CN101100545B - Shape memory epoxy resin system - Google Patents
Shape memory epoxy resin system Download PDFInfo
- Publication number
- CN101100545B CN101100545B CN2007100724319A CN200710072431A CN101100545B CN 101100545 B CN101100545 B CN 101100545B CN 2007100724319 A CN2007100724319 A CN 2007100724319A CN 200710072431 A CN200710072431 A CN 200710072431A CN 101100545 B CN101100545 B CN 101100545B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- shape memory
- solidify
- epoxy
- shape
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Epoxy Resins (AREA)
Abstract
A shape-memory epoxy-resin system consists of epoxy-resin and curing agent in proportion of 100:13.55-22.75; epoxy-resin is bisphenol A epoxy resin or bisphenol A epoxy and fatty epoxy blend resin, curing agent is p-p'-diamino-diphenyl-methane. It's light, efficient and non-toxic, and has less folding and packing volume, long storage period. It can be used for ultra-large spatial structure materials.
Description
Technical field
The present invention relates to a kind of shape-memory material, but be specifically related to the thermoset resin material of a kind of space structure with shape memory.
Background technology
Along with the mankind to the deepening continuously of space resources utilization, large space structure is proposed the intensive demand.In the recent period and in the future spacecraft all requires to use large scale structure and assembly, as the space science observatory of design construction large scale structure, antenna, solar array etc.But these large space structure delivery difficulties are loaded in order to pile these large scale structures with existing launch vehicle, require large-scale ultralight matter structure and assembly, can be effectively folded encapsulation before emission, can launch reliably on space orbit.Thermosetting resin base composite material of shape memory technology is a kind of new material technology that has just begun one's study in recent years and developed, it mainly is the exploitation of shape memory epoxy resin, because its high strain destructive rate, high unit modulus, low density, anti-environmental characteristics, energy mechanical deformation, storage strain and shape are recovered, be the ideal material of deployed configuration, with it produce simply, rigidity, light-weight deployed configuration.The thermosetting resin base composite material of shape memory can carry out testing experiment on the ground, and before emission folded package, serve behind the track and can simply and reliably launch with application of heat.By thermosetting resin base composite material of shape memory technology, the vibration problems in the time of can reducing risk, improve the rocket carrying capacity, reduce launch cost and eliminate space development.This technology has become the focus of space technology research.By this Research on New, development and application, not only can provide new technology for Space Science and Technology provides smaller launch mass, volume and a structure large space structure of usefulness, also be to create super giant simultaneously, the space structure of ultra lightweighting provides a more effective new way.A gordian technique developing strong space development structure is exactly to select suitable material to satisfy the system requirement.But,, only, also do not have the data relevant, and the shape memory resin material that use in the space must be a thermoset resin material with thermoset shape memory resin about the research of thermoplasticity shape-memory polymer from the domestic document of publishing.The TEMBO series of loops epoxy resins of the Composite Technology Development exploitation that external reported space use shape Resins, epoxy mainly is US Airways and the subordinate of space travel office (NASA) and the TP series of loops epoxy resins of ILC Dover exploitation, but its gordian technique and data are all maintained secrecy.
Summary of the invention
The objective of the invention is to deliver difficult problem, and a kind of shape memory epoxy resin system is provided in order to solve large space structure.
Shape memory epoxy resin system of the present invention (system is meant the mixture of Resins, epoxy and solidifying agent) is made by Resins, epoxy and solidifying agent, and the weight ratio of Resins, epoxy and solidifying agent is 100: 13.55～22.75.Described Resins, epoxy is bisphenol A type epoxy resin, bisphenol type epoxy or aliphatic epoxy blending resin commixed type Resins, epoxy, wherein bisphenol A type epoxy resin is bisphenol A type epoxy resin E-51 or bisphenol A type epoxy resin E-44, aliphatic epoxy resin polypropylene glycol diglycidyl ether or polyethyleneglycol diglycidylether, described solidifying agent is an amine curing agent, amine curing agent be right, right '-diamino-hexichol-methane.
Resins, epoxy is not limited to the cited material of the present invention, so long as energy and bisphenol type epoxy form lightly crosslinked stabilizing network structure and can improve epoxy-resin systems toughness, while and make system intensity reduce little aliphatic epoxy resin; Or commixed type Resins, epoxy that two orders of magnitude change can take place rapidly all within protection domain of the present invention in the modulus that has rigid structure in the molecular chain flexible structure, its lightly crosslinked cured article are arranged again when glass transition.
