CN102827350B - Modified epoxide resin with thermal driving shape memory function and preparation method thereof - Google Patents
Modified epoxide resin with thermal driving shape memory function and preparation method thereof Download PDFInfo
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- CN102827350B CN102827350B CN201210341620.2A CN201210341620A CN102827350B CN 102827350 B CN102827350 B CN 102827350B CN 201210341620 A CN201210341620 A CN 201210341620A CN 102827350 B CN102827350 B CN 102827350B
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Abstract
The invention relates to a modified epoxide resin with a shape memory function and a preparation method of the modified epoxide resin, belonging to the technical field of a functional high molecular material. The response temperature of the modified epoxide resin material provided by the invention can be adjusted within the range of 32-60 DEG C, the material can be bent at a large angle of 720 degrees at the temperature more than the thermal response temperature, and the shape fixed rate and recovery rate of the modified epoxide resin reach 100%. The preparation method of the modified epoxide resin comprises the following steps of: firstly, preparing end sulfydryl dihydric alcohol ester; secondly, preparing modified epoxide resin; and thirdly, preparing the modified epoxide resin with the shape memory function. Compared with the existing shape memory material, the modified epoxide resin has the advantages of being simple in preparation technology, capable of meeting a green environment protection requirement, low in thermal response temperature, capable of being adjusted, capable of realizing saturated solidifying, low in solidifying temperature, short in solidifying time, short in thermal response time, large in sample flexible angle, and high in shape recovery rate.
Description
Technical field
The invention belongs to functional high molecule material technical field.The present invention relates to a kind of shape-memory polymer, be specifically related to a kind of modified epoxy and preparation method with heat driving shape memory function.
Background technology
Shape-memory polymer (Shape Memory Polymer, SMP) refers to have original shape, after deformation fixing, can change external conditions by methods such as heating, makes it recover the polymkeric substance of original shape.Be a kind of stimulation--the new functional macromolecule material of induction type, having can be in the characteristic that is subject to change under external stimulus reaction its shape.Since early 1960s is found the shape memory effect of Ni-Ti alloy, the research of memorial alloy makes great progress.With respect to shape memory alloy, the unrivaled feature such as shape memory high molecule material has that density is low, recovery of shape rate is high, memory recovery temperature is wide, deformation quantity is large, workability good and cost is low.
It is a certain temperature deformation more than room temperature that heat drives shape-memory polymer, and can at room temperature fix deformation and long-term storage, and in the time again rising to a certain specified temp, material can return to the polymkeric substance of original shape very soon.First case shape-memory polymer is the polynorbornene that French coal chemistry company succeeded in developing in 1984 in the world.Japan has had the Industrialized processing technique of 4 kinds of SMP at present: polynorbornene, trans 1,4-polyisoprene, styrene/butadiene copolymers and urethane (PUR), these all belong to, and thermoplasticity shape memory is poly-will be used in civil area with owner.Due to mechanical property and stable on heating reason, above-mentioned thermoplasticity shape polymer can not be served as the resin matrix of aerospace matrix material.
Epoxy resin is a kind of main resin matrix of aerospace matrix material, Chinese patent " a kind of epoxy resin by using liquid crystal and preparation method and application with shape memory effect " (publication number CN102504202A) discloses and will after epoxy resin heat fused, pour in preheated mold, be heating and curing, first at 40 ~ 170 DEG C, solidify 4 ~ 8 hours, then at 200 ~ 220 DEG C, solidify 0.5 ~ 2 hour; Chinese patent " a kind of epoxy resin shape memory polymer material and preparation method thereof " (publication number CN101195701A) discloses and will after epoxy resin by using liquid crystal monomer and solidifying agent dissolving, add curing catalyst, Procuring in 5 ~ 12 hours at 50 ~ 120 DEG C under vacuum, then 150 ~ 160 DEG C of intermediate temperature settings 4 ~ 6 hours, 180 ~ 220 DEG C solidify 1 ~ 2 hour, obtain epoxy resin shape memory material; The epoxy resin shape memory polymkeric substance of aforesaid method report, be difficult to realize saturated shape memory effect, and thermal response temperature is high, and the time of response is long, and deformation angle is low, and recovery of shape rate is low.
