CN115490876B - Self-repairing dimer fatty acid based shape memory elastomer and preparation method thereof - Google Patents
Self-repairing dimer fatty acid based shape memory elastomer and preparation method thereof Download PDFInfo
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Abstract
Adding dimer fatty acid and epichlorohydrin into a reaction vessel, adding benzyl trimethyl ammonium bromide, reacting for 3 hours at 120 ℃, then adding sodium hydroxide and calcium oxide, and stirring for 6 hours at 60 ℃; filtering the product by a funnel paved by silica gel or diatomite, collecting filtrate, and recycling the redundant epichlorohydrin by rotary evaporation to obtain an intermediate A; at N 2 Under the atmosphere, taking the intermediate A obtained in the previous step to react with furfuryl amine, heating to 60 ℃ after the dripping is finished, and reacting for 2.5h to obtain a product B; the product B is mixed with 4,4' -bismaleimide diphenylmethane and an intermediate A to prepare the self-repairing dimer fatty acid based shape memory elastomer under the heating condition of 90 ℃. The invention has simple process and controllable performance, can realize self-repairing and shape memory functions under lower heating condition, and has less loss of shape memory performance and mechanical performance after repeated use.
Description
Technical Field
The invention belongs to the field of bio-based intelligent polymer materials, and particularly relates to a self-repairing dimer fatty acid based shape memory elastomer and a preparation method thereof.
Background
With the development of technology, intelligent polymer materials have become an important research field of material science. The intelligent material has a sensing function and can detect the stimulation intensity of the outside (or inside) of the disease identification; the system has an information transmission function, and selects and controls response in a set optimization mode; the system has the advantages of sensitive and proper response to the environment transformation and the executed functions; the external stimulus condition can be quickly restored to the original state after being eliminated. The intelligent high molecular material makes the inanimate organic material become 'feel' and 'perception' through organic and synthetic methods. Such materials have been used in real life and are becoming the subject of new research by technological workers in various countries.
Shape memory materials refer to materials that are deformed and fixed to another shape and then restored to the original shape by physical or chemical stimulation such as heat, light, electricity, etc. The application of shape memory materials relates to various fields of industry and daily life, such as smart textiles, flexible electronics, 3D or 4D printing, smart medical devices, etc. However, in the current practical application, the shape memory property and mechanical property of the shape memory polymer material tend to be gradually reduced after multiple cycles, and damage also tends to occur after repeated use. In addition, most of the raw materials for synthesizing the shape memory polymer which are commonly used at present are converted from petrochemical resources, and along with the increasing of carbon emission and the continuous consumption of petroleum resources, the use of biomass resources instead of non-sustainable resources is becoming the mainstream of the development of the era.
The conventional synthetic polymer materials can be classified into thermoplastic and thermosetting materials, and when the thermoplastic materials are heated to a certain temperature, intermolecular forces are destroyed to generate fluidity, so that the thermoplastic materials have repeated processability. While most common shape memory polymer materials are thermoset, thermoset materials are limited by cross-linked networks, traditional thermoset materials do not have reproducible processability and once cured, the material is neither melted nor dissolved. Thermoset materials generally have better dimensional stability than thermoplastic materials, but recycling of thermoset materials has been a major challenge in the polymer arts. Conventional landfills and incineration not only do not make efficient use of the remaining value of the material, but also place a burden on the environment. With the increasing awareness of human being on environmental protection, studies on recycling of thermosetting materials are paid attention to. The best method for solving the problem is to develop a novel thermosetting material, so that the material has the characteristics of easy processing, repair and degradation.
On the other hand, the bio-based material has the characteristics of green, environment-friendly, renewable raw materials and biodegradability which are not possessed by the traditional high polymer material, particularly the dimer fatty acid is prepared by DA reaction of polyunsaturated fatty acid or ester thereof (such as linoleic acid, linolenic acid and the like), and the bio-based material is a hot spot for researching bio-based polymers due to the fact that the raw materials are easily available, low in toxicity and high in universality. The dimer acid contains a reactive carbon-carbon double bond and carboxyl, can generate free radical copolymerization and esterification reaction, and more importantly, the larger alkyl in the dimer acid structure ensures that the dimer acid has better flexibility, water resistance, sealing property and good adhesion to metal materials. The dynamic Diels-Alder reaction performance is excellent, can be carried out under milder conditions, and basically does not need to introduce a catalyst. The invention prepares the intelligent functional polymer material by adopting the bio-based resource dimer fatty acid. Has certain theoretical guidance and application significance for promoting the progress of the application technology of vegetable oil-based polymers.
