CN110746582B - High-temperature-resistant high-performance shape memory polymer and preparation method and application thereof - Google Patents
High-temperature-resistant high-performance shape memory polymer and preparation method and application thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3227—Compounds containing acyclic nitrogen atoms
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2280/00—Compositions for creating shape memory
Abstract
The invention discloses a high-temperature-resistant high-performance shape memory polymer and a preparation method and application thereof. The epoxy resin, the curing agent, the modifier and the catalyst are uniformly stirred, react at 80-150 ℃ under the vacuum condition, and are naturally cooled to prepare the epoxy resin shape memory polymer. The glass transition temperature of the epoxy resin shape memory polymer is increased by introducing the modifier, so that the temperature resistance and the mechanical strength of the material can be increased, and the chemical stability can be kept.
Description
Technical Field
The invention belongs to the technical field of intelligent materials, and particularly relates to a high-temperature-resistant high-performance shape memory epoxy resin polymer and a preparation method and application thereof.
Background
In 2001, Sharpless et al proposed the concept of click chemistry, which has received much attention due to its characteristics of high efficiency, simplicity, controllability, etc. Click chemistry currently consists mainly of three types of reactions: cu (I) catalyzed alkynyl-azido cycloaddition reaction (CuAAC), Diels-Alder reaction of conjugated dienes with dienophiles, and reaction of sulfydryl with various functional groups. The reaction of mercapto group and epoxy group functional group has been one of the hot spots in the field of preparing high molecular material gradually due to the characteristics of no by-product and mild reaction condition. As a shape memory material in the new field, the unique shape memory property is also favored by researchers in various industries. The potential of the functional material field can be widened by applying click chemistry to the preparation of the shape memory material.
However, most of the literature reports that thiol-epoxy click reaction-prepared polymers have a long chain ratio of fat due to the molecular structureHigher crosslinking density and lower environmental temperature to which the material can adapt. By adding other types of modifiers, the crosslinking density can be improved to a certain extent, so that the glass transition temperature T of the material is increasedgHowever, the addition of the modifier increases functional groups with other properties, which may affect the shape memory properties, mechanical properties, chemical stability, etc. of the material. The invention is provided for improving the glass transition temperature of the material while maintaining the shape memory performance and chemical stability of the material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing a high-temperature-resistant shape memory epoxy resin polymer based on a click chemical reaction. Aims to prepare a high-temperature-resistant shape memory epoxy resin polymer with good shape memory performance, mechanical property and chemical stability so as to meet the requirements of related engineering.
The invention also improves the application of the high-temperature-resistant epoxy resin shape memory polymer.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a high-temperature-resistant high-performance epoxy resin shape memory polymer comprises the following steps:
(1) uniformly stirring the epoxy resin, the curing agent, the modifier and the catalyst under a vacuum condition; the catalyst is 0.45-0.55% of the total mass of the raw materials, the curing agent is 20-40% of the total mass of the raw materials, and the rest is epoxy resin and a modifier, wherein the mass ratio of the epoxy resin to the modifier is 6-9: 1-4;
the curing agent is trithiocyanuric acid, the modifier is N, N, N ', N ' -tetracyclooxypropyl-4, 4' -diaminodiphenylmethane, and the catalyst is imidazole.
(2) And pouring the uniformly stirred mixture into a mold, performing heating reaction for 6-9 hours at 80-150 ℃ under a vacuum condition, and performing subsequent natural cooling treatment to obtain the epoxy resin shape memory polymer.
According to the invention, the mass ratio of the epoxy resin to the modifier is preferably 9:1, 8:2, 7:3 or 6: 4.
According to the invention, the amount of the catalyst is preferably 0.5% of the total mass of the raw materials.
According to the invention, in the step (1), the stirring time is preferably 25-35 min.
According to the present invention, in the step (2), the temperature-raising reaction is performed in three stages: reacting at 80 ℃ for 3-4 h, at 120 ℃ for 2-3 h, and at 150 ℃ for 1-2 h. The optimal conditions of the temperature rise reaction are as follows: reacting at 80 ℃ for 3h, at 120 ℃ for 2h and at 150 ℃ for 1 h.
According to the present invention, in the step (2), the vacuum condition is preferably-0.05 MPa to-0.1 MPa; most preferably, the vacuum is-0.08 MPa.
According to the present invention, in the step (2), the natural cooling treatment time is preferably 20 to 24 hours.