Solidifying agent also is not limited only to the cited material of the present invention, in theory as long as and the Resins, epoxy solidifying agent commonly used that can react with generates crosslinking structure all can use, as amine curing agent (polyethylene polyamine, mphenylenediamine, two amido sulfobenzides etc.), acid anhydride type curing agent (Tetra hydro Phthalic anhydride, pyromellitic dianhydride, MALEIC ANHYDRIDE etc.), imidazole curing agent (glyoxal ethyline, 2-ethyl 4-methylimidazole etc.).
Because shape memory epoxy resin system is mainly used in the space and uses, and therefore, requires selected system to meet space use properties requirement.Obtain different shape-memory properties by controlling different degree of crosslinking, the 60%-90% of hardener dose when general hardener dose is completely solidified.
The principle that the present invention relates to the shape memory technology is: shape memory epoxy resin has two phase structure, and promptly the stationary phase by the memory original shape can reversibly solidify and the reversible phase composite of remollescent with varying with temperature.Among the epoxy resin-matrix SMP, lightly crosslinked part forms stationary phase, but anti-phase is for the phase structure of vitreous state and elastomeric state reversible transition takes place.When being heated to Tg, the micro-Brownian movement of reversible phase molecule chain aggravation, and stationary phase still is in solid state, and its molecular chain is in bond, and material is converted into elastomeric state by vitreous state.At this moment, the SMP of elastomeric state is out of shape under external force,, can tries hard to keep outside and hold down cooling, reversible solidifying because deformation lags behind STRESS VARIATION with certain working method.Just can obtain stable new shape, i.e. deformation states after removing external force.But the shape of this moment is kept molecular chain by anti-phase and is orientated, freezes along external force direction, and stationary phase is in heavily stressed deformed state.When deformation states is heated to shape recovery temperature (Tg), the stationary phase maintenance curing but anti-phase is softening.Reversible phase molecule chain movement brings back to life, and removes orientation under the recovery stress of stationary phase, and progressively reaches thermodynamic equilibrium state, shows as on the macroscopic view to return to form.
On ground shape memory epoxy resin system of the present invention and fiber composite are molded into the space structural shape, reheat is to more than the material glass transition temperature, folding packing after material is limbered up, launch behind the arrival planned orbit,, arrive the recovery temperature of composite material of shape memory the structure heating, after structure is launched to arrive predetermined shape, stop the heating, be lower than the shape memory recovery temperature of material when structure temperature after, structure promptly shows rigidity.Therefore, the present invention can be used as Space Science and Technology method launch mass and volume is less, can construct the material of large space structure, also provides a more effective approach for space structure super giant, ultra lightweighting simultaneously.In the material expansion process of the present invention, judge whether the help of needs external force, can adopt modes such as inflating help that it is launched as needs according to the intensity of material.
The present invention has following beneficial effect: shape memory epoxy resin system of the present invention adopts existing polymkeric substance and synthetics manufacturing processing, moulding process maturation; Low-cost expense.Material of the present invention is selected by resin formula, can make broad adjustable distortion and recovery temperature; Be distortion that can be repeatedly and recover circulating system, and can carry out ground test repeatedly; And need not carry out chemical reaction, only need heating just can launch and fold, so do not have the toxicity that chemical reaction brings, the problem of blast; And the volume of folded package significantly reduces, storage period very long (material of the present invention can be kept curved shape always).
Embodiment
Embodiment one: shape memory epoxy resin system is made by Resins, epoxy and solidifying agent in the present embodiment, and the weight ratio of Resins, epoxy and solidifying agent is 100: 13.55～22.75; Described Resins, epoxy is bisphenol A type epoxy resin or bisphenol type epoxy and aliphatic epoxy blending resin, wherein bisphenol A type epoxy resin is bisphenol A type epoxy resin E-51 or bisphenol A type epoxy resin E-44, and aliphatic epoxy resin is polypropylene glycol diglycidyl ether or polyethyleneglycol diglycidylether; Described solidifying agent is an amine curing agent, amine curing agent be right, right '-diamino-hexichol-methane.
Embodiment two: the weight ratio of Resins, epoxy and solidifying agent is 100: 14.15～17.7 in the present embodiment.Other is identical with embodiment one.
Embodiment three: the weight ratio of Resins, epoxy and solidifying agent is 100: 15.17 in the present embodiment.Other is identical with embodiment one.