Summary of the invention
The object of the present invention is to provide modified epoxy and the preparation method with heat driving shape memory function.
The above-mentioned modified epoxy with heat driving shape memory function is prepared according to the following steps:
The first step, the preparation of end mercaptan carboxylic acid binary alcohol esters: dibasic alcohol and end mercaptan carboxylic acid are dropped into and are equipped with in the reactor of water-and-oil separator by the mol ratio of 1:2, taking benzene as band aqua, tosic acid is catalyzer, be heated to boiling, isolate water that reaction generates until esterification completes by water-and-oil separator, make intermediate product end mercaptan carboxylic acid binary alcohol esters;
Second step, the preparation of modified epoxy: end mercaptan carboxylic acid the binary alcohol esters synthetic the first step and epoxy resin are dropped into and had in the reactor of stirring by the mol ratio of 5 ~ 20:100, be heated to 40 DEG C, react 2 hours, obtain Toughening Modification of Epoxy;
The 3rd step, there is the preparation that heat drives the modified epoxy of shape memory function: Toughening Modification of Epoxy synthetic second step and amine curing agent are carried out to proportioning, in epoxy resin, the amino mol ratio of unreacted epoxide group and amine curing agent is 2:1, after mixing, immerse in forming mould, 120 DEG C of hot pressing 2h moulding, must have the high-toughness epoxy resin test specimen of shape memory function.
Sulfydryl described in step 2 reacts with mol ratio 1:1 with epoxide group.
Described catalyzer tosic acid consumption is 0.3% ~ 1% of reactant total mass.
Described dibasic alcohol is any in Macrogol 200, glycol ether.
Described end mercaptan carboxylic acid is any in 2-Thiovanic acid, 3-thiohydracrylic acid.
Described epoxy resin consists of at least one in bisphenol A type epoxy resin E-44, bisphenol f type epoxy resin F-170.
Described amine curing agent is at least one in Amino Terminated polyether(ATPE) D-400, Amino Terminated polyether(ATPE) D-230, Amino Terminated polyether(ATPE) T-403.
Beneficial effect:
Above-mentioned high-toughness epoxy resin and the preparation method with shape memory function, it possesses following advantage:
1. in test material preparation process, except the first step reaction has water byproduct generation, all the other two-step reactions are polyaddition reaction, do not have small molecule by-product to generate;
2. in all preparation process, do not use any chemical reagent that environmental energy is caused to severe contamination, the band aqua using can recycle, there is no the discharge of waste liquid, waste residue, can meet environment protection requirement completely;
3. realize saturated solidifying, have the advantage that solidification value is low, set time is short; Mould is positioned in 120 DEG C of environment, and 2h is just curable complete;
Time of response short, the turnaround time of prepared sample is all within 2min;
5. thermal response temperature is low, and response temperature is adjustable in 32 ~ 60 DEG C;
6. material more than thermal response temperature all can be realized 720 ° of wide-angle bendings at it, and its shape fixed rate and response rate all can reach 100%;
7. part material just can be realized shape memory function under body temperature effect.
Specific implementation method
Below by specific embodiment narration product of the present invention and preparation method thereof.Unless stated otherwise, in the present invention, technique means used is method known in those skilled in the art.In addition, embodiment is interpreted as illustrative, but not limits the scope of the invention, and the spirit and scope of the invention are only limited by claims.To those skilled in the art, do not deviating under the prerequisite of essence of the present invention and scope various changes that the material component in these embodiments and consumption are carried out or change and also belong to protection scope of the present invention.
Embodiment mono-
Get 100g Macrogol 200, be that 1:2 takes 2-Thiovanic acid by the mol ratio of Macrogol 200 and 2-Thiovanic acid, input is equipped with in the 500ml four-hole boiling flask of water-and-oil separator, add 50ml benzene, the tosic acid of reactant total mass 1%, is heated to boiling, isolates by water-and-oil separator the water that reaction generates, after esterification completes, obtain intermediate product end Thiovanic acid macrogol ester.
Take 90g epoxy resin E-44, take the synthetic end Thiovanic acid macrogol ester of previous step by the mol ratio of end sulfydryl binary alcohol esters and epoxy resin 5:100, then input is equipped with in the reactor of stirring, is heated to 40 DEG C, react 2 hours, obtain corresponding modified epoxy.
