed from random into the diblock polymer is reduced.
According to the technical scheme, the ion self-repairing polymer obtained in the embodiment 2 of the invention is subjected to a repairing experiment test, and the test result is shown in fig. 6b, after 100 hours of repairing at room temperature, the repairing rate of the elongation at break reaches 42.8%, and when the temperature is raised to 50 ℃, about 85% of repairing can be realized within 12 hours, which indicates that the ion self-repairing polymer material obtained in the embodiment 2 of the invention has good self-repairing performance.
Example 3
Stirring and mixing 463mg of bis (biphenyl) norbornene compound and 5mL of methylene chloride, respectively, in a dry polymerization flask at 40 ℃ for 10min to obtain a mixture; adding 41.1mg of dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] (benzylidene) bis (3-bromopyridine) ruthenium (II) catalyst and 5mL of dichloromethane into a ampoule, and then carrying out ultrasonic treatment for 3min to fully dissolve the catalyst in the dichloromethane to obtain a catalyst solution; the catalyst solution was added to the above polymerization flask with stirring for 0.5h of polymerization. 5g of 5-norbornene-2-methylene-1-hexyl-3H-imidazole bistrifluoromethylsulfonyl imide compound and 10mL of methylene chloride were added to a ampoule, followed by 3min of ultrasonic treatment, and the monomer solution was added to the above polymerization flask with stirring for 6 hours of polymerization. A flask was charged with 463mg of a bis (biphenyl) norbornene compound and 5mL of methylene chloride, followed by sonication for 3min, and the resulting mixture was charged into the above polymerization flask to conduct polymerization for 0.5 h. After the polymerization is completed, adding 200eqv vinyl ethyl ether into the polymerization reaction bottle under the condition of stirring to terminate the polymerization reaction; after 30min, the resulting polymerization solution was dried in a vacuum oven at 30 ℃ for 24h to give 5.89g of a polymerization product. The polymerization reaction product obtained by the polymerization method provided in example 3 of the present invention had a yield of 99.5%.
According to the method of the technical scheme, the ionic polymerization reaction product obtained in the embodiment 3 of the invention is a triblock copolymer, and the nuclear magnetic resonance hydrogen spectrum detection is carried out, wherein the detection result is shown in fig. 1 c. The ionic self-repairing polymer obtained in the embodiment 3 has a structure shown in a formula I, wherein m is 200, and n is 50. According to the formula V, the molar content of the compound having the structure shown in the formula II in the ionic self-repairing polymer obtained in the example 3 of the present invention is 20%.
The ion self-repairing polymer obtained in the embodiment 3 of the present invention is subjected to a gel permeation chromatography test according to the method described in the above technical scheme, and the test result is shown in fig. 2 c. When bis (biphenyl) is addedYl) norbornene Compound after 0.5h the reaction was complete and the molecular weight determination was carried out and the polymer was found to exhibit a monomodal distribution with a molecular weight in the first stage of 1.0X 104g/mol, the molecular weight distribution is 1.23, after 5-norbornene-2-methylene-1-hexyl-3H-imidazole trifluoromethyl sulfonyl imine compound is added for 12 hours to react completely, the number average molecular weight of the ion self-repairing polymer is 11.0 multiplied by 104g/mol, molecular weight distribution of 1.28, GPC curve showing a monomodal distribution, and transferring to high molecular weight, and after 0.5h of further adding bis (biphenyl) norbornene compound, the reaction was completed to obtain an ionic polymer having a number average molecular weight of 12.6X 104g/mol, a molecular weight distribution of 1.37, the GPC curve was still monomodal, and the molecular weight peak was again shifted toward high molecular weight, indicating successful preparation of the triblock copolymer.
The dynamic thermo-mechanical property analysis of the ion self-repairing polymer obtained in the embodiment 3 of the present invention is performed according to the method described in the above technical solution, and the test result is shown in fig. 3 c. The glass transition temperature of the ionic self-repairing polymer obtained in the embodiment 3 of the invention is 23.3 ℃.
The ion self-repairing polymer obtained in the embodiment 3 of the present invention is subjected to a thermogravimetric method test according to the method described in the above technical solution, and the test result is shown in fig. 4 c. The ion self-repairing polymer obtained in the embodiment 3 of the invention is degraded at 300 ℃, and has better thermal stability.