Disclosure of Invention
The technical problems to be solved are as follows: the invention provides a self-repairing dimer fatty acid based shape memory elastomer and a preparation method thereof, wherein dimer fatty acid is used as a raw material to prepare a shape memory elastomer material fused with dynamic Diels-Alder bonds.
The technical scheme is as follows: the preparation method of the self-repairing dimer fatty acid based shape memory elastomer comprises the following steps: the first step: adding dimerized fatty acid and epichlorohydrin into a reaction vessel according to the following molar ratio of 1:20, adding benzyl trimethyl ammonium bromide with the mole number of 1.6% of dimerized fatty acid, reacting for 3 hours at 120 ℃, cooling the mixture to 60 ℃, and then adding dimerized fatty acidSodium hydroxide and calcium oxide with the mole numbers of the fatty acid of 200 percent are stirred for 6 hours at 60 ℃; filtering the product by a funnel paved by silica gel or diatomite, collecting filtrate, and recycling the redundant epichlorohydrin by rotary evaporation to obtain an intermediate A; and a second step of: at N 2 Under the atmosphere, taking the intermediate A obtained in the previous step, reacting with furfuryl amine, mixing furfuryl amine and the intermediate A according to the molar ratio of 2:1, heating to 60 ℃ after the dripping is finished, and reacting for 2.5 hours to obtain a product B; and a third step of: the product B is mixed with 4,4' -bismaleimide diphenylmethane and an intermediate A to prepare the self-repairing dimer fatty acid based shape memory elastomer under the heating condition of 90 ℃.
The addition molar quantity of the 4,4' -bismaleimide diphenylmethane is 50-100% of the molar quantity of the product B.
Preferably, the molar amount of the 4,4' -bismaleimide diphenylmethane added is 100% of the molar amount of the product B.
The molar amount of the intermediate A added in the third step is 50% -100% of the molar amount of the product B.
Preferably, the molar amount of intermediate A added in the third step is 50% of the molar amount of product B.
The self-repairing dimer fatty acid based shape memory elastomer prepared by the preparation method.
The beneficial effects are that: (1) The invention introduces reversible dynamic covalent bond, which can not only improve the shape memory capability of polymer material, but also make the material have certain self-repairing property. (2) The preparation process has the advantages of simple route, mild reaction, stable property of the prepared product and certain utilization value. (3) The stiffness and flexibility characteristics of this elastomer can be controlled by adjusting the amount of 4,4' -bismaleimide diphenylmethane and intermediate a that need to be added during the third cure step.
Drawings
FIG. 1 is an infrared spectrum of a dimerized fatty acid based shape memory polymer of example 1.
In the infrared spectrum, the dimer fatty acid is in the curve of 2500-3500cm −1 Broad peak sum 1706cm at −1 The absorption peak confirms the presence of carboxyl groups. In the course of bendingIn line product B, 910cm was found on the curve of intermediate A −1 The characteristic peak of epoxy group at the position disappeared, and 1740cm appeared in the curve product B and the intermediate A −1 Characteristic peaks of ester groups of 1706cm −1 The characteristic peak of the carboxyl group on the left and right disappeared, which indicates that the carboxyl group in the dimer fatty acid was completely reacted, and 3350 cm −1 The characteristic peak of hydrogen bond appears, which proves that the resin product B is successfully synthesized.
Detailed Description
No part is referred to herein as being identical to, or being implemented in, the prior art. The following are preferred embodiments of the present invention, but the present invention is not limited to the following only embodiments, and modifications of the embodiments are also considered as the protection scope of the present invention.