Take 34g Amino Terminated polyether(ATPE) D-400 and 2.4g Amino Terminated polyether(ATPE) D-230, get modified epoxy obtained in the previous step and above-mentioned amine curing agent proportioning, in epoxy resin, the amino mol ratio of unreacted epoxide group and amine curing agent is 2:1, proceed in another open reactor, after strong stirring mixes, immerse in forming mould, solidify 2h at 120 DEG C, must there is the modified epoxy test specimen of shape memory function.The thermal response temperature that records gained test specimen is 60 DEG C, and its tensile strength is 58MPa.
At 61 DEG C, by after 720 ° of gained sample rotoflectors, be down to rapidly room temperature, stress freezing; Be placed under 61 DEG C of environment, be 118s turnaround time again, and response rate is 100%.After repeatedly testing for nine times, recovery of shape rate still can reach 93%.
Embodiment bis-
Take 90g epoxy resin E-44, take the synthetic end Thiovanic acid macrogol ester of previous step by the mol ratio of end sulfydryl binary alcohol esters and epoxy resin 15:100, drop into and have in the reactor of stirring, be heated to 40 DEG C, react 2 hours, obtain corresponding modified epoxy.
Take 30g Amino Terminated polyether(ATPE) D-400 and 2.8g Amino Terminated polyether(ATPE) T-403, get modified epoxy obtained in the previous step and above-mentioned amine curing agent proportioning, in epoxy resin, the amino mol ratio of unreacted epoxide group and amine curing agent is 2:1, proceed in another open reactor, after strong stirring mixes, immerse in forming mould, solidify 2h at 120 DEG C, must there is the modified epoxy test specimen of shape memory function.The thermal response temperature that records gained test specimen is 40 DEG C, and its tensile strength is 53MPa.
At 41 DEG C, by after 720 ° of gained sample rotoflectors, be down to rapidly room temperature, stress freezing; Be placed under 41 DEG C of environment, be 115s turnaround time again, and response rate is 100%.After repeatedly testing for nine times, recovery of shape rate still can reach 94%.
Embodiment tri-
Take 90g epoxy resin E-44, take the synthetic end Thiovanic acid macrogol ester of previous step by the mol ratio of end sulfydryl binary alcohol esters and epoxy resin 20:100, drop into and be equipped with in the reactor of stirring, be heated to 40 DEG C, react 2 hours, obtain corresponding modified epoxy.
Take 32g Amino Terminated polyether(ATPE) D-400, get modified epoxy obtained in the previous step and above-mentioned amine curing agent proportioning, in epoxy resin, the amino mol ratio of unreacted epoxide group and amine curing agent is 2:1, proceed in another open reactor, after strong stirring mixes, immerse in forming mould, solidify 2h at 120 DEG C, must there is the modified epoxy test specimen of shape memory function.The thermal response temperature that records gained test specimen is 32 DEG C, and its tensile strength is 46MPa.
At 33 DEG C, by after 720 ° of gained sample rotoflectors, be down to rapidly room temperature, stress freezing; Be placed under 33 DEG C of environment, be 115s turnaround time again, and response rate is 100%.After repeatedly testing for nine times, recovery of shape rate still can reach 93%.
Embodiment tetra-
Get 106g glycol ether, be that 1:2 takes 2-Thiovanic acid by the mol ratio of glycol ether and 2-Thiovanic acid, input is equipped with in the 500ml four-hole boiling flask of water-and-oil separator, add 50ml benzene, the tosic acid of reactant total mass 0.3%, is heated to boiling, isolates by water-and-oil separator the water that reaction generates, after esterification completes, obtain intermediate product end Thiovanic acid glycol ether ester.
Take 90g epoxy resin E-44, take the synthetic end Thiovanic acid glycol ether ester of previous step by the mol ratio of end sulfydryl binary alcohol esters and epoxy resin 20:100, then input is equipped with in the reactor of stirring, is heated to 40 DEG C, react 2 hours, obtain corresponding modified epoxy.