The mechanical properties of the ionic self-repairing polymer obtained in example 3 of the present invention are tested according to the method described in the above technical solution, and the test result is shown in a curve in fig. 5 c. The Young modulus of the ionic self-repairing polymer obtained in the embodiment 3 of the invention is 20.3MPa, the breaking strength is 3.2MPa, and the elongation at break is 900%.
According to the technical scheme, the ion self-repairing polymer obtained in the embodiment 3 of the invention is subjected to a repairing experiment test, and the test result is shown in fig. 6c, after 100 hours at room temperature, the repairing rate of the elongation at break reaches 88.9%, and after 12 hours of repairing at 50 ℃, the repairing rate of the elongation at break approaches 100%, which indicates that the repairing temperature of the ion self-repairing polymer obtained in the embodiment 3 of the invention is increased to accelerate the repairing of the material.
Example 4
557.9mg of a bis (biphenyl) norbornene compound, 5g of 5-norbornene-2-methylene-1-decyl-3 hydro-imidazole bistrifluoromethylsulfonyl imide compound and 25mL of methylene chloride were each charged into a dry polymerization flask at 30 ℃ and mixed with stirring for 10min to obtain a mixture; adding 49.5mg of dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] (benzylidene) bis (3-bromopyridine) ruthenium (II) catalyst and 5mL of dichloromethane into a ampoule, and then carrying out ultrasonic treatment for 3min to fully dissolve the catalyst in the dichloromethane to obtain a catalyst solution; the catalyst solution was added to the above polymerization flask with stirring to conduct polymerization for 20 hours. After the polymerization is completed, 300eqv of vinyl ethyl ether is added into the polymerization reaction bottle under the condition of stirring to terminate the polymerization reaction; after 30min, the resulting polymerization solution was dried in a vacuum oven at 40 ℃ for 18h to give 5.77g of a polymerization product. The yield of the polymerization product obtained by the polymerization method provided in example 1 of the present invention was 98.8%.
According to the method of the above technical scheme, the polymerization reaction product obtained in the embodiment 4 of the present invention is a random copolymer, and the detection result is shown in fig. 1d by nmr hydrogen spectrum detection. The ionic self-repairing polymer obtained in the embodiment 4 has a structure shown in a formula I, wherein m is 150, and n is 25. According to the formula V, the molar content of the compound having the structure shown in the formula II in the ionic self-repairing polymer obtained in the example 4 of the invention is 14.3%.
The ion self-repairing polymer obtained in the embodiment 4 of the present invention is subjected to a gel permeation chromatography test according to the method described in the above technical scheme, and the test result is shown in fig. 2 d. The number average molecular weight of the ionic self-repairing polymer obtained in example 4 of the invention is 12.0 × 104g/mol, molecular weight distribution 1.49.
The dynamic thermo-mechanical property analysis of the ion self-repairing polymer obtained in the embodiment 4 of the present invention is performed according to the method described in the above technical solution, and the test result is shown in fig. 3 d. The glass transition temperature of the ionic self-repairing polymer obtained in the embodiment 4 of the invention is 42.3 ℃.
The ion self-repairing polymer obtained in the embodiment 4 of the present invention is subjected to a thermogravimetric method test according to the method described in the above technical solution, and the test result is shown in fig. 4 d. The ion self-repairing polymer obtained in the embodiment 4 of the invention is degraded at 300 ℃, and has better thermal stability.
The mechanical properties of the ionic self-repairing polymer obtained in example 4 of the present invention are tested according to the method described in the above technical solution, and the test result is shown in a curve in fig. 5 d. The Young modulus of the ionic self-repairing polymer obtained in the embodiment 4 of the invention is 133.1MPa, the yield strength is 4.8MPa, the breaking strength is 5.9MPa, and the elongation at break is 650%, which indicates that the ionic self-repairing polymer obtained in the embodiment 4 of the invention has excellent mechanical strength.
According to the technical scheme, the ionic self-repairing polymer obtained in the embodiment 4 of the invention is subjected to a repairing experiment test, the test result is shown in fig. 6d, and after the ionic self-repairing polymer is repaired for 3 hours at 70 ℃, the repairing rate of the elongation at break reaches 99%, which indicates that the ionic polymer obtained in the embodiment 4 of the invention has excellent mechanical strength and good repairing performance.