In the present invention, the epoxy resin is preferably epoxy resin E51. The mold in the step (2) is preferably a polytetrafluoroethylene mold.
The epoxy resin shape memory polymer prepared by the method has a structure shown in the following formula I:
the epoxy resin shape memory polymer prepared by the invention is applied as a functional material for shape memory and shape recovery.
The invention also provides a shape recovery method of the high-temperature-resistant high-performance epoxy resin shape memory polymer, which comprises the following steps:
a. preparing the high-temperature-resistant epoxy resin shape memory polymer into a memory shape above the glass transition temperature, keeping the memory shape at 150 ℃ for 1h, and cooling to room temperature to obtain a polymer material with the memory shape, thereby completing the shape memory process;
b. preparing the polymer material with the memory shape in the step a into a temporary shape above the glass transition temperature, and then cooling to room temperature to obtain the polymer material with the temporary shape;
c. and heating the polymer material with the temporary shape to be higher than the glass transition temperature to obtain the polymer material with the memory shape, and finishing the shape recovery process of the shape memory polymer.
In the technical scheme, the external temperature is increased to 10-20 ℃ above the glass transition temperature; the memory shape or the temporary shape is prepared by applying an external force.
The reaction route of the high-temperature-resistant epoxy resin shape memory polymer prepared by the invention is shown as follows:
compared with the prior art, the invention has the beneficial effects that:
the innovation of the invention is mainly selection of the modifier based on the mercapto-epoxy click chemical reaction, and the introduction of the N, N, N ', N ' -tetracyclooxypropyl-4, 4' -diaminodiphenylmethane modifier is unexpectedly found to improve the temperature resistance and the mechanical strength of the material, and the preferred modifier has benzene ring and tetracyclooxy group with stronger stability and does not contain other functional groups, so that the related performance of the epoxy resin shape memory polymer is not reduced. Through click chemical reaction, under the action of an imidazole catalyst, sulfydryl attacks epoxy groups to generate ring-opening polymerization reaction to form a space grid structure, and the preferable geometrically symmetric molecular structure of the modifier can greatly improve the crosslinking density of the epoxy resin shape memory polymer, improve the temperature resistance and mechanical strength of the material and make up for the defect of the temperature resistance of a cured product of common mercaptan and epoxy resin.
The adaptive temperature of the epoxy resin shape memory polymer prepared by the invention is 80-120 ℃, the application temperature of the epoxy resin prepared by the mercaptan curing agent is improved, the shape fixing rate is kept above 98%, and the shape recovery rate is kept above 94%. The click chemical reaction adopted in the prior art has lower application temperature of the prepared material due to the molecular structure of the sulfydryl curing agent, and the defect of lower application temperature can be overcome by introducing the specific modifier.
The preparation method of the epoxy resin shape memory polymer is efficient, rapid, controllable in reaction and simple to operate, and is suitable for industrial production; meanwhile, when the epoxy resin shape memory polymer prepared by the invention is applied, the methods of processing the epoxy resin shape memory polymer into a temporary shape and recovering the epoxy resin shape memory polymer into an initial shape are simple and easy to implement, and the prepared high-temperature-resistant epoxy resin shape memory polymer has good chemical stability and can meet the requirements of related engineering.
Drawings
FIG. 1 is a photograph showing the shape memory property at 120 ℃ of a high temperature resistant epoxy resin shape memory polymer prepared in example 4. a. Is a temporary shape, b-e is a recovery process shape, f is an initial shape.
FIG. 2 is a graph showing the chemical stability of example samples in acid-base solutions. PMP-10, PMP-20, PMP-30 and PMP-40 were prepared samples of examples 1 to 4, respectively.
Detailed Description
The invention will be further illustrated with reference to the following specific examples, without limiting the scope of the invention thereto.
Example 1:
epoxy resin E51, N, N, N ', N ' -tetracyclooxypropyl-4, 4' -diaminodiphenylmethane 9g and 1g, thiocyanuric acid 4.8g and catalyst 2-methylimidazole 0.075g were mixed, and the mixture was stirred under-0.08 MPa vacuum for 30 min. Pouring the uniformly stirred mixture into a polytetrafluoroethylene mold, placing the polytetrafluoroethylene mold under a vacuum condition, reacting for 3 hours at 80 ℃, reacting for 2 hours at 120 ℃, reacting for 1 hour at 150 ℃, and performing 24-hour subsequent natural cooling treatment to obtain the high-temperature-resistant epoxy resin shape memory polymer material.