Take 34g Amino Terminated polyether(ATPE) D-400, get modified epoxy obtained in the previous step and above-mentioned amine curing agent proportioning, in epoxy resin, the amino mol ratio of unreacted epoxide group and amine curing agent is 2:1, proceed in another open reactor, after strong stirring mixes, immerse in forming mould, solidify 2h at 120 DEG C, must there is the modified epoxy test specimen of shape memory function.The thermal response temperature that records gained test specimen is 44 DEG C, and its tensile strength is 61MPa.
At 45 DEG C, by after 720 ° of gained sample rotoflectors, be down to rapidly room temperature, stress freezing; Be placed under 45 DEG C of environment, be 112s turnaround time again, and response rate is 100%.After repeatedly testing for nine times, recovery of shape rate still can reach 95%.
Embodiment five
Get 100g Macrogol 200, be that 1:2 takes 3-thiohydracrylic acid by the mol ratio of Macrogol 200 and 3-thiohydracrylic acid, input is equipped with in the 500ml four-hole boiling flask of water-and-oil separator, add 50ml benzene, the tosic acid of reactant total mass 0.5%, is heated to boiling, isolates by water-and-oil separator the water that reaction generates, after esterification completes, obtain intermediate product end thiohydracrylic acid macrogol ester.
Take 45g epoxy resin E-44,36g epoxy resin F-170, take the synthetic end thiohydracrylic acid macrogol ester of previous step by the mol ratio of end sulfydryl binary alcohol esters and epoxy resin 10:100, drop into and be equipped with in the reactor of stirring again, be heated to 40 DEG C, react 2 hours, obtain corresponding modified epoxy.
Take 36g Amino Terminated polyether(ATPE) D-400, get modified epoxy obtained in the previous step and above-mentioned amine curing agent proportioning, in epoxy resin, the amino mol ratio of unreacted epoxide group and amine curing agent is 2:1, proceed in another open reactor, after strong stirring mixes, immerse in forming mould, solidify 2h at 120 DEG C, must there is the modified epoxy test specimen of shape memory function.The thermal response temperature that records gained test specimen is 45 DEG C, and its tensile strength is 58MPa.
At 46 DEG C, by after 720 ° of gained sample rotoflectors, be down to rapidly room temperature, stress freezing; Be placed under 46 DEG C of environment, be 113s turnaround time again, and response rate is 100%.After repeatedly testing for nine times, recovery of shape rate still can reach 93%.
Claims (7)
1. one kind has the modified epoxy of heat driving shape memory function, it is characterized in that, described modified epoxy material response temperature is adjustable in 32～60 DEG C, material more than thermal response temperature all can be realized 720 ° of wide-angle bendings at it, its shape fixed rate and response rate all can reach 100%, and described modified epoxy is prepared by following method:
The first step, the preparation of end mercaptan carboxylic acid binary alcohol esters: dibasic alcohol and end mercaptan carboxylic acid are dropped into and are equipped with in the reactor of water-and-oil separator by the mol ratio of 1:2, taking benzene as band aqua, tosic acid is catalyzer, be heated to boiling, isolate water that reaction generates until esterification completes by water-and-oil separator, make intermediate product end mercaptan carboxylic acid binary alcohol esters;
Second step, the preparation of modified epoxy: end mercaptan carboxylic acid the binary alcohol esters synthetic the first step and epoxy resin are dropped into and are equipped with in the reactor of stirring by the mol ratio of 5～20:100, be heated to 40 DEG C, react 2 hours, obtain Toughening Modification of Epoxy;
The 3rd step, there is the preparation that heat drives the modified epoxy of shape memory function: Toughening Modification of Epoxy synthetic second step and amine curing agent are carried out to proportioning, in epoxy resin, the amino mol ratio of unreacted epoxide group and amine curing agent is 2:1, after mixing, immerse in forming mould, 120 DEG C of hot pressing 2h moulding, must have the high-toughness epoxy resin test specimen of shape memory function.
2. a kind of modified epoxy with heat driving shape memory function according to claim 1, is characterized in that, described dibasic alcohol is any in Macrogol 200, glycol ether.
3. a kind of modified epoxy with heat driving shape memory function according to claim 1, is characterized in that, described end mercaptan carboxylic acid is any in 2-Thiovanic acid, 3-thiohydracrylic acid.