Example 5
Separately 838.7mg of bis (biphenyl) norbornene compound and 10mL of methylene chloride were stirred and mixed for 10min at 30 ℃ in a dry polymerization flask to obtain a mixture; adding 37.2mg of dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] (benzylidene) bis (3-bromopyridine) ruthenium (II) catalyst and 5mL of dichloromethane into a ampoule, and then carrying out ultrasonic treatment for 3min to fully dissolve the catalyst in the dichloromethane to obtain a catalyst solution; the catalyst solution was added to the above polymerization flask with stirring for 0.5h of polymerization. 5g of 5-norbornene-2-methylene-1-decyl-3 hydro-imidazole bistrifluoromethylsulfonyl imide compound and 10mL of methylene chloride were added to a ampoule, and then subjected to ultrasonic treatment for 3min, and the monomer solution was added to the above polymerization flask with stirring to conduct polymerization for 12 hours. After the polymerization is completed, 500eqv of vinyl ethyl ether is added into the polymerization reaction bottle under the condition of stirring to terminate the polymerization reaction; after 30min, the resulting polymerization solution was dried in a vacuum oven at 40 ℃ for 18h to give 5.8g of a polymerization product. The polymerization reaction product obtained by the polymerization method provided in example 5 of the present invention had a yield of 99.3%.
According to the method of the above technical scheme, the polymerization reaction product obtained in the embodiment 5 of the present invention is a random copolymer, and the detection result is shown in fig. 1e by performing nmr hydrogen spectrum detection. The ionic self-repairing polymer obtained in the embodiment 5 has a structure shown in a formula I, wherein m is 200, and n is 50. According to the formula V, the molar content of the compound having the structure shown in the formula II in the ionic self-repairing polymer obtained in the example 5 of the present invention is 20%.
The ion self-repairing polymer obtained in the embodiment 5 of the present invention is subjected to a gel permeation chromatography test according to the method described in the above technical scheme, and the test result is shown in fig. 2 e. When the reaction was completed 0.5h after the addition of the bis (biphenyl) norbornene compound, the polymer was found to exhibit a monomodal distribution in which the molecular weight at the first stage was 2.0X 104g/mol, the molecular weight distribution is 1.71, after 5-norbornene-2-methylene-1-decyl-3 hydrogen-imidazole bistrifluoromethylsulfonyl imine compound is added for 12 hours to react completely, the number average molecular weight of the ionic self-repairing polymer is 13.7 multiplied by 104g/mol, molecular weight distribution 1.36, a GPC curve showing a monomodal distribution with a peak of molecular weight shifted towards high molecular weight, indicating successful preparation of the diblock copolymer.
The dynamic thermo-mechanical property analysis of the ion self-repairing polymer obtained in the embodiment 5 of the present invention is performed according to the method described in the above technical solution, and the test result is shown in fig. 3 e. The glass transition temperature of the ionic self-repairing polymer obtained in the embodiment 5 of the invention is 21.1 ℃.
The ion self-repairing polymer obtained in the embodiment 5 of the present invention is subjected to a thermogravimetric method test according to the method described in the above technical solution, and the test result is shown in fig. 4 e. The ion self-repairing polymer obtained in the embodiment 5 of the invention is degraded at 300 ℃, and has better thermal stability.
The mechanical properties of the ionic self-repairing polymer obtained in example 5 of the present invention were tested according to the method described in the above technical solution, and the test results are shown in fig. 5 e. The Young modulus of the ionic self-repairing polymer obtained in the example 5 of the invention is 12.4MPa, the breaking strength is 2.2MPa, and the elongation at break is 1150%, which shows that when the monomer distribution sequence in the polymer is changed into two blocks, the mechanical strength of the high molecular material is reduced, and the elongation at break is increased, compared with the example 4, when the monomer proportion content is the same, the mechanical strength of the ionic polymer changed from random to two-block polymer is reduced.
According to the technical scheme, the ion self-repairing polymer obtained in the embodiment 5 of the invention is subjected to a repairing experiment test, and the test result is shown in fig. 6e, after the ion self-repairing polymer is repaired for 200 hours at room temperature, the repairing rate of the elongation at break reaches 91.3%, and when the temperature is raised to 50 ℃, the ion self-repairing polymer can be repaired by about 99% in 3 hours, which indicates that the ion self-repairing polymer material obtained in the embodiment 5 of the invention has good self-repairing performance.