Example 2:
epoxy resin E51, N, N, N ', N ' -tetracyclooxypropyl-4, 4' -diaminodiphenylmethane 8g and 2g respectively, thiocyanuric acid 5.1g, and catalyst 2-methylimidazole 0.075g were mixed, and stirred under-0.08 MPa vacuum for 30 min. Pouring the uniformly stirred mixture into a polytetrafluoroethylene mold, placing the polytetrafluoroethylene mold under a vacuum condition, reacting for 3 hours at 80 ℃, reacting for 2 hours at 120 ℃, reacting for 1 hour at 150 ℃, and performing 24-hour subsequent natural cooling treatment to obtain the high-temperature-resistant epoxy resin shape memory polymer material.
Example 3:
7g of epoxy resin E51, 3g of N, N, N ', N ' -tetracyclooxypropyl-4, 4' -diaminodiphenylmethane, 5.3g of trithiocyanuric acid and 0.075g of catalyst 2-methylimidazole were mixed and stirred under a vacuum condition of-0.08 MPa for 30 min. Pouring the uniformly stirred mixture into a polytetrafluoroethylene mold, placing the polytetrafluoroethylene mold under a vacuum condition, reacting for 3 hours at 80 ℃, reacting for 2 hours at 120 ℃, reacting for 1 hour at 150 ℃, and performing 24-hour subsequent natural cooling treatment to obtain the high-temperature-resistant epoxy resin shape memory polymer material.
Example 4:
epoxy resin E51, N, N, N ', N ' -tetracyclooxypropyl-4, 4' -diaminodiphenylmethane in a mass of 6g and 4g, thiocyanuric acid in a mass of 5.6g, and 2-methylimidazole in a mass of 0.075g as a catalyst were mixed. The polymerization monomer and the catalyst are placed under the vacuum condition of-0.08 MPa and stirred for 30 min. Pouring the uniformly stirred mixture into a polytetrafluoroethylene mold, placing the polytetrafluoroethylene mold under a vacuum condition, reacting for 3 hours at 80 ℃, reacting for 2 hours at 120 ℃, reacting for 1 hour at 150 ℃, and performing 24-hour subsequent natural cooling treatment to obtain the high-temperature-resistant epoxy resin shape memory polymer material. FIG. 1 is a photograph of a high temperature resistant epoxy shape memory polymer prepared in example 4, showing shape memory properties at 120 ℃ where a is a temporary shape and f is an initial shape.
Comparative example:
6g of epoxy resin E51, 2g of trithiocyanuric acid and 0.02g of catalyst 2-methylimidazole were mixed and stirred under vacuum for 30 min. Pouring the uniformly stirred mixture into a polytetrafluoroethylene mold, placing the polytetrafluoroethylene mold under the vacuum condition of-0.08 MPa, reacting for 3 hours at the temperature of 80 ℃, reacting for 2 hours at the temperature of 120 ℃, reacting for 1 hour at the temperature of 150 ℃, and naturally cooling for 24 hours to prepare the thermosetting epoxy resin shape memory polymer material. The prepared thermosetting epoxy resin shape memory polymer material sample is placed at the temperature of 62 ℃ plus 10 ℃ to deform, then is cooled to 25 ℃, the shape can be fixed into a temporary shape, and then is placed at 62 ℃ to restore the initial shape.
The mechanical properties and shape memory temperature contrast of the samples prepared in examples 1-4 above and the comparative samples are shown in Table 1 below.
TABLE 1
As can be seen from table 1: in the samples of the embodiment, as the proportion of the modifier in the raw materials is increased, firstly, the shape memory transition temperature is obviously improved, and the modifier has a good gain effect on the temperature resistance of the epoxy resin shape memory polymer; secondly, the shape fixation rate and the shape recovery rate are both kept above 90%, and the addition of the modifier does not have negative influence on the shape memory performance.
It can also be seen from table 1: the sample is placed at 81 ℃ to deform and then cooled to 25 ℃, the shape can be fixed into a temporary shape, and the sample can be placed at 81 ℃ again and can be restored into an initial shape; the sample is placed at 92 ℃ to deform and then cooled to 25 ℃, the shape can be fixed into a temporary shape, and the sample is placed at 92 ℃ to deform and can be restored into an initial shape; the sample is placed at 105 ℃ to deform and then cooled to 25 ℃, the shape can be fixed into a temporary shape, and then the sample is placed at 105 ℃ to deform and can be restored into an initial shape; and (3) placing the sample at 118 ℃ for deformation, cooling to 25 ℃, fixing the shape to be a temporary shape, and then placing the sample at 118 ℃ for deformation and recovering to be the initial shape.