Example 1
The first step: adding dimeric fatty acid and epichlorohydrin into a reaction vessel according to the following molar ratio of 1:20, adding benzyl trimethyl ammonium bromide with the molar ratio of 1.6% of the dimeric fatty acid, reacting for 3 hours at 120 ℃, cooling the mixture to 60 ℃, then adding sodium hydroxide and calcium oxide with the molar ratio of 200% of the dimeric fatty acid, and stirring for 6 hours at 60 ℃; filtering the product by a funnel paved by silica gel or diatomite, collecting filtrate, and recycling the redundant epichlorohydrin by rotary evaporation to obtain an intermediate A; and a second step of: at N 2 Under the atmosphere, taking the intermediate A obtained in the previous step, and reacting with furfuryl amine, wherein the mol ratio of furfuryl amine to the intermediate A is 2:1, mixing, heating to 60 ℃ after dripping, and reacting for 2.5 hours to obtain a product B; and a third step of: the product B was mixed with 4,4' -bismaleimide diphenylmethane (molar amount is 50% of the molar amount of the product B), the intermediate a (molar amount is 100% of the molar amount of the product B), and heated in an oven at 90 ℃ for 2 hours to obtain a self-repairing dimer fatty acid based shape memory elastomer.
Example 2
The first step: adding dimer fatty acid and epichlorohydrin into a reaction vessel according to the following molar ratio of 1:20, adding benzyl trimethyl ammonium bromide with the mole number of 1.6% of the dimer fatty acid, reacting for 3 hours at 120 ℃, and cooling the mixture to 60 DEG CThen adding sodium hydroxide and calcium oxide with the mole numbers of dimer fatty acid of 200%, and stirring for 6 hours at 60 ℃; filtering the product by a funnel paved by silica gel or diatomite, collecting filtrate, and recycling the redundant epichlorohydrin by rotary evaporation to obtain an intermediate A; and a second step of: at N 2 Under the atmosphere, taking the intermediate A obtained in the previous step, and reacting with furfuryl amine, wherein the mol ratio of furfuryl amine to the intermediate A is 2:1, mixing, heating to 60 ℃ after dripping, and reacting for 2.5 hours to obtain a product B; and a third step of: the product B was mixed with 4,4' -bismaleimide diphenylmethane (molar amount is 100% of the molar amount of the product B), intermediate a (molar amount is 50% of the molar amount of the product B), and heated in an oven at 90 ℃ for 2 hours to obtain a self-repairing dimer fatty acid based shape memory elastomer.
Example 3
The first step: adding dimeric fatty acid and epichlorohydrin into a reaction vessel according to the following molar ratio of 1:20, adding benzyl trimethyl ammonium bromide with the molar ratio of 1.6% of the dimeric fatty acid, reacting for 3 hours at 120 ℃, cooling the mixture to 60 ℃, then adding sodium hydroxide and calcium oxide with the molar ratio of 200% of the dimeric fatty acid, and stirring for 6 hours at 60 ℃; filtering the product by a funnel paved by silica gel or diatomite, collecting filtrate, and recycling the redundant epichlorohydrin by rotary evaporation to obtain an intermediate A; and a second step of: at N 2 Under the atmosphere, taking the intermediate A obtained in the previous step, and reacting with furfuryl amine, wherein the mol ratio of furfuryl amine to the intermediate A is 2:1, mixing, heating to 60 ℃ after dripping, and reacting for 2.5 hours to obtain a product B; and a third step of: the product B was mixed with 4,4' -bismaleimide diphenylmethane (molar amount of which is 75% of the molar amount of the product B) and intermediate A (molar amount of which is 75% of the molar amount of the product B), and heated in an oven at 90℃for 2 hours to obtain a self-repairing dimer fatty acid based shape memory elastomer.
Example 4
The first step: adding dimerized fatty acid and epichlorohydrin into a reaction vessel according to the following molar ratio of 1:20, adding benzyl trimethyl ammonium bromide with the mole number of 1.6% of dimerized fatty acid, reacting for 3 hours at 120 ℃, cooling the mixture to 60 ℃, and then adding two componentsSodium hydroxide and calcium oxide, the molar numbers of which are 200%, are respectively mixed for 6 hours at 60 ℃; filtering the product by a funnel paved by silica gel or diatomite, collecting filtrate, and recycling the redundant epichlorohydrin by rotary evaporation to obtain an intermediate A; and a second step of: at N 2 Under the atmosphere, taking the intermediate A obtained in the previous step, and reacting with furfuryl amine, wherein the mol ratio of furfuryl amine to the intermediate A is 2:1, mixing, heating to 60 ℃ after dripping, and reacting for 2.5 hours to obtain a product B; and a third step of: the product B was mixed with 4,4' -bismaleimide diphenylmethane (molar amount of 100% of the molar amount of the product B) and intermediate A (molar amount of 100% of the molar amount of the product B), and heated in an oven at 90℃for 2 hours to obtain a self-repairing dimer fatty acid based shape memory elastomer.