Example 6
Separately 419.4mg of bis (biphenyl) norbornene compound and 5mL of methylene chloride were stirred and mixed for 10min at 35 ℃ in a dry polymerization flask to obtain a mixture; adding 37.2mg of dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] (benzylidene) bis (3-bromopyridine) ruthenium (II) catalyst and 5mL of dichloromethane into a ampoule, and then carrying out ultrasonic treatment for 3min to fully dissolve the catalyst in the dichloromethane to obtain a catalyst solution; the catalyst solution was added to the above polymerization flask with stirring to conduct polymerization for 2 hours. 5g of 5-norbornene-2-methylene-1-decyl-3 hydro-imidazole bistrifluoromethylsulfonyl imide compound and 10mL of methylene chloride were added to a ampoule, and then subjected to ultrasonic treatment for 3min, and the monomer solution was added to the above polymerization flask with stirring to conduct polymerization for 24 hours. 419.4mg of a bis (biphenyl) norbornene compound and 5mL of methylene chloride were charged in a small ampoule, and then subjected to ultrasonic treatment for 3min, and then charged into the above polymerization flask to conduct polymerization for 2 hours. After the polymerization is completed, 300eqv of vinyl ethyl ether is added into the polymerization reaction bottle under the condition of stirring to terminate the polymerization reaction; after 40min, the resulting polymerization solution was dried in a vacuum oven at 60 ℃ for 12h to give 5.75g of a polymerization product. The yield of the polymerization product obtained by the polymerization method provided in example 6 of the present invention was 98.5%.
According to the method of the technical scheme, the ionic polymerization reaction product obtained in the embodiment 6 of the invention is a triblock copolymer, and the nuclear magnetic resonance hydrogen spectrum detection is carried out, wherein the detection result is shown in fig. 1 f. The ion self-repairing polymer obtained in the embodiment 6 has a structure shown in a formula I, wherein m is 200, and n is 50. According to the formula V, the molar content of the compound having the structure shown in the formula II in the ionic self-repairing polymer obtained in example 6 of the present invention is 20%.
The ion self-repairing polymer obtained in the embodiment 6 of the present invention is subjected to a gel permeation chromatography test according to the method described in the above technical scheme, and the test result is shown in fig. 2 f. When the reaction was completed 0.5h after the addition of the bis (biphenyl) norbornene compound, the polymer was found to exhibit a monomodal distribution in which the molecular weight at the first stage was 1.0X 104g/mol, the molecular weight distribution is 1.26, after 5-norbornene-2-methylene-1-decyl-3 hydrogen-imidazole trifluoromethyl sulfonyl imine compound is added for 12 hours to react completely, the number average molecular weight of the ion self-repairing polymer is 10.7 multiplied by 104g/mol, molecular weight distribution of 1.28, GPC curve showing unimodal distribution, and molecular weight peak shifted to high molecular weight, and subsequently adding bis (biphenyl) norbornene compound for 0.5h to complete the reaction, to obtain ionic polymer with number average molecular weight of 10.9 × 104g/mol, a molecular weight distribution of 1.37, a GPC curve showing a monomodal distribution, and a peak of molecular weight shifted toward high molecular weight again, indicate that the triblock copolymer was successfully prepared.
The dynamic thermo-mechanical property analysis of the ion self-repairing polymer obtained in the embodiment 6 of the present invention is performed according to the method described in the above technical solution, and the test result is shown in fig. 3 f. The glass transition temperature of the ionic self-repairing polymer obtained in the embodiment 6 of the invention is 21.6 ℃.
The ion self-repairing polymer obtained in the embodiment 6 of the present invention is subjected to a thermogravimetric method test according to the method described in the above technical scheme, and the test result is shown in fig. 4 f. The ion self-repairing polymer obtained in the embodiment 6 of the invention is degraded at 300 ℃, and has better thermal stability.
The mechanical properties of the ionic self-repairing polymer obtained in example 6 of the present invention were tested according to the method described in the above technical solution, and the test results are shown in fig. 5 f. The Young modulus of the ionic self-repairing polymer obtained in the embodiment 6 of the invention is 13.0MPa, the breaking strength is 1.4MPa, and the elongation at break is 1190%. Compared with example 5, the triblock copolymer has higher Young's modulus and elongation at break and slightly lower breaking strength than the diblock copolymer under the condition of the same monomer content and different sequence distribution.