Chemical stability of example samples in acid-base solutions is shown in figure 2. As can be seen from fig. 2: in the embodiment, the sample has good chemical stability in acid-base solution, the change of the mass is very small in the environment with different acidity and alkalinity, and even if the sample is placed in the environment with very strong acidity, the maximum loss amount of the mass is only 0.25 percent, which shows that the chemical stability of the high-temperature-resistant epoxy resin shape memory polymer prepared by the preparation method disclosed by the invention is enough to meet the requirements of most engineering environments.
Claims (10)
1. An epoxy shape memory polymer having the structure shown in formula I below:
the polymer is prepared by the reaction of epoxy resin E51, curing agent trithiocyanuric acid and modifier N, N, N ', N ' -tetracyclooxypropyl-4, 4' -diaminodiphenylmethane, wherein the mass ratio of the epoxy resin to the modifier is 7:3 or 6: 4.
2. A preparation method of a high-temperature-resistant high-performance epoxy resin shape memory polymer comprises the following steps:
(1) uniformly stirring the epoxy resin E51, the curing agent, the modifier and the catalyst under a vacuum condition; wherein the dosage of the catalyst is 0.45-0.55% of the total mass of the raw materials, the dosage of the curing agent is 20-40% of the total mass of the raw materials, and the balance is epoxy resin and a modifier, and the mass ratio of the epoxy resin to the modifier is 7:3 or 6: 4;
the curing agent is trithiocyanuric acid, the modifier is N, N, N ', N ' -tetracyclooxypropyl-4, 4' -diaminodiphenylmethane, and the catalyst is imidazole;
(2) and pouring the uniformly stirred mixture into a mold, performing heating reaction for 6-9 hours at 80-150 ℃ under a vacuum condition, and performing subsequent natural cooling treatment to obtain the epoxy resin shape memory polymer.
3. The method for preparing the high temperature resistant high performance epoxy resin shape memory polymer according to claim 2, wherein the amount of the catalyst is 0.5% of the total mass of the raw materials.
4. The method for preparing the high temperature resistant high performance epoxy resin shape memory polymer according to claim 2, wherein in the step (1), the stirring time is 25-35 min.
5. The method for preparing the high temperature resistant high performance epoxy resin shape memory polymer according to claim 2, wherein in the step (2), the temperature-rising reaction conditions are as follows: reacting at 80 ℃ for 3h, at 120 ℃ for 2h and at 150 ℃ for 1 h.
6. The method for preparing a high temperature resistant high performance epoxy resin shape memory polymer according to claim 2, wherein in the step (2), the vacuum condition is-0.05 MPa to-0.1 MPa.
7. The method for preparing the high temperature resistant high performance epoxy resin shape memory polymer according to claim 2, wherein in the step (2), the vacuum condition is-0.08 MPa.
8. The method for preparing the high temperature resistant high performance epoxy resin shape memory polymer according to claim 2, wherein in the step (2), the natural cooling treatment time is 20 to 24 hours.
9. Use of the epoxy resin shape memory polymer of claim 1 as a functional material for shape memory and shape recovery.
10. A shape recovery method of high-temperature-resistant high-performance epoxy resin shape memory polymer comprises the following steps:
a. preparing the epoxy resin shape memory polymer of claim 1 into a memory shape above the glass transition temperature, then keeping the shape memory polymer at 150 ℃ for 1h, and then cooling to room temperature to obtain a polymer material with the memory shape, thereby completing the shape memory process;
b. preparing the polymer material with the memory shape in the step a into a temporary shape above the glass transition temperature, and then cooling to room temperature to obtain the polymer material with the temporary shape;
c. heating the polymer material with the temporary shape to be above the glass transition temperature to obtain the polymer material with the memory shape, and finishing the shape recovery process of the shape memory polymer.
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| JP2008255217A (en) * | 2007-04-04 | 2008-10-23 | Yokohama Rubber Co Ltd:The | Curable resin composition |
| JP2014031461A (en) * | 2012-08-06 | 2014-02-20 | Panasonic Corp | Liquid epoxy resin composition and composite member as well as electronic component device |
| US9290462B1 (en) * | 2013-12-17 | 2016-03-22 | Tda Research, Inc. | Polythiol curing agents with low odor |
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