Embodiment four: the difference of present embodiment and embodiment one is that shape memory epoxy resin system has increased nanometer SiO
2And γ-An Bingjisanyiyangjiguiwan (KH550), wherein Resins, epoxy: solidifying agent: nanometer SiO
2: KH550=100: 13.55～22.75: 5: 0.05.Other is identical with embodiment one.
The nanometer SiO that present embodiment increases
2Can improve the tensile strength of shape memory epoxy resin system.
Embodiment five: the present embodiment shape memory epoxy resin system is right by 15.17 weight parts, right '-the bisphenol A type epoxy resin E-51 of diamino-hexichol-methane (DDM) and 100 weight parts makes; The preparation method of described shape memory epoxy resin system is as follows: 15.17 weight parts are right, right '-diamino-hexichol-methane places heating and melting under 104 ℃ of temperature, and mix with 100 weight part E-51 under synthermal, stir, under 80 ℃ of conditions, solidify 2.4h then, be warming up to 150 ℃ again and solidify 1.8h.
The product test specimen that with the specification that adopts present embodiment to make is 150mm * 20mm * 2mm was 80 ℃ of heating 3 minutes, under this temperature, it is folded into the U type that radius is 15mm again, and the rapid cool to room temperature of maintenance external force active state, remove external force and with cooled product test specimen reheat to 70 ℃, the product test specimen can recover initial excipient shape fully in this temperature, and the time is 190s.This test specimen is folding along the same line, after recovering to circulate through 9 shape folded deformation-shapes, still can recover original shape fully, and be 240s time of recovery.When placing 80 ℃ to carry out the shape recovery as the fruit product test specimen, test specimen is after a shape folded deformation-shape is recovered circulation, and the time that complete shape is recovered is 80s, and the time of shape recovery is 90s fully after 9 shape folded deformation-shapes recovery circulations.Tensile strength was 62MPa before product test specimen shape was folding, and recovering circulation back draft intensity through a shape folded deformation-shape is 64Mpa, and tensile strength slightly increases; After 9 shape folded deformation-shapes were recovered circulation, tensile strength was 58Mpa, strength degradation 6.5%.
Embodiment six: the weight ratio of E-51 and DDM is 100: 15.17～22.75 in the present embodiment, solidifies 3h under 80 ℃ of conditions, is warming up to 150 ℃ and solidifies 3h.Other is identical with embodiment five.
Present embodiment gets testing method embodiment six, DDM: E-51=15.17: the product test specimen that 100 systems are made is 73 ℃ of heating, and be stretched to 130% of former length, keep external force active state and cooling rapidly, remove external force then and again test specimen is placed the recovery that freely bounces back of 73 ℃ of environment.The product test specimen can recover fully, and recovery intensity is 2.3Mpa.
When the DDM consumption was between 17.7～22.75 weight parts, its shape memory temperature scope was from 90 ℃ to 110 ℃, and shape scope time of recovery is that 150s is to 40s.
When the highest consumption of DDM was 22.75 weight parts, also there was the distortion of shape stretching-retraction in this system; But, just there is not shape memory function when DDM surpasses just amount of this ratio.
This shows, can obtain shape memory temperature by controlling different formula rates from 45 ℃ to 150 ℃, can obtain time of recovering fully by controlling different recovery temperatures, recover ratio by controlling the shape that different recovery temperatures can also 100% to 50% from 1～9min shape memory.
Embodiment seven: the E-51 of shape memory epoxy resin system in the present embodiment: polypropylene glycol diglycidyl ether: DDM=82: 18: 14.15 (mass ratio); The preparation method of described shape memory epoxy resin system is as follows: 14.15 parts of DDM are placed heating and melting under 104 ℃ of temperature, and mix with E-51 under synthermal, stir, add polypropylene glycol diglycidyl ether again, under 80 ℃ of conditions, solidify 3h then, be warming up to 150 ℃ again and solidify 3h.
The shape of product reminiscence temperature range that present embodiment makes is that shape recovery temperature 1min does not wait to 4min from 48 ℃ to 70 ℃.This system toughness is big, occurs surrender when resin stretched, and elongation at break is 70%, and itself and the compound matrix material that makes of fortifying fibre relatively are difficult for destroyed when shape flexural deformation.