According to the technical scheme, the ion self-repairing polymer obtained in the embodiment 6 of the invention is subjected to a repairing experiment test, and a test result is shown in fig. 6f, wherein after 100 hours at room temperature, the repairing rate of the elongation at break reaches 99.2%, and after 3 hours of repairing at 50 ℃, the repairing rate of the elongation at break is close to 78%, which indicates that the repairing temperature of the ion self-repairing polymer obtained in the embodiment 6 of the invention is increased to accelerate the repairing of the material.
The embodiment shows that the invention provides the ion self-repairing polymer material and the preparation method thereof, and the ion self-repairing polymer material has the structure shown in the formula I, wherein m and n are polymerization degrees, m is more than or equal to 150 and less than or equal to 250, and n is more than or equal to 20 and less than or equal to 70. The invention discloses an ion self-repairing high polymer material with controllable mechanical properties, which successfully prepares random, two-block and three-block ionic copolymers, adjusts the mechanical properties of the high polymer material by adjusting the length of an alkyl chain in a norbornene derivative containing imidazole and the sequence distribution of monomers in the polymer, and simultaneously all the prepared ion self-repairing high polymer materials with different mechanical properties have excellent repairing properties.
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 attributes thereof, and it is therefore intended that the present embodiments 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.

Claims (4)

1. An ion self-repairing high polymer material with controllable mechanical properties has a structure shown in a formula I:
Figure FDA0002884488080000011
wherein x is 5 or 9; tf2N is bis (trifluoromethyl) sulfonylimino; m and n are polymerization degrees, wherein m is 150-250, and n is 25-75;
the structural units in the polymer of the high molecular material are distributed into two blocks and three blocks; the structure is as follows:
Figure FDA0002884488080000012
o bis (biphenyl) norbornene
● derivatives of imidazolium norbornene;
wherein O is a bis (biphenyl) norbornene structural unit having a structure represented by formula II, and ● is an imidazole salt ion-containing norbornene derivative structural unit having a structure represented by formula III;
Figure FDA0002884488080000013
in formula III, x is 5 or 9; tf2N is bis (trifluoromethyl) sulfonylimino.
2. The method for preparing the ion self-repairing high molecular material with controllable mechanical properties according to claim 1 is characterized in that under the action of a dichloro [1, 3-bis (2,4, 6-trimethylphenyl) -2-imidazolidinylidene ] (benzylidene) bis (3-bromopyridine) ruthenium (II) catalyst, a compound of bis (biphenyl) norbornene and a compound of a norbornene derivative containing imidazole ions are subjected to ring-opening metathesis polymerization in a dichloromethane solvent by adopting a multi-sequence feeding method, and a terminator is added to terminate the reaction after the reaction is finished, so that a diblock and triblock ionic copolymer self-repairing material is respectively obtained;
starting to add the monomers, and then calculating the total reaction time of the ring-opening metathesis polymerization to be 7-28 h; the temperature of the polymerization reaction is 20-40 ℃;
the molar ratio of the bis (biphenyl) norbornene, the norbornene derivative containing the imidazole ion and the catalyst is 25-75: 150-250: 1; the terminating agent is vinyl ethyl ether; the molar ratio of the terminating agent to the catalyst is (100-500) to 1, and the time for terminating the polymerization reaction is 20-40 min.
3. The method of claim 2, wherein the diblock or triblock distribution of structural units in the polymer is achieved by varying the monomer feed during ring opening metathesis polymerization comprising:
firstly, adding a compound with a formula II structure for polymerization for 0.5-2 h, then adding a compound with a formula III structure for polymerization for 6-24 h, and obtaining a diblock copolymer;
or: firstly, adding half of the fed compound with the structure of the formula II for polymerization for 0.5-2 h, then adding the compound with the structure of the formula III for polymerization for 6-24 h, and then adding half of the fed compound with the structure of the formula II for polymerization for 0.5-2 h to obtain the triblock copolymer.
4. The method according to claim 2, wherein the mass ratio of the compound having the structure represented by the formula II to the dichloromethane solvent used in the polymerization reaction is 1: 2 to 10.
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