4. a kind of modified epoxy with heat driving shape memory function according to claim 1, is characterized in that, described catalyzer tosic acid consumption is 0.3%～1% of reactant total mass.
5. a kind of modified epoxy with heat driving shape memory function according to claim 1, is characterized in that, described epoxy resin consists of at least one in bisphenol A type epoxy resin E-44, bisphenol f type epoxy resin F-170.
6. a kind of modified epoxy with heat driving shape memory function according to claim 1, is characterized in that, described amine curing agent is at least one in Amino Terminated polyether(ATPE) D-400, Amino Terminated polyether(ATPE) D-230, Amino Terminated polyether(ATPE) T-403.
7. a kind of modified epoxy with heat driving shape memory function according to claim 1, is characterized in that, described modified epoxy is prepared by following method:
Get 100g Macrogol 200, be that 1:2 takes 2-Thiovanic acid by the mol ratio of Macrogol 200 and 2-Thiovanic acid, input is equipped with in the 500ml four-hole boiling flask of water-and-oil separator, add 50ml benzene, the tosic acid of reactant total mass 1%, is heated to boiling, isolates by water-and-oil separator the water that reaction generates, after esterification completes, obtain intermediate product end Thiovanic acid macrogol ester;
Take 90g epoxy resin E-44, take the synthetic end Thiovanic acid macrogol ester of previous step by the mol ratio of end mercaptan carboxylic acid's binary alcohol esters and epoxy resin 5:100, then input is equipped with in the reactor of stirring, is heated to 40 DEG C, react 2 hours, obtain corresponding modified epoxy;
Take 34g Amino Terminated polyether(ATPE) D-400 and 2.4g Amino Terminated polyether(ATPE) D-230, get modified epoxy obtained in the previous step and above-mentioned amine curing agent proportioning, in epoxy resin, the amino mol ratio of unreacted epoxide group and amine curing agent is 2:1, proceed in another open reactor, after strong stirring mixes, immerse in forming mould, at 120 DEG C, solidify 2h, must there is the modified epoxy test specimen of shape memory function, the thermal response temperature that records gained test specimen is 60 DEG C, and its tensile strength is 58MPa.
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| CN109627423A (en) * | 2018-12-07 | 2019-04-16 | 湖南普瑞迪新材料有限公司 | Flexible chain modified epoxy acrylic ester resin and preparation method thereof |
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| CN103013322B (en) * | 2013-01-07 | 2015-07-22 | 中北大学 | Preparation method of epoxy non-isocyanate polyurethane heavy anti-corrosion coating |
| CN103554838A (en) * | 2013-11-05 | 2014-02-05 | 东莞市杰乐盛世运动用品有限公司 | Epoxy resin with shape memory property and preparation method thereof |
| CN106497341A (en) * | 2016-10-27 | 2017-03-15 | 北京科技大学 | Compound coatings of a kind of thermal response shape memory and preparation method thereof |
| CN109694461A (en) * | 2017-10-20 | 2019-04-30 | 中国林业科学研究院林产化学工业研究所 | It is a kind of based on anacardol, to the preparation method of the shape memory epoxy resin material of Meng's alkane diamines and furfural |
| CN109575334B (en) * | 2018-11-27 | 2021-11-30 | 哈尔滨工业大学 | Shape memory epoxy resin prepreg and preparation method thereof |
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| CN102449021A (en) * | 2009-05-28 | 2012-05-09 | 昭和电工株式会社 | Epoxy resin-based coating composition |
| CN102443139A (en) * | 2011-09-22 | 2012-05-09 | 福建省东协橡塑实业有限公司 | Polymercaptan curing agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102449021A (en) * | 2009-05-28 | 2012-05-09 | 昭和电工株式会社 | Epoxy resin-based coating composition |
| CN102443139A (en) * | 2011-09-22 | 2012-05-09 | 福建省东协橡塑实业有限公司 | Polymercaptan curing agent and preparation method thereof |
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| CN109627423A (en) * | 2018-12-07 | 2019-04-16 | 湖南普瑞迪新材料有限公司 | Flexible chain modified epoxy acrylic ester resin and preparation method thereof |
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