Embodiment eight: shape memory epoxy resin system prescription: E-51: DDM: nanometer SiO in the present embodiment
2: KH550=100: 15.17: 5: 0.05; Its preparation and forming method: KH550 is dissolved in the dehydrated alcohol, again with nanometer SiO
2Mix, carry out ultrasonic dispersing and handle, and reheat stirs to vacuumize simultaneously and removes dehydrated alcohol; Again with the mixture heating up to 104 that makes ℃, and with mix at 104 ℃ of fused DDM, stir, under 80 ℃ of conditions, solidify 3h then, be warming up to 100 ℃ again and solidify 3h.
The product that present embodiment makes also has shape memory function, and the shape memory recovery temperature is that tensile strength is than not adding nanometer SiO from 70 ℃ to 100 ℃
2System strengthen 8%, the feasibility of nano-material modified shape memory epoxy resin system is described.
Claims (3)
1. shape memory epoxy resin system, it is characterized in that it by 15.17 weight parts right, right '-the bisphenol A type epoxy resin E-51 of diamino-hexichol-methane and 100 weight parts makes; Described shape memory epoxy resin system divides two segment to solidify, preparation according to the following steps: 15.17 weight parts are right, right '-diamino-hexichol-methane places heating and melting under 104 ℃ of temperature, and mix with 100 weight part E-51 under synthermal, stir, under 80 ℃ of conditions, solidify 2.4h then, be warming up to 150 ℃ again and solidify 1.8h.
2. shape memory epoxy resin system, it is characterized in that it by 15.17～22.75 weight parts right, right '-the bisphenol A type epoxy resin E-51 of diamino-hexichol-methane and 100 weight parts makes; Described shape memory epoxy resin system divides two segment to solidify, preparation according to the following steps: 15.17～22.75 weight parts are right, right '-diamino-hexichol-methane places heating and melting under 104 ℃ of temperature, and mix with 100 weight part E-51 under synthermal, stir, under 80 ℃ of conditions, solidify 3h then, be warming up to 150 ℃ again and solidify 3h.
3. shape memory epoxy resin system, it is characterized in that it by mass fraction by 82 parts bisphenol A type epoxy resin E-51,18 parts polypropylene glycol diglycidyl ether and 14.15 parts right, right '-diamino-hexichol-methane makes; Described shape memory epoxy resin system divides two segment to solidify, preparation according to the following steps: right with 14.15 parts, right '-diamino-hexichol-methane places heating and melting under 104 ℃ of temperature, and mix with E-51 under synthermal, stir, add polypropylene glycol diglycidyl ether again, under 80 ℃ of conditions, solidify 3h then, be warming up to 150 ℃ again and solidify 3h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100724319A CN101100545B (en) | 2007-06-29 | 2007-06-29 | Shape memory epoxy resin system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100724319A CN101100545B (en) | 2007-06-29 | 2007-06-29 | Shape memory epoxy resin system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101100545A CN101100545A (en) | 2008-01-09 |
| CN101100545B true CN101100545B (en) | 2010-08-04 |
Family
ID=39035002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100724319A Expired - Fee Related CN101100545B (en) | 2007-06-29 | 2007-06-29 | Shape memory epoxy resin system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101100545B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8618238B2 (en) | 2007-04-20 | 2013-12-31 | GM Global Technology Operations LLC | Shape memory epoxy polymers |
| CN101560286B (en) * | 2007-10-04 | 2013-11-06 | 通用汽车环球科技运作公司 | Epoxide polymer of shape memory |
| CN102504202B (en) * | 2011-10-10 | 2013-03-20 | 中科院广州化学有限公司 | Liquid crystal epoxy resin with shape memory effect and preparation method and application thereof |
| CN102514132B (en) * | 2011-12-28 | 2013-11-06 | 西安航天复合材料研究所 | Method for manufacturing shape memory polymer core mold by winding composite material component |
| DE102012218204A1 (en) * | 2012-10-05 | 2014-04-10 | Krones Ag | Clamp gripper for containers |
| CN103897337A (en) * | 2012-12-24 | 2014-07-02 | 北京有色金属研究总院 | Nano graphite flake reinforced shape-memory composite material and preparation method thereof |
| 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 |
| CN105885090A (en) * | 2016-04-26 | 2016-08-24 | 哈尔滨工程大学 | Method for enhancing interfacial properties of SMA (styrene maleic anhydride) reinforced resin intelligent composite materials |