The elastomeric materials prepared in each example were cut into bars of 40 mm ×6 mm ×0.8 mm and tested for tensile mechanical properties, shape memory and self-healing properties, the results of which are set forth in table 1.
Claims (6)
1. The preparation method of the self-repairing dimer fatty acid based shape memory elastomer is characterized by comprising the following steps: the first step: adding dimeric fatty acid and epichlorohydrin into a reaction vessel according to the following molar ratio of 1:20, adding benzyl trimethyl ammonium bromide with the molar ratio of 1.6% of the dimeric fatty acid, reacting for 3 hours at 120 ℃, cooling the mixture to 60 ℃, then adding sodium hydroxide and calcium oxide with the molar ratio of 200% of the dimeric fatty acid, and stirring for 6 hours at 60 ℃; filtering the product by a funnel paved by silica gel or diatomite, collecting filtrate, and recycling the redundant epichlorohydrin by rotary evaporation to obtain an intermediate A; and a second step of: at N 2 Under the atmosphere, taking the intermediate A obtained in the previous step, reacting with furfuryl amine, mixing furfuryl amine and the intermediate A according to the molar ratio of 2:1, heating to 60 ℃ after the dripping is finished, and reacting for 2.5 hours to obtain a product B; and a third step of: product B was reacted with 4,4' -bismaleimide diphenylmethane and an intermediateThe self-repairing dimer fatty acid based shape memory elastomer is prepared by mixing the body A and heating at 90 ℃.
2. The method for preparing a self-repairing dimer fatty acid based shape memory elastomer according to claim 1, wherein the addition molar amount of 4,4' -bismaleimide diphenylmethane is 50% -100% of the molar amount of product B.
3. The method for preparing a self-repairing dimer fatty acid based shape memory elastomer according to claim 1, wherein the addition molar amount of 4,4' -bismaleimide diphenylmethane is 100% of the molar amount of product B.
4. The method for producing a self-repairing dimer fatty acid based shape memory elastomer according to claim 1, wherein the added molar amount of the intermediate a in the third step is 50% to 100% of the molar amount of the product B.
5. The method for producing a self-repairing dimer fatty acid based shape memory elastomer according to claim 1, wherein the added molar amount of the intermediate a in the third step is 50% of the molar amount of the product B.
6. A self-healing dimer fatty acid based shape memory elastomer prepared by the method of any one of claims 1-5.
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| CN104194269A (en) * | 2014-08-31 | 2014-12-10 | 海安南京大学高新技术研究院 | Reversible repair functional matrix resin for pultrusion and preparation method of matrix resin |
| CN107955161A (en) * | 2017-11-30 | 2018-04-24 | 华南理工大学 | A kind of self-healing elastomeric material based on the effect of reversible non-covalent key and preparation method thereof |
| CN110790958A (en) * | 2018-08-01 | 2020-02-14 | 北京化工大学 | Thermally reversible crosslinked rubber and preparation method thereof |
| CN112210194A (en) * | 2020-09-17 | 2021-01-12 | 中山大学 | Self-repairing heat-conducting epoxy resin composite material and preparation method and application thereof |
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| EP2348063B1 (en) * | 2009-05-15 | 2020-04-29 | Kingfa Science & Technology Co., Ltd. | Biodegradable polyesters and preparing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104194269A (en) * | 2014-08-31 | 2014-12-10 | 海安南京大学高新技术研究院 | Reversible repair functional matrix resin for pultrusion and preparation method of matrix resin |
| CN107955161A (en) * | 2017-11-30 | 2018-04-24 | 华南理工大学 | A kind of self-healing elastomeric material based on the effect of reversible non-covalent key and preparation method thereof |
| CN110790958A (en) * | 2018-08-01 | 2020-02-14 | 北京化工大学 | Thermally reversible crosslinked rubber and preparation method thereof |
| CN112210194A (en) * | 2020-09-17 | 2021-01-12 | 中山大学 | Self-repairing heat-conducting epoxy resin composite material and preparation method and application thereof |
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