| CN106519567B (en) * | 2016-10-17 | 2018-12-04 | 长安大学 | A kind of preparation method of shape memory epoxy resin particle |
| CN108264618A (en) * | 2018-01-29 | 2018-07-10 | 哈尔滨工业大学 | A kind of shape memory polymer networks formation system of light and heat two-stage reaction and preparation method thereof |
| CN109233205A (en) * | 2018-08-31 | 2019-01-18 | 王雪峰 | A kind of preparation method of triple shape memory epoxy resin composite materials |
| CN109627695B (en) * | 2018-12-21 | 2021-04-23 | 航天特种材料及工艺技术研究所 | Shape memory wave-absorbing material and preparation method thereof |
| CN109666262B (en) * | 2018-12-21 | 2021-04-23 | 航天特种材料及工艺技术研究所 | Shape self-repairing wave-absorbing material and preparation method thereof |
| CN113736066A (en) * | 2020-05-28 | 2021-12-03 | 中国工程物理研究院化工材料研究所 | Shape memory epoxy resin with adjustable recovery stress and recovery stress regulation and control method of shape memory epoxy resin |
| CN112876816A (en) * | 2021-02-25 | 2021-06-01 | 刘龙汇 | Resin-based foam composite board and preparation method thereof |
| CN113881279A (en) * | 2021-11-03 | 2022-01-04 | 中国科学院兰州化学物理研究所 | 3D printing shape memory epoxy resin ink, preparation method and application thereof, and 3D printing epoxy resin |
| CN115536814A (en) * | 2022-09-27 | 2022-12-30 | 哈尔滨工业大学 | Shape memory epoxy resin and preparation method and application thereof |
-
2007
- 2007-06-29 CN CN2007100724319A patent/CN101100545B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101100545A (en) | 2008-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101100545B (en) | Shape memory epoxy resin system | |
| CN102504202B (en) | Liquid crystal epoxy resin with shape memory effect and preparation method and application thereof | |
| Capricho et al. | Multifunctionality in epoxy resins | |
| Jing et al. | Melamine foam-supported form-stable phase change materials with simultaneous thermal energy storage and shape memory properties for thermal management of electronic devices | |
| CN104119827B (en) | A kind of room-temperature curing epoxy-acid anhydrides tackiness agent and preparation method thereof | |
| Luo et al. | Shape memory epoxy resin and its composites: from materials to applications | |
| CN102822227B (en) | Epoxy resin composition for use in a carbon-fiber-reinforced composite material, prepreg, and carbon-fiber-reinforced composite material | |
| US20100144962A1 (en) | Shape memory polymer aerogel composites | |
| CN103642199A (en) | Reversible covalent crosslinked polyurethane and epoxy resin composite and preparation method thereof | |
| CN104918987A (en) | Epoxy resin composition, prepreg, fiber reinforced plastic material, and manufacturing method for fiber reinforced plastic material | |
| CN104744893A (en) | Shape memory epoxy resin and preparation method thereof | |
| ES2788463T3 (en) | Fiber-reinforced composite molding | |
| CN113276440B (en) | Preparation method and unfolding and recycling method of thin-wall column shell structure | |
| RU2682250C2 (en) | Curing agents for epoxy resins | |
| JP2011079983A (en) | Epoxy resin composition for carbon fiber-reinforced composite material, prepreg and carbon fiber-reinforced composite material | |
| Luo et al. | Shape-stabilized phase change materials with superior thermal conductivity for thermal energy harvesting | |
| Zhang et al. | Progress in utilizing dynamic bonds to fabricate structurally adaptive self‐healing, shape memory, and liquid crystal polymers | |
| CN106987113A (en) | Rapidly and efficiently self-repair type shape memory polymer composite material and preparation method thereof by all kinds of means | |
| Yao et al. | Actuation performances of catkin fibers reinforced thiol-acrylate main-chain liquid crystalline elastomer | |
| Jiang et al. | Preparation of flexible solid-solid phase change materials with simultaneously thermal energy storage capability, reprocessability and dual-actuated shape memory performance | |
| CN106751503B (en) | The preparation method of high-modules carbon fibre prepreg intermediate temperature setting epoxy-resin systems | |
| CN101186742B (en) | Shape memory composite material and preparation method thereof | |
| Everhart et al. | High-temperature reusable shape memory polymer mandrels | |
| Huang et al. | New star-shape memory polyurethanes capable of thermally induced recovery and hydrogen bond-self-healing | |
| Herath et al. | 4D printed shape memory polymer composite structures for deployable small spacecrafts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100804 Termination date: 20110629 |